Gargnano (Garda Lake) – Italy 14-16 September 2016 PROGRAMME · Xosé Ramón Nóvoa, Universidad...

2nd E3 Mediterranean Symposium:

Electrochemistry for Environment and Energy

Gargnano (Garda Lake) – Italy

14-16 September 2016

PROGRAMME

SPONSORS

PATRONAGES

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Scientific COMMITTEE

Catia Arbizzani, Università di Bologna

Vincenzo Baglio, CNR-ITAE, Messina

Mariachiara Benedetto, Industrie De Nora, Milano

Enric Brillas, Universidad de Barcelona

Alessandra D'Epifanio, Università di Roma "Tor Vergata"

Debora Fino, Politecnico di Torino

Iluminada Gallardo, Universidad Autonoma de

Barcelona

Jose García Antón, Universidad Politecnica de Valencia

Enrique Herrero, Universidad de Alicante

Vicente Montiel, Universidad de Alicante

Maria Assunta Navarra, Università di Roma "La Sapienza"

Xosé Ramón Nóvoa, Universidad de Vigo

Simonetta Palmas, Università degli Studi di Cagliari

Marco Panizza, Università degli Studi di Genova

Elisabetta Petrucci, Università di Roma "La Sapienza"

Manuel Rodrigo, Universidad de Castilla-la-Mancha

Maria Angeles Sanromán, Universidad de Vigo

Onofrio Scialdone, Università degli Studi di Palermo

Ana Urtiaga, Universidad de Cantabri

Elisa Vallés, Universidad de Barcelona

Alberto Vertova, Università di Milano

Organizing COMMITTEE

Serena Arnaboldi, Università degli Studi di Milano

Giuseppe Cappelletti, Università degli Studi di Milano

Luigi Falciola, Università degli Studi di Milano, (co-Chair)

Silvia Franz, Politecnico di Milano

Mariangela Longhi, Università degli Studi di Milano

Alessandro Minguzzi, Università degli Studi di Milano, (co-Chair)

Vicente Montiel, Universidad de Alicante

Patrizia Mussini, Università degli Studi di Milano

Valentina Pifferi, Università degli Studi di Milano

Manuel Rodrigo, Universidad de Castilla-la-Mancha

Riccardo Ruffo, Università degli Studi di Milano Bicocca

Monica Trueba, Università degli Studi di Milano

The Programme of Wednesday is joint with the GEI 2016 Meeting.

08.50-09.00 E3 Welcome & Opening 09.00-09.30 Keynote - Benedetto 09.00-09.20 SOLER Sergio

09.00-09.20 ASENSIO Yeray 09.30-10.00 Keynote - Bouzek 09.20-09.40 PALMAS Simonetta

09.20-09.40 D'ANGELO Adriana 10.00-10.30 Keynote - La Mantia 09.40-10.00 RIDRUEJO Carlota

09.40-10.00 SAEZ Alfonso 10.30-11.00 Coffee break 10.00-10.20 SABATINO Simona

10.00-10.20 SOAVI Francesca 11.00-11.30 Keynote - Lapicque 10.20-10.40 SORIANO Alvaro

10.20-10.40 ZAFFOU Rachid 11.30-11.50 LOBATO Justo 10.40-11.10 Coffee break

10.40-11.10 Coffee break 11.50-12.10 LO FARO Massimiliano 11.10-11.30 STETER Juliana

12.10-12.30 SAEZ Cristina 11.30-11.50 TSURUMAKI Akiko

12.30-13.30 Lunch time 11.50-12.10 PEREZ Valentin

14.20-14.40 FELIU Juan 12.10-12.30 BARAN Tomasz

14.40-15.00 PEREZ Jose 12.30-12.50 MUSIANI Marco

12.30-13.30 Lunch time 15.00-15.20 SECHI Elisa 12.50-13.00 Conclusions

15.20-15.40 GENESTE Florence 13.00-14.00 Lunch time

15.40-16.00 ANIA Conchi

16.00-16.30 Coffee break

16.30-16.50 BOCOS Elvira

16.50-17.10 PETRUCCI Elisabetta

17.10-17.30 DIEZ Aida

PROGRAMMEWednesday 14/09 Thursday 15/09

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17.30-18.50Poster Flash

Presentation

Friday 16/09

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11.10-12.30Electrochemistry & Industrial

Applications

14.30-…Social Events including Social

Dinner

18.50-….POSTER SESSION &

Cocktail Buffet

Program

Wednesday, September 14th 2016

8.50 E3 Welcome & Opening

9.00 Y. Asensio Influence of Stacked Microbial Fuel Cells (MFC) in Energy Generation and Organic Matter Removal.

O1 p. 2

9.20 A. D’Angelo Abatement of recalcitrant pollutants using Microbial fuel cells, Reverse Electrodialysis and Microbial Reverse Electrodialysis cells

O2 p. 3

9.40 A. Saez Acid-Base Electrochemical Flow Battery (ABEFB) O3 p. 4

10.00 F. Soavi Novel Concepts of Bioelectrochemical Energy Devices O4 p. 5

10.20 R. Zaffou Flow-Batteries for Large-Scale Electrical Energy Storage: Beyond Conventional Batteries

O5 p. 6

10.40 Coffee Break

11.10

Ele

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CHEMICAL NEWTECH S.p.a. - Titanium Anodes

Activated Titanium Anodes for Electrochemical Industrial Processes: Applications, Standards and Testing.

O6 p. 7

11.30 ENGITEC S.p.a. Electrochemistry in the Processes of Metals Recovery: Technologies to Rediscover

O7 p. 8

11.50 ITELCOND S.r.l. Aluminum Electrolytic Capacitors: History, Components, Applications

O8 p. 9

12.10 NANOMATERIALS.IT S.r.l

Electrochemical Photocatalysis on Supported Nanoporous TiO2: A Novel Advanced Oxidation Process for Water Treatment

O9 p. 10

12.30 Lunch Time

14.30 Social Events

Thursday, September 15th 2016

9.00 Keynote M. Benedetto Electrolytic Cell equipped with Concentric Electrode pairs K1 p. 12

9.30 Keynote K. Bouzek Fuel Cell Flow Field Optimization – from a Single Channel Experiment to the Fuel Cell Stack Model

K2 p. 13

10.00 Keynote F. La Mantia Aging Mechanism of Prussian Blue Derivatives during Zinc-Ion Intercalation

K3 p. 14

10.30 Coffee Break

11.00 Keynote F. Lapicque Electrocoagulation and other Techniques for Water Treatment: a Couple of Relevant Examples

K4 p. 15

11.30 J. Lobato

First Approach to develop Self-Sustainable Photo Microbial Cells (PMC)

O10 p. 16

11.50 M. Lo Faro From Button Cell to 500 W SOFC Stack fed with Dodecane O11 p. 17

12.10 C. Saez Different Strategies for the Electro-remediation of Soils Polluted with Herbicides

O12 p. 18

12.40 Lunch Time

14.20 J. Feliu Interfacial Reactivity on Shape-Selected Nanocatalysts O13 p. 20

14.40 J. Perez Jet-cell Reactor for Hydrogen Peroxide Generation: a Proof of Concept

O14 p. 21

15.00 E. Sechi Preparation of Nickel Foams by Selective Corrosion of Ni/Cu films in different Solvents

O15 p. 22

15.20 F. Geneste Indirect Electroreduction on a Titanocene/Nafion®-Modified Electrode as Pretreatment to Enhance Biodegradability of Metronidazole

O16 p. 23

15.40 C. Ania Nanoporous Carbon as Efficient Materials for Electrochemical Applications: the Role of the Pore Architecture and Surface Chemistry

O17 p. 24

16.00 Coffee Break

16.30 E. Bocos Application of Electrochemical Technology for Ionic Liquid Degradation and the in situ Monitoring of the Process

O18 p. 25

16.50 E. Petrucci Mitigating the Formation and Persistence of Inorganic Chlorine Compounds in the Anodic Oxidation of Chloride-Containing Solutions

O19 p. 26

17.10 A. Diez Remediation of Ionic Liquid Polluted Soils by Enhanced Electrokinetic Treatment

O20 p. 27

17.30 Poster Flash presentation

18.50 Poster Session & Cocktail Buffet

Friday, September 16th 2016

9.00 S. Soler Room-Temperature Electrochemical Induced Direct C-H-Arylation

O21 p. 30

9.20 L. Mais Electrochemical behaviour of Copper-based substrates for CO2 electroreduction in both aqueous and non-aqueous electrolytes.

O22 p. 31

9.40 C. Ridruejo Development of Air-Diffusion Cathodes for Electrochemical Water Treatment: From Synthesis to Use

O23 p. 32

10.00 S. Sabatino Investigation of an Electrochemical Process for the Conversion of Carbon Dioxide to Higher Value Products

O24 p. 33

10.20 A. Soriano Removal of Perfluorohexanoic Acid (PFHxA) from Industrial Effluents by Nanofiltration Followed by Electrochemical Oxidation of the NF Concentrate

O25 p. 34

10.40 Coffee Break

11.10 J. Steter Electrochemical Removal of Methyl Paraben using Different Anodes and Aqueous Matrices

O26 p. 35

11.30 A. Tsurumaki Preparation of Novel Polymer Electrolytes Based on Poly(tetrafluoroethylene) and Ionic Liquids for Lithium Ion Batteries

O27 p. 36

11.50 V. Perez Influence of Na2SO4 Concentration on the Abatement of Norfloxacin using BDD Electrodes

O28 p. 37

12.10 T. Baran Semiconductor Structures for Hydrogen Peroxide Production on Photoelectrochemical Way

O29 p. 38

12.30 M. Musiani Preparation of Ag-modified Ni Foams by Galvanic Displacement and their Use as Cathodes for the Reductive Dechlorination of Herbicides

O30 p. 39

12.50 Conclusions

13.00 Lunch Time

Oral Contributions

_____________________________________________________________________________________ E3 2016, 14-16 September 2016 – Gargnano (Garda Lake), Italy 1

Wednesday, September 14th 2016

8.50 E3 Welcome & Opening 9.00 Y. Asensio Influence of Stacked Microbial

Fuel Cells (MFC) in Energy Generation and Organic Matter Removal.

O1 p. 2

9.20 A. D’Angelo Abatement of recalcitrant pollutants using Microbial fuel cells, Reverse Electrodialysis and Microbial Reverse Electrodialysis cells

O2 p. 3

9.40 A. Saez

Acid-Base Electrochemical Flow Battery (ABEFB)

O3 p. 4

10.00 F. Soavi

Novel Concepts of Bioelectrochemical Energy Devices

O4 p. 5

10.20 R. Zaffou Flow-Batteries for Large-Scale Electrical Energy Storage: Beyond Conventional Batteries

O5 p. 6

10.40 Coffee Break

11.10

Ele

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Ind

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pp

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CHEMICAL NEWTECH S.p.a. - Titanium Anodes

Activated Titanium Anodes for Electrochemical Industrial Processes: Applications, Standards and Testing.

O6 p. 7

11.30 ENGITEC S.p.a. Electrochemistry in the Processes of Metals Recovery: Technologies to Rediscover

O7 p. 8

11.50 ITELCOND S.r.l.

Aluminum Electrolytic Capacitors: History, Components, Applications

O8 p. 9

12.10 NANOMATERIALS.IT S.r.l Electrochemical Photocatalysis on Supported Nanoporous TiO2: A Novel Advanced Oxidation Process for Water Treatment

O9 p. 10

12.30 Lunch Time

14.30 Social Events

O1 _____________________________________________________________________________________


Influence of Stacked Microbial Fuel Cells (MFC) in Energy Generation and Organic Matter Removal.

Yeray Asensio, Sara Mateo, Carmen M. Fernández-Marchante, Francisco J. Fernández,

Pablo Cañizares, Justo Lobato, Manuel A. Rodrigo

University of Castilla-La Mancha Department of Chemical Engineering, Faculty of Chemical Sciences and Technologies, Ciudad Real, Spain

In recent years, research activity on microbial fuel cell (MFC) technology has increased markedly. This technology consists of bioelectrochemical reactors that convert chemical energy contained in organic matter directly into electricity, using only microorganisms. However, the maximum energy that can be obtained from a single MFC unit is insufficient for use in practical applications and it is required the association of MFC either in series or in parallel, in order to generate continuously energy enough for powering low power consumption portable electronic devices. In this work, three different stacked-MFCs were designed and tested (combining 2, 5 and 10 MFC modules) in order to evaluate the influence of the type of connection (series connection and parallel connection) on the organic matter removal and the electricity generation. As expected, the higher the number of cells connected, the higher was the energy obtained and important differences were observed with the electric connection made between the individual cells. Hence, stacked-MFC improves the energy generation and organic matter removal of single MFC. In addition, a proof of concept of the system was carried out by connecting the 10 MFC serially-stacked to a light emitting diode (LED), providing the necessary energy to light up the device. Acknowledgements: Financial support from Spanish Ministry of Economy and Competitiveness (MINECO) through project SUNLIVINGENERGY (CTQ2013-49748-EXP, Explora Program) is gratefully acknowledged. In addition, financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is acknowledged.

O2 _____________________________________________________________________________________


Abatement of recalcitrant pollutants using Microbial fuel cells, Reverse Electrodialysis and Microbial Reverse Electrodialysis cells

Adriana D’Angelo, Simona Sabatino, Fabrizio Vicari, Onofrio Scialdone, Alessandro

Galia

aUniversità degli Studi di Palermo, Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica.Palermo, Italy, [email protected]

Promising electrochemical technologies for the treatment of waste water containing pollutants resistant to conventional biological processes[1,2], that do not require to supply of electric energy, include: - Microbial fuel cell, which uses an anode-bacteria where active microorganisms are capable to oxidize organic matter to generate electrons, protons, and other metabolic products; - Reverse electrodialysis process, a membrane based technology that use the salinity gradient power (SGP) as valuable renewable energy source that can be generated from reversible mixing of two waters with different salt contents.

In the last years, we have studied the possibility to use also another system, a microbial reverse electrodialysis cell (MRC) in which we have the combination of a MFC with a RED stack into a single process (Fig.1). MRC represents a new approach for energy production and abatement of organic pollutants with the aim to increase MFC voltages and power densities and to limit the number of membrane pair in a RED process to treat contaminated water.

Figure 1. Simple schemes of a) Microbial fuel cell, b) Reverse electrodialysis cell and

c) Microbial reverse electrodialysis cell.

In this study, we examined the utilization of MFC, RED and MRC for the treatment of wastewater contaminated by pollutants resistant to conventional biological processes[3]. The pollutants chosen as model were, AO7 as organic and Cr(VI) as inorganic pollutant. In particular, the treatment of both pollutants with MRC was successfully achieved by electro-Fenton process and cathodic reduction, respectively, in short times using a drastically lower number of membrane pairs with respect to that required by a conventional RED. References [1] O. Scialdone, A. D’Angelo, A. Galia, J. Electroanal. Chem, 738, (2015), 61–68. [2] O. Scialdone, A. D’Angelo, E. De Lumè, A. Galia, Electrochim. Acta, 137, (2014), 258–265. [3] A. D’Angelo, A. Galia, O. Scialdone, J. Electroanal. Chem, 748, (2015), 40–46.

O3 _____________________________________________________________________________________


Acid-Base Electrochemical Flow Battery (ABEFB)

Alfonso Sáez, Vicente Montiel, Eduardo Expósito, Antonio Aldaz†

[email protected]

University of Alicante, Institute of Electrochemistry, Alicante, Spain † Died on 27th October 2015.

Redox Flow Batteries are considered as useful charge/discharge energy storage systems, basically composed of two electrolytes called posilyte and negalyte (solutions in contact with positive and negative electrodes, respectively) [1]. In this communication, we present a new Acid-Base Electrochemical Flow Battery (ABEFB) as a pseudo-redox flow battery. This is a simply but clever system formed by acidic and alkaline solutions, both with a high supporting electrolyte concentration and are separated by a proton exchange membrane. Moreover, hydrogen is utilized as both a reactant and a product so hydrogen self-supply could be considered. On the one hand, in the charging process, hydrogen is oxidized to form hydronium ions (hydrogen oxidation reaction –HOR-) at the positive electrode that acidifies posilyte, while hydrogen is formed from water (hydrogen evolution reaction –HER-) at the negative electrode that basifies negalyte. On the other hand, during the discharging process, posilyte and negalyte are neutralized through hydrogen oxidation and hydrogen evolution reactions. A platinised titanium electrode was chosen for HER and a platinum-catalysed gas diffusion electrode was used for HOR. In this sense, electrochemical behaviour has been separately studied both charging and discharging processes for several charge capacities. Both charging and discharging processes have been evaluated using charging or discharging and power curves as well as constant current density experiments (figure 1). Note that, in an alkaline medium a higher overpotential was observed, especially in the HOR at the discharging process. Finally, maximum values of power density of 20 mW cm-2 at 49 mA cm-2, energy efficiency of 55% and a faradic efficiency close to 95 % were obtained.

Figure 1. Electrochemical behaviour: discharging and charging curves and power curves (left side), charging/ discharging cycles for two charge capacities (right side). References [1] A.Z. Weber, M.M. Mench, J.P. Meyers, P.N. Ross, J.T. Gostick, Q. Liu, J. Appl. Electrochem., 41, (2011), 1137-1164.

O4 _____________________________________________________________________________________


Novel Concepts of Bioelectrochemical Energy Devices

Francesca Soavia, Catia Arbizzania, Carlo Santorob, Alexey Serovb, Plamen Atanassovb

aAlma Mater Studiorum – Università di Bologna, Dipartimento di Chimica “Giacomo

Ciamician”, Bologna, Italy, [email protected] bUniversity of New Mexico, Department of Chemical and Biological Engineering,

Center Micro-Engineered Materials (CMEM), Albuquerque-N, USA

Microbial Fuel Cells (MFCs) are interesting and relatively novel systems that combine traditional electrochemistry and microbiology. MFC utilizes organic wastes as fuel for generating electricity. Due to the slow kinetics processes, the electricity output is quite low and not directly usable for powering low demanding power devices. Consequently, MFC are combined with external supercapacitors (SCs) that boost up current/power output. The combination of MFC with external supercapacitors allowed to make practical applications. At the MFC anode, bacteria degrade organics releasing electrons directly to the solid electrode. Electrons flow through the external circuit generating useful electricity. The circuit is then closed at the cathode in which oxygen reduction reaction (ORR) takes place. Bacteria at the anode consume completely the oxygen into the chamber creating an anaerobic environment. At the cathode, the reaction is driven by the oxygen that is the electron acceptor and an aerobic environment is created.

MFC electrodes are based on conductive high surface area materials in order to i) enhance bacteria-surface interaction (anode); ii) enhance oxygen reduction reaction (ORR). Different environments are generated inside the same electrolyte, allowing the self-polarization of the electrodes. Particularly, the anode is negatively polarized and the cathode is positively polarized. It is then interesting to utilize anode and cathode of the MFC as negative and positive electrode of an internal supercapacitor as we previously showed [1,2]. This is a novel way of harvesting current/power output from a MFC. The combination of MFC electrode as internal SC electrode allowed to simplify the system with a pulsed current/power that increased at least one order of magnitude.

Here, different approaches to exploit the supercapacitive behavior of the MFC in order to boost up power are reported and discussed. References [1] C. Santoro, F. Soavi, A. Serov, C. Arbizzani, P. Atanassov. Biosens. Bioelectron., 78, (2016), 229-235. [2] F. Soavi, L.G. Bettini, P Piseri, P Milani, C Santoro, P. Atanassov, C. Arbizzani. Journal of Power Sources. doi:10.1016/j.jpowsour.2016.04.131

O5 _____________________________________________________________________________________


Flow-Batteries for Large-Scale Electrical Energy Storage: Beyond Conventional Batteries

Rachid Zaffou a, Belabbes Merzougui b, Hicham Hamoudi c

a Qatar Environment & Energy Research Institute, Qatar, Doha, [email protected]

b Qatar Environment & Energy Research Institute, Qatar, Doha, [email protected] c Qatar Environment & Energy Research Institute, Qatar, Doha, [email protected]

A Flow-Battery System is an Electrical Energy Storage approach that was

originally conceived by NASA during the energy crises of the 1970s. A flow battery utilizes reversible redox couples on two electrodes to store chemical energy. However, instead of storing the electrochemical reactants within the electrode, as in a conventional battery, the reactants are dissolved in electrolytic solutions and stored in tanks external to the flow battery stack. Flow batteries are emerging as a potential electricity storage technology to support an efficient, reliable and cleaner energy market. Some of the promising applications of flow batteries are related to load management of large-scale electricity supply to the grid (e.g., peak shaving, power quality, spinning reserves). Flow battery technology can also offer solutions to issues associated with the integration of intermittent renewable energy resources (e.g., wind, solar) with the power grid by making these power resources more stable, dependable, and dispatchable [1]. Despite all of these inherent advantages, FBS products have not been commercialized. The cell performance of flow batteries including the most mature flow battery technology (Vanadium Redox Battery) is poor (e.g., typically 0.1 W/cm2 of active area or less) [2], which makes the cell-stack assembly large and expensive. The reduction in stack size by improving stack performance is required to lower the stack cost which is considered the key driver to make flow batteries economically attractive. The objective of this poster is to provide a summary of our recent flow battery work in developing and demonstrating high power density flow battery system. This new flow battery design can deliver up to 10X higher power density than current state-of-the-art flow batteries while maintaining high energy efficiencies.

References [1] EPRI-DOE Handbook, 2003 [2] P. Zhao, H. Zhang, H. Zhou, J. Chen, S. Gao, B. Yi, J. Power Sources, 162, (2006), 1416. .

O6 _____________________________________________________________________________________


Activated Titanium Anodes for Electrochemical Industrial Processes: Applications, Standards and Testing

CHEMICAL NEWTECH S.p.a.- Titanium Anodes

Capriolo (BS), Italy

Electrodes, referred as anodes and cathodes depending on the polarity of the circulating current, are a fundamental part of every electrochemical industrial process. In the past, graphite, iron and lead have been widely used despite concerns due to electrode corrosion or mechanical wear resulting in the release of impurities and loss of the geometrical shape. In the late ‘60s, Dimensionally Stable Anodes (DSA) were introduced, and immediately obtained a wide success for most of the industrial applications. DSA are composed of a base material (Titanium) characterized by good workability, high chemical resistance and electrical conductivity, which is covered by a suitable electroactive surface layer. The surface layer composition is made of mixed metal oxides (MMO) of the platinum group (Ruthenium, Iridium, Palladium, Rhodium, Platinum); its composition varies in terms of metal oxides and their relative percentages as a function of the desired electrode application. The main advantage of DSA electrode is that only the catalytic coating wears, while the structural integrity of the electrode is preserved.

Activated titanium electrodes are widely used in different industrial applications: for chlorine evolution such as in the chlor-alkali processes and in electrolyzers for chlorate and hypochlorite production, alternatively for oxygen evolution such as in the electrometallurgical processes of electrogalvanizing and electrowinning. A third important application field of DSA applications is the impressed current cathodic protection, which is in turn extremely differentiated as a function of the structure to be protected, ranging from small metallic tank, to buried pipelines and offshore platforms.

As above mentioned, also DSA electrodes suffer from deterioration mechanisms due to both the aggressive operating environment and the continuous anodic current flow, thus leading to the exhaustion of the electroactive layer over time. As a consequence, the development of standard testing methods with the aim of assessing the log-term electrode durability at given experimental conditions, represents a key step towards the optimization of the electrodic materials and in turn to the whole electrochemical industrial process. DSA Registered trademark of Industrie De Nora Spa

O7 _____________________________________________________________________________________


Electrochemistry in the Processes of Metals Recovery: Technologies to Rediscover

ENGITEC S.p.a., Novate Milanese (MI), Italy

From the beginning, industrial processes had to meet proper efficiency and economic targets, with a less accurate care of environmental and working conditions. The continuous modifications of environmental constrains force to novel solutions and to a continuous research for the definition of alternative processes. The most popular words used for these processes are “green”, “sustainable”, “healthy”, “novel”, “eco-friendly”, etc. In the field of metals extraction and metals recovery (primary and secondary sources), “novelty” is sometimes confused with the re-discover of reactions well known in literature, but rarely applied in a real production plant. Economical fluctuations of raw materials, connected with the growing needs of lower-emissions production plants, can transform questionable reactions into viable solutions. In this contribution, a historical and electrochemical evolution of explicative processes will be presented.

- a thermo-chemical process for lead recovery form lead-acid batteries can be replaced by a hydro-thermal process, where electrochemistry plays a key role in many parts of the whole batteries treatment.

- Oxygen and Iron electrode depolarization reactions act as money-savers in Copper and Zinc refinery.

- The familiar water splitting reaction may act as in-situ reactant production in the amphiphilic metal recovery. Processes can thus be designed, answering worldwide to still-silent environmental issues.

- Membranes research and electrochemistry can give unexpected solutions to design a system where no vapors, dusts or liquids are released, and reactants can be formed and recycled in a closed loop.

Figure 1: Spent Pot Liners in Aluminum cryolitic baths

O8 _____________________________________________________________________________________


Aluminum Electrolytic Capacitors: History, Components, Applications.

ITELCOND S.r.l., Bareggio (Mi), Italy

Capacitors are components that store energy in an electric field, located in their dielectric, as observed for the first time by Alessandro Volta around 1775. Although the scientific community had to wait until 1886 when Charles Pollack, while studying aluminum anodisation, discovered an electrolyte able to preserve this thin oxide layer even when no power was supplied to the system. Various attempts occurred in the following years but only in 1945 a major step in the understanding of the electrochemistry of the capacitor was taken by Pourbaix with his description of the potential/pH behavior of metals. Therefore the core of the process for building a capacitor is to provide the correct electrochemical balance, for the entire lifetime of the object, between all the elements composing it, especially regarding to the anodic foil and its etching, the dielectric with its forming voltage, and the electrolytic solution, namely the cathode. A modern capacitor is a more complex system than it was 70 years ago, required to provide higher reliability, better performance and shrunk dimensions from a market moving towards the “zero defect”, while still following to the same chemical models described before. Overcoming the criticality aroused by the optimization of a component that is known to be the factor determining the expected lifetime of an apparel is the assignment of any capacitor manufacturer. A task that involves two major fields of expertise: increasing stringent requirements in the choice of material, quality and test as well as in operations control and a strong push on predictive methods to allow new products to reach the market in the shortest time possible.

O9 _____________________________________________________________________________________


Electrochemical Photocatalysis on Supported Nanoporous TiO2: A Novel Advanced Oxidation Process for Water Treatment

NANOMATERIALS.IT S.r.l, Milano, Italy

Electrochemical photocatalysis on nanostructured TiO2 is an innovative and rather unknown water treatment technique belonging to the class of advanced oxidation processes (AOP). In this work, the industrial viability of this technique is evaluated by investigating the decontamination of aqueous solutions containing either the azo-dye RR243 or the pharmaceutical drug Carbamazepine, which can be considered bench-mark pollutants for the treatment of industrial and municipal wastewaters, respectively. The process is carried out in a laboratory-scale tubular photocatalytic reactor working in semi-batch mode under electrical polarization of the catalyst. The catalyst is a supported titanium dioxide having a sub-micrometer porosity, obtained by Plasma Electrolytic Oxidation (PEO). Neither UV irradiation of the TiO2 catalysts nor the electrical bias individually considered lead to a significant reduction of the pollutant concentration. By irradiating the catalysts with UV-C light while applying an electrical bias to the same, the concentration of the dye dramatically decreases. The technique is compared to conventional photocatalysis on Degussa P-25 TiO2 powders. The main advantages of this method over current approaches for the degradation of pollutants are that it can effectively target an extremely wide spectra of organic pollutants, a considerable processing time reduction, a suitable and easy-to-scale-up reactor design and operation costs comparable to current advanced oxidation processes. A further advantage is the relatively easiness in the production of the TiO2 catalyst by PEO.


Thursday morning, September 15th 2016

9.00 Keynote

M. Benedetto Electrolytic Cell equipped with Concentric Electrode pairs

K1 p. 12

9.30 Keynote K. Bouzek Fuel Cell Flow Field Optimization – from a Single Channel Experiment to the Fuel Cell Stack Model

K2 p. 13

10.00 Keynote F. La Mantia Aging Mechanism of Prussian Blue Derivatives during Zinc-Ion Intercalation

K3 p. 14

10.30 Coffee Break

11.00 Keynote F. Lapicque Electrocoagulation and other Techniques for Water Treatment: a Couple of Relevant Examples

K4 p. 15

11.30 J. Lobato


O10 p. 16

11.50 M. Lo Faro From Button Cell to 500 W SOFC Stack fed with Dodecane

O11 p. 17

12.10 C. Saez Different Strategies for the Electro-remediation of Soils Polluted with Herbicides

O12 p. 18

12.40 Lunch Time

K1 _____________________________________________________________________________________


Electrolytic Cell equipped with Concentric Electrode pairs

Mariachiara Benedetto

Industrie De Nora S.p.A., Milano, Italy,. [email protected]

A new electrolyzer design was invented and protected by two patent applications: mono-polar [1] and by-polar [2] configuration. The invention relates to a bipolar electrolytic cell particularly useful for electrochemical processes carried out with periodic reversal of polarity. The cell is equipped with a series of concentric electrode pairs, the innermost pair and the outermost pair being connected to the poles of a DC generator and the intermediate pairs acting as bipolar electrodes. The different pairs of electrodes are arranged and connected in such a way that, at each stage of the process, the overall cathodic area is equal to the anodic area

This new multipurpose electrolyzer design can be employed in different fields obtaining improved results compared with applied electrolyzers for products existing on the market. Testing results will be presented. References [1] WO2013189670: Applicants: Industrie de Nora S.p.A.; Inventor:, M. Benedetto. [2] WO/2015/082527: Applicants: Industrie de Nora S.p.A.; Inventor:, M. Benedetto.

Fig. 1

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Fuel Cell Flow Field Optimization – from a Single Channel Experiment to the Fuel Cell Stack Model

Karel Bouzek, Roman Kodým, Monika Drakselová, Adam Giurg, Martin Paidar

University of Chemistry and Technology Prague, Czech Republic, [email protected]

Utilization of methods of the mathematical modelling represents well established approach in an effective design and optimization of chemical, including electrochemical, technologies. In the case of electrochemical engineering, it has primarily been used to solve problems related to the optimization of the local values of electrode potential and current density. With rapid development of methods of numerical mathematics accompanied by the increasing calculating power of desk-top computers, the numerical simulation approach has penetrated a broad range of aspects of electrochemical technology design, including flow dynamics (CFD). In the present contribution an example of CFD methods application to the problem of the reactants flow distribution will be presented for an example of the HT PEM type fuel cell system.

In order to accomplish this task, a series of experiments and calculations have been performed allowing assessing impact of the individual components of this complex system on the resulting fuel cell stack performance. These quantities may potentially also significantly impact fuel cell or stack life time. In a first step, simplified flow channels geometry have been manufactured and used to determine a pressure drop associated with gas flow under typical fuel cell operating conditions. Results obtained for the system without gas diffusion layer (GDL), i.e. smooth flow channels, have been used to validate the CFD mathematical model developed. In the next step selected types of the GDLs have been added to simulate real fuel cell conditions as closely as possible. The data obtained allowed to evaluate GDLs gas permeability in through-plane and in-plane direction. These local studies have been followed by developing and validating corresponding simplification of numerical model of industrial scale flow fields. Typical geometries were studied. On base of the results obtained reactants CFD was calculated for a full scale flow field. This validated model allows effective optimization of flow field geometry at relatively low computational demands. In the last step the data and modelling approaches developed have been applied to simulate flow distribution in an operating industrial scale fuel cell stack. Macrohomogeneous approach developed previously [1] in a combination with flow field description simplification developed here were used to accomplish this task.

The study of flow distribution inside the fuel cells stack thus exhibits a complex multiscale problem with different possible solutions. The presented one allows detailed analysis of local values distribution while maintaining reasonable efficiency and flexibility using standard computational hardware, in case of complex geometries with extended operational memory.

Financial support by the FCH JU within the framework of the project CISTEM, contract No. 325262, is gratefully acknowledged. References [1] R. Kodým, M. Drakselová, P. Pánek, M. Němeček, D. Šnita, K. Bouzek, Electrochim. Acta, 179, (2015), 538–555.

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Aging Mechanism of Prussian Blue Derivatives during Zinc-Ion Intercalation

Fabio La Mantia

Universität Bremen, Energiespeicher- und Energiewandlersysteme, Bremen, Germany,

[email protected]

Aqueous zinc-ion batteries have recently shown a good potential for stationary application and storage of energy from volatile alternative sources, such as wind and solar [1]. Using copper hexacyanoferrate (CuHCF) as intercalating active material for the positive electrode, it was possible to reach 100 life cycles, a specific energy equal to 46 Wh kg-1, and a specific power equal to 480 W kg-1, with a charge efficiency of 98% [2]. With the aim of reaching a longer cycle life, ideally 10000 cycles, we investigated the aging mechanism of CuHCF, in particular looking at the effect of the electrolyte’s nature and concentration on the life cycle and performance of the material. We observed

that the aging mechanism of CuHCF during Zn2+ intercalation is not related to the dissolution of the active material, but rather to a phase transformation of the intercalating structure. This is evidenced by the appearance of a reversible redox peak in the differential specific charge profile at circa 0.8 V vs. Ag/AgCl upon cycling (see Figure). The appearance of this second redox peak shows not only a gradual transformation in the intercalating phase, but as well a change in the intercalation mechanism. We observed also that the phase transformation was strongly

influenced by the concentration of the salt, where high concentrations were favoring it, and by the nature of the anions. In particular, it appeared that perchlorates are favoring the transformation, while sulfates are slowing it down. XRD measures have confirmed the phase transformation upon cycling, however the new phase could not be identified with already known forms of zinc hexacyanoferrate or copper hexacyanoferrate. References [1] C. Xu, B. Li, H. Du, F. Kang, Angew. Chem. Int. Ed., 51, (2012), 933–935. [2] R. Trócoli, F. La Mantia, ChemSusChem, 8, (2015), 481-485.

Figure: Differential specific charge profile for different cycles of CuHCF measured at current rate of 5C in 100 mM ZnSO4.

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Electrocoagulation and other Techniques for Water Treatment: a Couple of Relevant Examples

François Lapicque, Marie Le Page Mostefa

CNRS – Université de Lorraine, Laboratory for Reactions and Chemical Engineering,

Nancy, France, [email protected] Pollution and hazard can be generated by low-toxic compounds such as a couple of transition metals and by phosphate. This latter although largely involved in biochemical processes is not fully harmless in environment since responsible to a part of eutrophization of many natural water systems (lakes, ponds, rivers …) rendering more problematic the air oxygen transfer to the considered water, so threatening development of life in ponds and rivers. Besides, zinc (II) and iron (II) cations in waste waters are often generated by mere rainfalls on the roofs and in gutters of houses and buildings: the local acidity of the water aggravated by the more acidic conditions in urban areas are to render more acute the presence of Zn (II) and Fe (II) ions at levels ranging from 1 to 20 ppm in urban waters for this reason. In addition, combination of these light pollutants, coupled to the presence of calcium – in addition to anions e.g. carbonate and sulfate - often at high levels are responsible of severe fouling and clogging of pipes, valves and taps, in particular in warm areas such as Northern Africa. For treatment of this “little-toxic” pollution, electrocoagulation can be thought of, but other techniques such as precipitation at the right pH can be thought of. The comparison is made in terms of • Removal efficiency, • Energy cost, • Significance of the volume of the sludge produced by the different techniques, • Possible implementation in water purification systems, and • Environmental impact.

On a more fundamental result, the mechanisms of elimination of the two cations and phosphate have been investigated, depending on the technique employed. It appears for instance that upon anodic dissolution of aluminium, the amounts of Zn (II) and Fe (II) cations removed are directly proportional to the amount of Al hydroxide – in the form of boehmite – generated: the hydroxides of transition metals simply adsorb on the surface of aluminium flocs.

O10 _____________________________________________________________________________________



Justo Lobato, Yeray Asensio, Carmen M Fernández-Marchante, Pablo Cañizares,

Manuel A. Rodrigo

University of Castilla-La Mancha, Department of Chemical Engineering, Faculty of Chemical Sciences and Technologies, Ciudad Real, Spain, [email protected]

In the last twenty years, the emission of greenhouse gases has increased drastically. In order to limit this environmental crisis, future energy sources should be renewable and carbon neutral. Microbial fuel cells (MFC) are a promising technology for the generation of clean energy, in which microorganisms are able to produce electricity oxidizing the organic matter contained in wastewater [1]. However, disadvantages as the high cost of metal catalysts used in the cathode electrodes to increase the power output or the cost of an external oxygen supply in the cathode compartment limit the application of this devices for industrial applications [2].

The development of a novel technology based on the concept of solar MFC could reduce the disadvantages of the conventional MFC configurations. Therefore, the use of a photosynthetic biocathode consisting of a culture of algae could provide oxygen in the cathode compartment as electron acceptor, while the algal biomass produced due to the growth of algae could be recirculated to the anode compartment and be used as fuel. In this way, the devices can be understood as photo microbial cells (PMC) by comparison with photovoltaic cells (PVC), where electricity is produced using a light-excited semiconducting material. On the contrary, in the PMC, synergistic interaction of several microbial and electrochemical processes could produce electricity directly from Sun.

First of all, microalgae were cultured in sterilized Bold Modified Basal freshwater nutrient solution under cycles of light-darkness of 12:12 h. Secondly, the algae culture was treated at three different temperatures (25°C, 55°C and 95°C), in order to create an algal biomass to be used as a fuel for PMC. In all cases, this biomass produced energy in the PMC, but the best results were achieved when the algal biomass was produced at the lowest temperature. This means that algal biomass can be directly use as a fuel in the PMCs. Acknowledgements: Financial support from Spanish Ministry of Economy and Competitiveness (MINECO) through project SUNLIVINGENERGY (CTQ2013-49748-EXP, Explora Program) is gratefully acknowledged. In addition, financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is acknowledged. References [1] B.E. Logan, B. Hamelers, R. Rozendal, U. Schröder, J. Keller, S. Freguia, P. Aelterman, W. Verstraete, K. Rabaey, Environmental Science & Technology, 40, (2006), 5181-5192. [2] A. Gonzalez Del Campo, J.F. Perez, P. Cañizares, M.A. Rodrigo, F.J. Fernandez, J. Lobato, Fuel, 140, (2014), 209-216.

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From Button Cell to 500 W SOFC Stack fed with Dodecane

Massimiliano Lo Faro, Stefano Trocino, Sabrina C. Zignani, Giuseppe Monforte, Antonino S. Aricò

CNR-ITAE, Messina, Italy, [email protected]

A proof-of-concept Solid Oxide Fuel Cell (SOFC) system of 500 Wel fed with n-dodecane reformate was realized in order to prove the reliability of SOFC technology for naval uses. The cells used for the prototype consisted of Ni-YSZ/YSZ/YDC/LSFC whereas the catalyst for the reformer of n-dodecane was Rh-CeO2-ZrO2. At the preliminary stage and as to a propaedeutic approach, a microplant consisting of a reformer for the treatment of 7 Wh of dodecane and a single button cell were coupled in order to determinate the proper conditions of operation and the degradation effects occurring during 300 h of stressed tests. Then, a single large area cell and a stack were fed with n-dodecane reformate to determinate the performance achievable under practical conditions. Electrochemical ac-impedance spectra (EIS) and polarizations curves were carried out to study the systems above mentioned. As well, post-operation scanning electron microscopy analysis (SEM) on the cell and thermal analysis on the catalyst were conducted in order to demonstrate the ageing effect observed during the operation of the coupled system.

Proof-of-concept of an integrated system SOFC

Acknowledgements The authors acknowledge the Italian Ministry of Education, Universities and Research (MIUR) for the grant agreement PON2_00153_2939517 for the project entitled TESEO

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Different Strategies for the Electro-remediation of Soils Polluted with Herbicides

Cristina Sáeza, Carolina Riscoa, Sandra Rodrigoa, Ruben López-Vizcaínob,Vicente

Navarrob, Pablo Cañizaresa, Manuel A. Rodrigoa

aUniversity of Castilla-La Mancha, Department of Chemical Engineering, Facultad de Ciencias y Tecnologías Químicas, Ciudad Real, Spain, [email protected]

bUniversity of Castilla-La Mancha, Geoenvironmental Group, Civil Engineering School, Ciudad Real, Spain

Over the last decades there is a growing concern about the application of herbicides and, particularly about their effect on environment. Negative environmental impact is related to the contamination of water and soil with herbicides, and it has received great deal of attention from the scientific community. One of the worst types of events related to the pollution carried out by these herbicides is the associated to accidental leakage, which may become a major source of diffuse pollution. In order to prevent serious environmental problems under accidental discharges of these species, it is very important the rapid actuation against accidental discharges of hazardous species with efficient technologies that help to remediate the soil rapidly. In this point, the electrokinetic (EK) remediation seems to be a very promising alternative for the treatment of low-permeability soils polluted with ionic and water soluble pollutants, although it can also be used to remove hydrophobic compounds by the use of special flushing-fluids. In EK remediation, the transport of pollutants is driven by electro-osmotic, electromigration or electrophoresis fluxes, whose magnitude and direction depend on the electric potential applied between electrodes sited in the soils. This versatility makes that its combination with permeable reactive barriers (PRB) in which contaminants may be degraded or sequestered appears as a good alternative to enhance EK-remediation. With this background, different strategies for the EK-remediation of soils polluted with herbicides have been evaluated: 1) EK technologies for the control of the pollution of soils (fence technology), 2) EK technologies for the pollutant mobilization towards an aqueous phase (flushing technology), and 3) combined EK – PRB technologies to enhance the removal of herbicides contained in the soil. To do this, bench-scale set-ups from 25 to 175 dm3 of capacity and a pilot-scale plant of 16 and 32 m3 have been used. A natural soil with high clay content were used as low permeable soil, and four pesticides (two polar and two non-polar) were used as models of pollutant. All the experiments were performed in a potentiostatic way using graphite as electrodic materials, and with a duration up to 40 days. Results show that EK remediation is an efficient technology for the removal of polar and non-polar herbicides from soils, but it depends on the electrode configuration used. Likewise, the physico-chemical characteristics of the discharged waste influence on the primary mechanism (drag by electro-osmosis, electromigration or even evaporation).

Acknowledgments Financial support from the Ministry of Economy and Competitiveness (MINECO) of Spain under project CTM2013-45612-R and the excellence network E3TECH funded by the project CTQ2015-71650-RDT are acknowledged.


Thursday afternoon, September 15th 2016

14.20 J. Feliu Interfacial Reactivity on Shape-Selected Nanocatalysts

O13 p. 20

14.40 J. Perez Jet-cell Reactor for Hydrogen Peroxide Generation: a Proof of Concept

O14 p. 21

15.00 E. Sechi Preparation of Nickel Foams by Selective Corrosion of Ni/Cu films in different Solvents

O15 p. 22

15.20 F. Geneste Indirect Electroreduction on a Titanocene/Nafion®-Modified Electrode as Pretreatment to Enhance Biodegradability of Metronidazole

O16 p. 23

15.40 C. Ania Nanoporous Carbon as Efficient Materials for Electrochemical Applications: the Role of the Pore Architecture and Surface Chemistry

O17 p. 24

16.00 Coffee Break

16.30 E. Bocos Application of Electrochemical Technology for Ionic Liquid Degradation and the in situ Monitoring of the Process

O18 p. 25

16.50 E. Petrucci Mitigating the Formation and Persistence of Inorganic Chlorine Compounds in the Anodic Oxidation of Chloride-Containing Solutions

O19 p. 26

17.10 A. Diez Remediation of Ionic Liquid Polluted Soils by Enhanced Electrokinetic Treatment

O20 p. 27

17.30 Poster Flash presentation

18.50 Poster Session & Cocktail Buffet

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Interfacial Reactivity on Shape-Selected Nanocatalysts

Rosa M. Arán-Ais, José Solla-Gullón, Enrique Herrero, Juan M. Feliu

Universidad de Alicante, Instituto de Electroquímica, Alicante, Spain, [email protected]

Surface structure effects in electrocatalytic reactivity can be assessed through the use of structure sensitive reactions, and the use of single crystal electrodes. Shape-controlled nanoparticles are the ideal tools to apply these knowledge obtained to practical purposes [1]. They have been shown to be powerful tools to tune the activity, selectivity and stability of very relevant electrocatalytic surface reactions, in particular oxygen reduction reaction (ORR), by tailoring their size, shape and composition [2, 3]. In most cases, the use of surfactants or shape-directing agents is needed to grow the nanocrystals in a specific direction. Therefore, a subsequent decontamination procedure to remove these agents becomes compulsory [4]. In this regard, some post-treatments applied to the as-prepared materials can strongly affect their final surface structure and composition, and consequently, their resulting electrocatalytic activity. We point the self-consistency of the electrocatalytic properties of shape-selected Pt nanoparticles and the local changes induced on these nanocatalysts as a result of classical electrochemical activation [5].

Finally, we aim to understand the electrochemical properties of shape-controlled Pt-based multimetallic nanoparticles. This approach has been possible by combining microscopic, spectroscopic and electrochemical measurements on octahedral PtNi and PtNiCo nanoparticles. A deeper insight in the understanding of the reactivity of these multimetallic nanoparticles would be desirable for tailoring better catalysts.

References

[1] J. Solla-Gullon, F.J. Vidal-Iglesias, J.M. Feliu, Annu. Rep. Prog. Chem., Sect. C, 107, (2011), 263. [2] W. Wang, B. Lei, S. Guo, Advanced Energy Materials (2016) DOI: 10.1002/aenm.201600236. [3] R.M. Arán-Ais, F. Dionigi, T. Merzdorf, M. Gocyla, M. Heggen, R.E. Dunin-Borkowski, M. Gliech, J. Solla-Gullón, E. Herrero, J.M. Feliu, P. Strasser, Nano Lett., 15, (2015), 7473. [4] R.M. Arán-Ais, F.J. Vidal-Iglesias, J. Solla-Gullon, E. Herrero, J.M. Feliu, Electroanalysis, 27, (2015), 945. [5] R.M. Arán-Ais, Y. Yu, R. Hovden, J. Solla-Gullón, E. Herrero, J.M. Feliu, H.D. Abruña, J. Am. Chem. Soc., 137, (2015), 14992.

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Jet-cell Reactor for Hydrogen Peroxide Generation: a Proof of Concept

Jose F. Pérez, Javier Llanos, Cristina Sáez, C. López, Pablo Cañizares, Manuel A.

Rodrigo

University of Castilla-La Mancha, Department of Chemical Engineering, Facultad de Ciencias y Tecnologías Químicas, Ciudad Real, Spain, [email protected]

Hydrogen peroxide is a common and widely used compound in the chemical

industry. At present, most of it is manufactured by means of the Anthraquinone process [1]. Although commercially profitable, the aforementioned way of production is intensive in the use of energy and generates large quantities of residues. Because of this, new approaches to hydrogen peroxide are interesting.

In this context, electrochemical production through oxygen reduction reaction (ORR, Eq. 1) stands as an efficient and clean way of production [2]:

(1) In this work, a proof of concept of a new electrochemical reactor for hydrogen

peroxide generation through ORR is presented. The key features of this reactor are a venturi-based jet-injector for oxygen feed and a porous 3D modified carbon felt cathode. With these improvements, a higher space time yield and a lower energy consumption are expected. As a way of example, Figure 1 shows generation-time curves and its corresponding current efficiency.

Electrolyte: Na2SO4 0.05 M; Reaction volume: 1 dm3; Liquid flow: 64 dm3 h-1; Air flow: 0.25

dm3 min-1; I: 1 A. H2O2 concentration; Current efficiency.

After 3 hours of electrolysis, hydrogen peroxide concentration up to 1,130 mg dm-3 was measured with 60% current efficiency and a resulting specific energy consumption of 15.38 kWh per kg H2O2 Those preliminary results suggest that hydrogen peroxide generation in the jet-cell may be fast, efficient and economical.

Acknowledgments The authors acknowledge funding support from the Regional Goberment

(Project PEII-2014-039) and the excellence network E3TECH funded by Ministry of Economy and Competitiveness (MINECO) the project CTQ2015-71650-RDT. References [1] J.M. Campos-Martin, et al., Angewandte Chemie Int. Ed., 45. (2006), 6962-6984. [2] E. Petrucci, A. Da Pozzo, L. Di Palma, Chemical Engineering Journal, 283, (2016), 750-758.

O15 _____________________________________________________________________________________


Preparation of Nickel Foams by Selective Corrosion of Ni/Cu films in different Solvents

Elisa Sechi, Annalisa Vacca, Michele Mascia, Simonetta Palmas, Simona Corgiolu,

Pablo Ampudia,

Università degli Studi di Cagliari, Dipartimento di Ingegneria Meccanica, Chimica, e dei Materiali, Cagliari, Italy. [email protected]

Electrochemical selective dissolution of a less noble component from a binary alloy or a two phase codeposit has been used to obtain nanoporous structures of noble metals such as gold, silver and platinum. Porous nickel is a potentially low-cost alternative to precious-metal catalysts and it can be obtained from selective corrosion of Ni/Al or Ni/Zn systems. More recently also Ni/Cu alloy has been used as precursor to fabricate porous Nickel by electrochemical dealloying: because Cu is chemically more stable than Ni, the selective dissolution of Cu is based on the passivation of Ni under suitable electrochemical conditions. In this work we investigate the corrosion of Ni/Cu films using different solvents and different composition of the films. Electrodeposition was performed in aqueous electrolytes, composed by 0.5M boric acid, with different concentrations of nickel (II) sulfate hexahydrate and copper (II) sulfate pentahydrate. The anodic dissolution was carried out both in glycerol and ethyleglicol containing different amount of water: as a comparison, also aqueous solution has been used in corrosion test. The supporting electrolyte was constituted by 0.5 M of sodium sulfate and boric acid 0.5 M. Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) were used to examine the morphology and the chemical compositions of the samples. Electrochemical impedance spectroscopies and linear sweep voltammetries have been used to characterize the sample both for determination of the specific surface and catalytic properties toward the hydrogen evolution reaction. Results shown that porous structure can be obtained using water and glycerol as solvent. Moreover, content of copper of 70-80% allows to obtain a ordered porous structure. This work was partially funded by Regione Autonoma della Sardegna, Fundamental Research Programme, L.R. 7/2007 ``Promotion of the scientific research and technological innovation in Sardinia'' under grant agreement CRP- 59886 AMBROSIA Project.

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Indirect Electroreduction on a Titanocene/Nafion®-Modified Electrode

as Pretreatment to Enhance Biodegradability of Metronidazole

Florence Genestea, I. Saidia,b,c, Isabelle Soutrelb, Didier Flonera, Florence Fourcadeb, Nizar Bellakhalc, Abdeltif Amraneb

a ISCR, Université de Rennes 1, Rennes, France, [email protected] b ENSCR, Université Rennes1, CNRS, Rennes, France c , INSAT, Laboratoire de recherche de Catalyse d’Electrochimie de Nanomatériaux et leurs applications et de didactique, CENAD, Tunis, Tunisie The treatment of recalcitrant compounds requires physico-chemical methods for their degradation that often suffer from a lack of selectivity and high cost. Integrated processes, combining physico-chemical and biological treatments have received a growing attention for their efficiency in complete mineralization of biorecalcitrant compounds at reduced operating costs. In this work, we investigated a coupling method involving an indirect electrochemical reduction process as a possible pretreatment for the degradation of recalcitrant compounds [1]. The feasibility of the proposed coupled process was demonstrated on metronidazole, a recalcitrant antibiotic. The pretreatment was achieved in a home-made electrochemical flow cell using a graphite felt electrode of high specific area, allowing a rapid and quantitative transformation of polluted solutions.

Indirect electrolyses of metronidazole were performed with a titanium complex known to reduce selectively nitro compounds into amines. Direct electrolyses were also carried out for comparison. The biodegradability of the resulting products was first estimated using classical parameters and then validated through a biological treatment. Electrochemical pretreatment led to a more efficient biological degradation compared with a single biological treatment, with overall mineralization yields up to 87% within 16 days, confirming the feasibility of the proposed coupled process. A titanocene/Nafion®-modified graphite felt electrode was then achieved [2]. Flow heterogeneous catalytic reduction of metronidazole carried out with the titanocene/Nafion®-modified graphite felt as working electrode led to total reduction of metronidazole and to a significant increase of biodegradability with a higher turnover number than in homogeneous conditions.

References [1] I. Saidi, I. Soutrel, D. Floner, F. Fourcade, N. Bellakhal, A. Amrane, F. Geneste, J. Haz. Mat., 278, (2014), 172. [2] I. Saidi, I. Soutrel, F. Fourcade, A. Amrane, N. Bellakhal, F. Geneste, Electrochim. Acta, 191, (2016), 821.

O17 _____________________________________________________________________________________


Nanoporous Carbon as Efficient Materials for Electrochemical Applications: the Role of the Pore Architecture and Surface Chemistry

Conchi ANIA, Alicia Gomis-Berenguer, Raquel García-González

Instituto Nacional del Carbón (INCAR, CSIC), Oviedo, Spain,

[email protected]

Recently the application nanostructured carbons such as graphene, carbon nanotubes and graphite oxides has gained a considerable attention in electrochemical and photochemical reactions, due to the role of conductive carbons as charge transferring media and the possibility of tuning the optical properties of the carbon, wettability and hydrophobicity via surface functionalization [1]. Despite their limited electronic conductivity derived from a poor structural order, nanoporous carbons having large surface areas have also been widely used as electrodes in various electrochemical reactions. This communication explores the electrochemical performance of nanoporous carbon electrodes prepared from various precursors in different applications related to energy conversion and environmental remediation (i.e., electrosynthesis, electrocatalysis, photoelectrochemistry). Our results showed that the nanoconfinement in the porosity of the carbon electrode leads to an increase in the electron transfer rate and electrical contact in biosensing applications. This demonstrates the critical role of matching the molecular dimensions of the target molecule with the mean pore size of the carbon electrode for an optimal and efficient molecular orientation minimizing the random distribution at non-efficient positions [2]. We also report the unique photoelectrochemical activity of metal-free nanoporous carbon for the oxygen evolution reaction. Owing to the specificity of the precursor and synthesis conditions, the highly porous carbon surface is rich in “photosensitizers” (i.e., N-, O- and S- containing groups) and conductive graphite units. The combination of these features leads to the photogeneration of charge carriers due to light absorption on certain regions of the carbon surface (chromophore-like moieties) that leads to the photoelectrochemical oxidation of water at a very low overpotential [3]. Acknowledgements The authors thank the financial support of the Spanish MINECO through an excellence network E3TECH (grant CTQ2015-71650-RDT).

References [1] J. Iniesta, L. Garcia-Cruz, A. Gomis-Berenguer A, C.O. Ania, Carbon materials based on screen printing electrochemical platforms in biosensing applications, in Electrochemistry Series, RSC Publishing, 13 (2016), 133-169. [2] L.F. Velasco. A. Gomis-Berenguer, J.C. Lima, C.O. Ania CO, ChemCatChem, 7, (2015), 3012-319. [3] C.O. Ania, M. Seredych, E. Rodriguez Castellon, T.J. Bandosz, Carbon, 79, (2014), 432-441.

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Application of Electrochemical Technology for Ionic Liquid Degradation and the in situ Monitoring of the Process

Elvira Bocosa, Aida Díeza, Marta Pazosa, Elisa González-Romerob, M. Angeles

Sanromána aUniversity of Vigo, Department of Chemical Engineering, Vigo, Spain,

[email protected] bUniversity of Vigo, Department of Analytical Chemistry, Vigo, Spain

Over the last years, environmental concerns have generated the implementation of industrial processes using greener solvents. In this context, the replacement of volatile organic compounds by ionic liquids is paying close attention by the scientific community for the achievement of truly green processes. This fact has contributed to introduce the use of these compounds at industrial scale. Although the low vapor pressure of ionic liquids may reduce the air pollution in relation to the typical volatile organic compounds, some of them show a high solubility in water and great affinity for soil, thus becoming persistent pollutants in both the aquatic and the soil environment. Due to their complex structure, the ionic liquid can be considered as new emerging contaminants. Hence, the search of efficient wastewater treatment of this kind of pollutant is a subject in the limelight [1]. Therefore, the present study is focused on the development of two innovative scenarios by application of electrochemical technology: i) verification of the electro-Fenton process to treat emerging pollutants such as ionic liquids, and ii) application of differential pulse voltammetry (DPV) analysis on Screen-Printed electrodes as transducer that permits the in situ monitoring of the process. With these objectives, several commercial families of ionic liquids were used to evaluate the efficiency of the electro-Fenton. Initial trials were performed using different experimental conditions, in order to optimize several key parameters such as current intensity, iron concentration and electrolyte. Based on HPLC and GC/MS analysis the main degradation products and the carboxylic acids formed along the treatment were identified, thus proposing their plausible degradation pathways. Further, during the treatment it is necessary the in situ monitoring of the process for a rapid decision-making to improve the degradation yields as long as reducing its energy cost. One possible solution is the application of a simple, feasible, and relatively cheap technique as DPV through a DropSens DSC connector and Screen-Printed Carbon electrodes for monitoring the evolution of electroactive compounds from the electro-Fenton process. The DPV data reported different peaks of current and potential which permit the evaluation of the ionic interaction of the complex formed along the treatment. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT, CTQ2015-71955-REDT and GRC 2013/003). The authors would like to thank to MINECO for financial support of E. Bocos and A. Díez under FPI program and M. Pazos under Ramón y Cajal program. References [1] E. Bocos, et al., Chem. Eng. J. (2016), doi:10.1016/j.cej.2016.04.058.

O19 _____________________________________________________________________________________


Mitigating the Formation and Persistence of Inorganic Chlorine Compounds in the Anodic Oxidation of Chloride-Containing Solutions

Elisabetta Petrucci, Daniele Montanaro, Luca Di Palma

Sapienza University of Rome, Dipartimento di Ingegneria Chimica Materiali Ambiente, Roma, Italy, [email protected]

Electrochemical technologies are nowadays considered effective and environmentally friendly methods for disinfection and degradation of a wide range of pollutants. However, under particular conditions, the electrogeneration of persistent and toxic compounds can occur thus limiting the possible applications of this technology due to issues concerning human consumption of drinking water and wastewater disposal. Direct anodic oxidation can be enhanced by synergistic effect of electrogenerated oxidants. In particular, electrolysis of chloride-containing solutions produces free chlorine, a mixture of chlorine, hypochlorous acid and hypochlorite, which exhibits great efficiency in bleaching treatment and water disinfection. Problems arise when further oxidations result in the formation of chlorate and perchlorate that are suspected of causing severe impacts on humans’ health and aquatic ecosystems. Due to the introduction of increasingly stringent environmental regulations, advances in mitigating the presence of these ions in the treated solutions are needed. In this work, an experimental comparison among different approaches to reduce either the formation or the persistence of inorganic chlorine compounds, from electrolysis of chloride-containing solutions is presented. The effect of anode materials, of operative conditions as well as the co-presence of reducing species, either added or simultaneously electrogenerated, have been all investigated. Moreover, the effect of combined UV light irradiation and cell design has been also considered. The results indicate that, in all the above-mentioned approaches, the formation of inorganic chlorine compounds is reduced by mitigating the bulk concentration of free chlorine or by limiting the presence and reactivity of oxidizing species capable of transforming hypoclorite into chlorate and then perchlorate. However, since the electrogeneration of inorganic chlorine compounds cannot be ever completely avoided, the feasibility of a post-treatment to convert these species back to chloride has been also evaluated. To this aim, we have tested both electrochemical and chemical reduction. Results show that cathodic reduction, strictly depending on cathode material, is unlikely to occur on common platinum or graphite electrodes. Chemical reduction by addition of home-made nano-zero valent iron (nZVI) have enabled complete conversion of residual free chlorine and chlorate thus resulting in a valid method to enhance the environmental sustainability of electrochemical treatment of solutions containing chloride.

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Remediation of Ionic Liquid Polluted Soils by Enhanced Electrokinetic Treatment

Aida Díez, Marta Pazos, M. Angeles Sanromán

University of Vigo, Department of Chemical Engineering, Vigo, Spain, [email protected]

In recent studies, the interactions of novel ionic liquids with soils have been studied. It is known that the mechanisms of ionic liquid sorption onto selected natural soils differ due to their organic content, cation exchange capacity, and particle size distribution. In addition, biological studies revealed the toxic effect of the presence of ionic liquid in soils [1]. Therefore, as part of the chemical fate of these compounds in the environment, their removal from the soil matrix is considered as challenge in the area of soil remediation. In the present work, the sorption of ionic liquid, 1-butyl-2,3-dimethylimidazolium chloride, onto different soil matrixes (kaolinite and montmorillonite clay) was investigated. Kinetics and isotherm studies were carried out to evaluate the effect of contact time, cation exchange capacity and particle size fraction. It was detected a low sorption capacity of kaolinite and near complete sorption when montmorillonite was used as soil matrix. In addition, the sorption experimental data were satisfactory fitted to the Langmuir isotherm model. It was corroborated that the desorption of the ionic liquid is hard because it remains strongly linked to the soil matrix increasing the difficulty to apply conventional technologies of soil treatment. After the characterization of the sorption process, the degradation of this pollutant sorbed into montmorillonite was evaluated by electrokinetic process with Fenton oxidation. This treatment has emerged as an interesting alternative to conventional soil treatments due to its peculiar advantages, namely the capability of treating fine and low-permeability materials, as well as that of achieving a high yield in the removals of salt content and inorganic and organic pollutants [2]. In this combined treatment, the hydrogen peroxide transported in the soil through the electrokinetic phenomena and electro-osmotic flow, is decomposed by iron or other transition minerals present in the soil into the active oxygen species, such as hydroxyl radicals (OH·), superoxide anions (O2

-), and hydroperoxyl radicals (HO2·), which are capable of oxidizing directly the

ionic liquid sorbed into the soil matrix. It was determined that in order to enhance this treatment it was necessary to bring the ionic liquid into solution by addition of facilitating agents or controlling pH. Operating at the optimized conditions, it was possible to reduce the presence of this pollutant in the soil reducing its phytotoxicity. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT and GRC 2013/003). The authors are grateful to MINECO for the financial support of Aida Díez under FPI program and Marta Pazos under Ramón y Cajal program. References [1] P. Stepnowski, W. Mrozik, J. Nichthauser, Environm. Sci. Technol. 41, (2007), 511-516. [2] O. Iglesias, M.A. Sanromán, M. Pazos, Ind. Eng. Chem. Res. 53 (2014), 2917-2923.

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Friday, September 16th 2016

9.00 S. Soler Room-Temperature Electrochemical Induced Direct C-H-Arylation

O21 p. 30

9.20 L. Mais Electrochemical behaviour of Copper-based substrates for CO2 electroreduction in both aqueous and non-aqueous electrolytes.

O22 p. 31

9.40 C. Ridruejo Development of Air-Diffusion Cathodes for Electrochemical Water Treatment: From Synthesis to Use

O23 p. 32

10.00 S. Sabatino Investigation of an Electrochemical Process for the Conversion of Carbon Dioxide to Higher Value Products

O24 p. 33

10.20 A. Soriano Removal of Perfluorohexanoic Acid (PFHxA) from Industrial Effluents by Nanofiltration Followed by Electrochemical Oxidation of the NF Concentrate

O25 p. 34

10.40 Coffee Break

11.10 J. Steter Electrochemical Removal of Methyl Paraben using Different Anodes and Aqueous Matrices

O26 p. 35

11.30 A. Tsurumaki Preparation of Novel Polymer Electrolytes Based on Poly(tetrafluoroethylene) and Ionic Liquids for Lithium Ion Batteries

O27 p. 36

11.50 V. Perez Influence of Na2SO4 Concentration on the Abatement of Norfloxacin using BDD Electrodes

O28 p. 37

12.10 T. Baran Semiconductor Structures for Hydrogen Peroxide Production on Photoelectrochemical Way

O29 p. 38

12.30 M. Musiani Preparation of Ag-modified Ni Foams by Galvanic Displacement and their Use as Cathodes for the Reductive Dechlorination of Herbicides

O30 p. 39

12.50 Conclusions

13.00 Lunch Time

O21 _____________________________________________________________________________________


Room-Temperature Electrochemical Induced Direct C-H-Arylation

Iluminada Gallardo Sergio Soler

Universitat Autònoma de Barcelona, Departament de Química, barcelona, Spain, [email protected]

A large variety of bioactive molecules, ligands for homogenous catalysis and materials contain biarylic moieties. [1] The most widely used synthesis of these compounds are based on well-known transition metals mediated reactions. [2] Recently, organocatalytic and photochemical methods involving C-H bond activation of benzene using t-BuOK have added to the synthetic tools to produce biarylic compounds. For these reactions, radicals and anion-radical intermediates have been suggested. [3, 4] Electrosynthesis of biaryl motifs could be a cheaper and environmental-friendly process. Along this line, a systematic electrochemical study of several iodoarenes (I-C6H4-R, R = H, p-CN, o-NO2, m-NO2, p-NO2, p-CH3, p-OCH3 in DMF + 0.1 M TBABF4 and DMF: Benzene (2:8) + 0.6 M TBABF4) is presented here. When the reaction was carried out in pure DMF, p-iodobenzonitrile, iodobenzene, p-iodotoluene and p-iodoanisole show I-E curves corresponding to bielectronic processes (ECE mechanism). Controlled-potential electrolysis of these compounds leads to the formation of benzonitrile, benzene, toluene, and anisole, respectively. On the other hand, o-iodonitrobenzene, m-iodonitrobenzene and p-iodonitrobenzene show I-E curves corresponding to an EC mechanism, and nitrobenzene is the only product obtained by controlled-potential electrolysis in these cases. Therefore, the homocoupled product was never observed in these reactions. However, when a mixture of DMF: Benzene (2:8) was used as solvent, controlled-potential electrolysis of p-iodobenzonitrile and iodobenzene produced p-phenylbenzonitrile and benzonitrile (50:50) and biphenyl and benzene (50:50) respectively. For o-iodonitrobenzene, m-iodonitrobenzene and p-iodonitrobenzene, the corresponding phenylnitrobenzenes and nitrobenzene (25:75) were obtained, being the electron number in these cases equal to 1.2. Finally, electrolysis of p-iodotoluene and p-iodoanisole does not show the formation the corresponding cross-coupling product. These results show that the output of the reaction is very sensitive to the iodoarene substituent and they suggest that the anionic intermediate R-C6H4

- is the crucial intermediate. Acknowledgment Financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is acknowledged. References [1] McGlacken, G. P.; Bateman, L. M. Chem. Soc. Rev., 38, (2009), 2447. [2] Dyker, G. Handbook of CH transformations: Applications in organic synthesis;

Wiley-VCH, (2005). [3] Liu, W.; Cao, H.; Zhang, H.; Zhang, H.; Chung, K. H.; He, C.; Wang, H.; Kwong, F.

Y.; Lei, A. J. Am. Chem. Soc.,132, (2010), 16737. [4] Budén, M. E.; Guastavino, J. F.; Rossi, R. A. Org. Lett., 15, (2013) 1174.

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Electrochemical behaviour of Copper-based substrates for CO2 electroreduction in both aqueous and non-aqueous electrolytes.

Simonetta Palmasa, Laura Maisa, Pablo Ampudia Castresanaa, Annalisa Vaccaa, Michele

Masciaa, Francesca Ferrarab,

aUniversità degli studi di Cagliari, Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali, Cagliari, Italy, [email protected]

b Sotacarbo S.p.A., Carbonia, Italy

The concentration of carbon dioxide in the atmosphere is increased up to 400 mg/l over the last century. This high atmospheric CO2 concentration is related to severe environmental problems, such as global warming; in this context, decreasing the CO2 concentration is a critical issue for a sustainable development. The electroreduction of CO2 to valuable hydrocarbon products is a promising process that would create a significant impact to the global carbon balance by recycling waste CO2 into usable hydrocarbons. Actually, chemical reduction of carbon dioxide is thermodynamically feasible but only in the presence of strong reducing agents. In alternative, electroreduction of CO2 has been widely studied. The literature reports excellent overview of possible products obtained by electrochemical CO2 reduction, at different electrode materials and experimental conditions [1]. Researchers over the past three decades have identified several materials that are able to reduce CO2 electrochemically in aqueous solutions, but these materials are not efficient and stable enough for practical use. A copper electrode was found to perform the direct reduction of CO2 to hydrocarbons (methane and ethylene) with a reasonable current density and current efficiency [2]. Achieving efficient Cu-catalyzed CO2 reduction requires preparing Cu particles whose surfaces have active sites that are different from those on the surface of a polycrystalline Cu electrode. In the present work, the electrochemical behaviour of Copper-based electrodes has been studied in both aqueous and non-aqueous solutions containing CO2. The copper-based electrodes were prepared by electrodeposition of either Cu or Cu2O/CuO using different solutions, as CuSO4 (0.1 M) or CuSO4 (0.1 M) in lactic acid. The electrodeposition was performed using different substrates, such as boron doped diamond (BDD) or 3D nanostructures (TiO2 nanotubes). The morphology of the obtained samples was investigated by scanning electron microscopy analysis. Experiments were carried out in an electrochemical cell, in which either a bicarbonate solution (0.1 M) or an organic solution were employed. Cyclic voltammograms were recorded in both presence and absence of CO2: a different behaviour can be observed in the saturated solution. The activity of the working electrode was studied in controlled potential electrolyses performed in CO2 saturated electrolyte. References [1] G. Magesh, E.S. Kim, H.J. Kang, M. Banu, J.Y. Kim, J.H. Kimb and J.S. Lee, Journal of Materials Chemistry A, 2, (2014), 2044-2049 [2] P. Hirunsit, W. Soodsawang and J.Limtrakul, The Journal of Physical Chemistry C, 119, (2015), 8238-8249

O23 _____________________________________________________________________________________


Development of Air-Diffusion Cathodes for Electrochemical Water Treatment: From Synthesis to Use

Carlota Ridruejoa, Francisco Alcaideb, Garbiñe Álvarezb, Enric Brillasa, Ignasi Sirésa

aUniversitat de Barcelona, Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Barcelona, Spain,

[email protected], [email protected], [email protected] bIK4-CIDETEC, Energy Division, San Sebastián, Spain, [email protected]

The electrochemical advanced oxidation processes (EAOPs) based on Fenton’s reaction are very powerful technologies for the removal of organic pollutants from wastewater, being the industrial effluents at acidic or near-neutral pH a particularly interesting niche market in years to come. However, at present the performance of electro-Fenton (EF) and photoelectro-Fenton (PEF) processes is partly limited by the non-optimal characteristics of commercial gas-diffusion electrodes that are currently employed for the in situ H2O2 electrogeneration. Indeed, such electrodes are not usually optimized, regarding their durability and stability for specific experimental conditions. In this work, various air-diffusion cathodes have been developed and characterized by using carbon-based materials, like carbon nanotubes, graphene and carbon nanofibers, more chemically stable than carbon and acetylene blacks conventionally used in such electrodes. Modification with quinones and transition metals has been addressed aiming to improve their activity towards H2O2 electrogeneration. The electrochemical characterization of thin-film model and practical air-diffusion electrodes towards O2 reduction reaction has been carried out in a three-electrode cell, under experimental conditions relevant to those found in real wastewater treatment, namely acidic pH and presence of characteristic anions. Furthermore, the H2O2 electrogeneration in a small undivided tank reactor was studied in such media to treat the anesthetic pharmaceutical tetracaine by EF and PEF in the presence and absence of active chlorine electrogenerated at the anode surface. On the other hand, the best synthesized cathodes were scale-up and fitted in a parallel-plate flow reactor to treat up to 2.5 or 10 L of contaminated solutions. From the results obtained, the solar PEF process is envisaged as a good alternative for the treatment of real industrial wastewater, which is currently under study. Acknowledgments Financial support from projects CTQ2013-48897-C2-1-R and CTQ2013-48897-C2-2-R (MINECO/FEDER, EU), as well as from excellence network E3TECH under project CTQ2015-71650-RDT (MINECO, Spain) and from the FPI grant awarded to C. Ridruejo (MINECO, Spain) is acknowledged.

O24 _____________________________________________________________________________________


Investigation of an Electrochemical Process for the Conversion of Carbon Dioxide to Higher Value Products

Simona Sabatino, Adriana D’Angelo, Alessandro Galia, Federica Proietto, Gianluca Lo

Nero, Benedetto Schiavo, Onofrio Scialdone

Università degli Studi di Palermo, Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Palermo, Italy, [email protected]

The electrochemical reduction of carbon dioxide is considered a relevant topic for both the synthesis of chemicals and the decrease of global warming. Electrochemical processes could utilize excess energy from intermittent renewable sources to convert carbon dioxide in various products such as CO, formate and formic acid, methane and ethylene in water and oxalic acid, formic acid, CO as well as carboxylic acids (by reaction with suitable reagents such as aromatic ketones or benzylic halides) in aprotic solvents [1-4]. It has been shown that the selectivity of the process dramatically depends on the nature of the cathode. In the last years, an increasing attention has been devoted to the conversion of carbon dioxide to formic acid in water. In particular, it has been shown that the utilization of cheap tin cathodes allow the production of formic acid with good Faradic Efficiencies (FE) [5-6], even higher under suitable operating conditions than that obtained at lead cathode. In the present work the electrochemical reduction of CO2 to formic Acid at tin cathode was studied in both divided and undivided cells in order to evaluate the performances of the process. The effect of some operating parameters, including the working potential and the nature of supporting electrolyte and cathode, on both the cathodic reduction of CO2 and the anodic oxidation of formic acid was investigated in a divided cell. The reduction of carbon dioxide was also performed in an undivided cell with the aim of studying the effect on the generation of formic acid of various operating parameters such as current density, cathode to anode area ratio, mixing rate, nature of the anode and of the supporting electrolyte. A detailed investigation on the effect of the carbon dioxide pressure was also carried out. References [1] G. Centi, S. Perathoner, Stud. Surf. Sci. Catal., 153, (2004), 1–8. [2] H.M. Jhong, S. Ma, P.J. Kenis, Current Opinion in Chem. Engin., 2, (2013), 191-

199; [3] M. Azuma, et al., J. Electrochem. Soc., 137, (1990), 1772-1778. [4] S. Ikeda, T. Takagi, K. Ito, Bull. Chem. Soc. Jpn., 60, (1987), 2517. [5] P. Bumroongsakulsawat, G.H. Kelsall, Electrochim. Acta, 141, (2014), 216 – 225. [6] O. Scialdone, et al., Electrochimica Acta, 199, (2016), 332-341.

O25 _____________________________________________________________________________________


Removal of Perfluorohexanoic Acid (PFHxA) from Industrial Effluents by Nanofiltration Followed by Electrochemical Oxidation of

the NF Concentrate

Álvaro Soriano, Daniel Gorri, Ane Urtiaga

Universidad de Cantabria, Departamento de Ingenierías Química y Biomolecular, Santander, Spain, [email protected]

Perfluorinated chemicals (PFCs) are highly persistant organic compounds that are released to the environment from various industrial activities as well as from different consumer goods. The concern about their potential health risks is leading to the inclusion of PFCs in several environmental regulations [1,2]. Perfluorinated compounds have gained the reputation of being refractory to degradation, due to the strength of the C-F bond. However, we have recently demonstrated that electrooxidation by means of boron doped diamond anodes allows to achieve the complete mineralization of perflurooctanoic acid [3,4].

This work evaluates the use of membrane technology coupled to electrochemical oxidation (ELOX) for the removal of perfluorohexanoic acid (PFHxA) present in real industrial effluents. In the nanofiltration unit, the organic compound is retained in the concentrate stream, together with the dissolved salts that will act as electrolyte in the electro-oxidation step [5]. The electro-oxidation experiments were carried out under galvanostatic conditions using an electrochemical cell consisting of two parallel flow-by compartments made of a central bipolar p-Si/BDD anode and two BDD cathodes. The coupling of these two technologies (NF and ELOX) leads to an integrated process that is more effective in removing pollutants and more efficient in terms of energy consumption per volume of water treated. The influence of the main operating variables on the process performance was assessed: 1) the effect of the effective fluid pressure on the permeate flux and rejection of PFHxA and salts; 2) the effect of current density in the kinetics of PFHxA degradation by electro-oxidation. The electrochemical tests were initially conducted using model aqueous solutions, in order to select the most appropriate current density value, following a criterion of minimization of the energy consumption, and finally validated for the treatment of the industrial effluents. Acknowledgment This research was supported by the project CTM2013-44081-R (MINECO, SPAIN-FEDER 2014–2020). Funding from the Spanish excellence network E3TECH (reference CTQ2015-71650-RDT, MINECO) for the attendance to the 2nd E3 Mediterranean Symposium: Electrochemistry for Environment and Energy is also acknowledged. References [1] Directive 2013/39/EU, Off. J. Eur. Union, L 226/1, (2013), 1-17. [2] Stockholm Convention Secretariat, Decision SC-4/17, (2009), 1-4. [3] A. Urtiaga, et al., Chemosphere, 129, (2015), 20-26. [4] C.E. Schaefer, et al., J. Hazard. Mater., 295, (2015), 170-175. [5] A. Urtiaga, G. Pérez, R. Ibáñez, I. Ortiz, Desalination, 331, (2013), 23-34.

O26 _____________________________________________________________________________________


Electrochemical Removal of Methyl Paraben using Different Anodes and Aqueous Matrices

Juliana R. Steter, Enric Brillas, Ignasi Sirés

Universitat de Barcelona, Laboratori d’Electroquímica dels Materials i del Medi

Ambient, Departament de Química Física, Facultat de Química, Barcelona, Spain, [email protected], [email protected], [email protected]

Parabens are characterized by their large stability, liposolubility and hydrophilicity, which promote their facile absorption by inhalation, ingestion or topical application of manufactured products, as well as their efficient dispersion and bioaccumulation in the environment [1]. As a result, concerns have been raised about their role as endocrine disruptors and their association with the occurrence of human cancers. Several technologies have been proposed for their removal from water, although further studies are required to fully optimize the treatments. This work addresses the degradation of aqueous solutions of methyl paraben (MP) at pH 3.0 by three electrochemical processes, namely electro-oxidation with H2O2 electrogeneration (EO-H2O2), electro-Fenton (EF) and UVA photoelectro-Fenton (PEF). The electrochemical trials have been conducted in undivided, thermostated (35 ºC) tank reactors with 100 mL capacity equipped with an air-diffusion cathode (3 cm2) to electrogenerate H2O2 on site. All the electrolyses were made at constant current density in different aqueous media containing Na2SO4, NaCl or Na2SO4 + NaCl and 158 mg L-1 MP. The performance of the electrochemical processes using boron-doped diamond (BDD), Pt or two kinds of dimensionally stable anodes (DSA) has been compared from the analysis of mineralization profiles and decay kinetics. The use of BDD ensured the overall mineralization in all three processes according to the sequence: PEF > EF > EO-H2O2, thanks to the contribution of BDD(•OH). Pt and DSA became an interesting alternative in PEF, with slower organic matter removal but similar final mineralization percentages, being much less powerful than BDD in EO-H2O2. The presence of Cl− was beneficial in the latter process and yielded a much faster decay of MP. Conversely, it became significantly detrimental in EF due to the partial destruction of H2O2 and •OH in the bulk. The oxidation power of PEF was so high that similar decay kinetics was found in all media regardless of the anode, although the mineralization was decelerated owing to the accumulation of halogenated by-products. GC-MS and HPLC analysis allowed the identification of chlorinated and non-chlorinated aromatic MP derivatives. These molecules were gradually transformed into oxalic and formic acids, along with four chlorinated aliphatic carboxylic acids formed in Cl−-containing media. DSA Registered trademark of Industrie De Nora Spa

Acknowledgments Financial support from project CTQ2013-48897-C2-1-R (MINECO/FEDER, EU), as well as from excellence network E3TECH under project CTQ2015-71650-RDT (MINECO, Spain) is acknowledged. J. Ribeiro thanks funding from process N. 234142/2014-6 (CNPq, Brazil).

References [1] C. Haman, X. Dauchy, C. Rosin, J.-F. Munoz, Water Res., 68, (2015), 1-11.

O27 _____________________________________________________________________________________


Preparation of Novel Polymer Electrolytes Based on Poly(tetrafluoroethylene) and Ionic Liquids for Lithium Ion Batteries

Akiko Tsurumakia,b, Maria Assunta Navarraa, Hiroyuki Ohnob, Stefania Paneroa

a Sapienza University of Rome, Department of Chemistry, Rome Italy,

[email protected] (S. Panero) b Tokyo University of Agriculture and Technology, Functional Ionic Liquid

Laboratories and Department of Biotechnology, Tokyo, Japan.

Poly(tetrafluoroethylene) (PTFE) has been acknowledged as the most inert polymer owing to its low surface free energy. On the other hand, the inertness of PTFE restricts preparations of stable composites with liquid materials such as electrolyte solutions. There is a strong demand to design additive salts for fluorinated polymers. Ionic liquids (ILs), low-temperature molten salts, have been recognized as potential additive salts, because they are composed of only organic ions possessing structural diversity of ions. In this study, novel ILs having fluorophilic functions have been designed, and PTFE-based composites containing the ILs were evaluated in terms of a presence of repelled ILs and electrochemical properties. As a model compound of PTFE, perfluorohexane (C6F14) was used to analyze its solubility in various ILs using thermal gravimetric analysis. Non-functionalized ILs such as 1-ethyl-3-methylimidazolium bis(tri-fluoromethanesulfonyl)imide ([C2mim][Tf2N]) were found to dissolve C6F14 less than 26.0 mmol mol-1. The solubility was found to increase with increase in number and length of fluoroalkyl chain in ILs. For the case of trihexyl(heptadecafluoroundecyl) phosphonium [Tf2N] ([P666F][Tf 2N]), the solubility was improved to 420.5 mmol mol-1. Replacement of [Tf2N] anion to C8F17SO3 anion of this IL attained the highest fluorophilicity. Then, the composites were prepared by mixing PTFE powder and these ILs in ratio of 1:1 (w/w). ILs functionalized with fluoroalkyl chain(s) enable the preparation of homogeneous composites based on PTFE which did not accompany the bleed out of the ILs even after pressing with a pair of glasses, whereas [C2mim] salts were easily repelled from PTFE (Figure 1). The composites of PTFE and [P666F]-IL were proposed for electrochemical analysis, and a suitable ionic conductivity was found for the composites. Further electrochemical properties will be characterized and shown at the presentation. Acknowledgement A.T. acknowledge the HYDRO-ECO Research Center of Sapienza University of Rome for the support. A.T. and H.O. acknowledge a Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (KAKENHI).

Figure 1. Pictures of PTFE-IL composites pressed with two glass plates with 0.05 mm spacer.

O29 _____________________________________________________________________________________


Influence of Na2SO4 Concentration on the Abatement of Norfloxacin using BDD Electrodes

Salatiel W. da Silvaa,b, Emma M. Ortegaa, Andréa M. Bernardesb, Valentín P. Herranza

a Universitat Politècnica de València, Departamento de Ingeniería Química y Nuclear, E.T.S.I. Industriales, Valencia, Spain, [email protected]

b Universidade Federal do Rio Grande do Sul, Departamento de Materiais, Porto Alegre, Brazil

In this work, the influence of Na2SO4 concentration and the current density on the abatement of norfloxacin (NOR) using an electrolytic flow cell operating in batch recycle mode under galvanostatic conditions was studied. The cell was equipped with a boron-doped diamond (BDD) anode and a stainless steel cathode. 1 L of the electrolytic solution feed the reactor at a flow rate of 8.33 10-6 m³/s. The abatement of NOR was assessed by UV/Visible spectroscopy, chemical oxygen demand (COD) and pH was measured. The results of figure 1 show that the removal of NOR increased with the increase of Na2SO4 concentration, but the similar tendency of COD removal was not observed. The high-applied current and high-Na2SO4 concentration can favour mediated oxidation by sulphate radicals electro-generated from supporting electrolyte versus the oxidation by hydroxyl radicals electro-generated from water decomposition. The reaction rate showed a first order kinetics (inset graph), which not leads to the complete oxidation to CO2 but rather to more resistant by-product formation (figure 2). It is also important to note that an increase in current density for 1 A to 5 A does not enhance significantly the COD removal due to the occurrence of the oxygen evolution reaction and/or mass transport limitations. The results lead to conclude that the fast removal of NOR and low COD removal when use 1 N/L of Na2SO4 leads an intermediate formation, causing an increase in the pH values from 4 to ~10. In alkaline condition, the decomposition of hydroxyl radicals is more pronounced and the reaction of oxygen evolution is favoured which decreases the ability to remove the COD [1].

Acknowledgements. The authors thank CNPq, CAPES (Brasil) and the Spanish Ministry of Economy and Competitiveness for the financial support under the projects CTQ2015-65202-C2-1-R (MINECO/FEDER) and network E3TECH CTQ2015-71650-RDT (MINECO). References [1] L. Szpyrkowicz, et al., Ind. Eng. Chem. Res, 39, (2000), 3241–3248.

O29 _____________________________________________________________________________________


Semiconductor Structures for Hydrogen Peroxide Production on Photoelectrochemical Way

Tomasz Baran, Sandra Rondinini

a Università degli Studi di Milano, Department of Chemistry; INSTM Milano Unit, Milano, Italy, [email protected]

Photocatalytic production of hydrogen peroxide (H2O2) on semiconductor

materials with water or alcohol as the hydrogen source and molecular oxygen (O2) as the oxygen source has attracted much attention as a potential method for safe H2O2 synthesis as well as method of is situ hydrogen peroxide production for wastewater treatment, disinfection and industrial synthesis [1]. Several examples of titanium dioxide based materials has been reported in literature as an active materials for photocatalytic and photoelectrocatalytic H2O2 production [1–4]. In this work, a series of novel semiconducting nanomaterials has been prepared, characterized and tested. Among them, photosensitized copper iodide and titanium dioxide, transition metals titanates, tantanates and vanadates are particularly interesting. These materials has been selected based on analysis of their band structures and favorable potential of conduction and valence bands edges. Therefore, we examine the formation of H2O2 in the photocatalytic reactions under various reaction conditions and then elucidate the relationship between the photocatalytic activity and the H2O2 concentration. The most possible mechanism of H2O2 formation is based on reduction of oxygen by photogenerated electrons from the conduction band of the semiconductor. However, other mechanism like oxidation of water and other hydrogen donors are also considered. Acknowledgements Project is realized within Oronzio and Niccolò De Nora fellowship. References [1] Y. Shiraishi, S. Kanazawa, D. Tsukamoto, A. Shiro, Y. Sugano, T. Hirai, ACS Catal. 3, (2013), 2222–2227. [2] F. Shiraishi, T. Nakasako, Z. Hua, J. Phys. Chem. A, 107, (2003), 11072–11081. [3] T. Hirakawa, Y. Nosaka, J. Phys. Chem. C., 112, (2008), 15818–15823. [4] H. Goto, Y. Hanada, T. Ohno, M. Matsumura, J. Catal., 225, (2004), 223–229.

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Preparation of Ag-modified Ni Foams by Galvanic Displacement and their Use as Cathodes for the Reductive Dechlorination of Herbicides

Marco Musiania, Enrico Verlatoa, Wenyan Heb,c, Abdeltif Amranec, Simona Barisona,

Didier Flonerb, Florence Fourcadec, Florence Genesteb, Roberta Seragliaa,

ICMATE - CNR, Padova, Italy, [email protected] b. Université de Rennes 1, CNRS, UMR 6226, Equipe Matière Condensée et Systèmes

Electroactifs, Rennes, France c. Ecole Nationale Supérieure de Chimie de Rennes / Université de Rennes 1, CNRS,

UMR 6226, Rennes, France

Chloroacetanilides are a commonly used class of herbicides. Since they may pollute surface waters, they must be removed from the environment. Chloroacetanilides cannot be eliminated by direct biological treatment because they are biorecalcitrant and so a sequence of two steps is needed. An electrochemical pre-treatment converts chlorinated molecules to less toxic and more biodegradable intermediates that undergo complete mineralization in a subsequent biological treatment. The efficiency of both steps is crucial for the success of the overall process. Therefore, an active and reliable electrocatalyst is needed for the electrochemical dechlorination step. In this communication, we report on the preparation of Ag-modified Ni foam electrodes and their use as cathodes for the reductive dechlorination of AlachlorTM. Commercial Ni foams were modified through the spontaneous deposition of Ag nanoparticles. Ag was chosen because it is an effective catalyst for the cathodic reduction of the C-Cl bond. The Ag+ ion solutions employed in the galvanic displacement reactions contained complexing agents, like thiosulfate or thiocyanate. Foams with a regular distribution of Ag nanoparticles, with narrowly distributed dimensions, were obtained using thiosulfate solutions containing polyvinylpyrrolidone (PVP), a capping agent that influenced Ag morphology and growth kinetics. When used as cathodes for the reductive dechlorination of AlachlorTM, Ag-modified foams allowed extensive dechlorination, yielding deschloroalachlor as the only dechlorinated product. Minor amounts of reduction products still containing Cl were also formed. Ag-modified Ni foams were re-used in successive electrolyses, providing essentially identical performances.

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E3 2016, 14-16 September 2016 – Gargnano (Garda Lake), Italy 41

Poster Contributions

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C. Alegre Cost-effective Bifunctional Perovskite-Carbon Composite for the Oxygen Evolution and the Oxygen Reduction in Alkaline Environment

P1 p. 45

Y. Asensio Importance of the Cathodic Chamber Configuration in the Performance of Microbial Fuel Cells (MFC)

P2 p. 46

E. Bocos New Electroanalytical Approaches for Monitoring of Electroactive Dyes

P3 p. 47

S. Calcaterra An Innovative Green Tri-material negative Electrode Based on Li 3V1.95Ni0.05(PO4)3/C, Li4Ti5O12 and Activated Carbon for Li-ion Supercapacitors

P4 p. 48

A. D'Angelo Study of thermally regenerative ammonia-based batteries (TRABs) P5 p. 49

A. Diez Advantages of Electro-Fenton Process over Current Trend Treatments in the Degradation of Emerging Pollutants

P6 p. 50

T. Dolla Mesoporous MnxNiyCo3-x-yO4 and Their Composites with Multiwalled Carbon Nanotubes as Anode Materials for Li-ion Batteries

P7 p. 51

R.M. Fernandez Domene

Electrochemical Characterization of Iron Based Photoelectrodes obtained by Anodization under Hydrodynamic Conditions

P8 p. 52

R.M. Fernandez Domene

Polycondensation of WO3 Nanostructures by Anodizing Tungsten in the Presence of Complexing Agents

P9 p. 53

J. Lobato Preparation and Characterization of PtCo Alloys on Novel non Carbonaceous Support for Electrodes in High Temperature PEMFCs

P10 p. 54

G. Longoni Effect of Crystalline Faces Exposure on Na+ Uptake Mechanism in Anatase TiO2 Nanocrystals for Energy Storage

P11 p. 55

S. Mateo Influence of the Anodic Material in the Performance of a Microbial Fuel Cell

P12 p. 56

J. Nair Graphene-based Materials as Electrode Constituents of Energy Storage Devices

P13 p. 57

F. Orts Electrochemical Treatment of Real Textile Wastewater: Tricromy Procion HEXL

P14 p. 58

M. Panizza Electrochemical Oxidation of Synthetic Dyes Using BDD Anode With Solid Polymer Electrolyte

P15 p. 59

M. Pazos Regeneration and Recovery of Adsorbents by Electrochemical Advanced Oxidation Process

P16 p. 60

M. Pazos Comprehensive Solution for the Treatment of Wastewater: Combined Electro-Fenton and Adsorption Process

P17 p. 61

J.F. Perez The Role of Hydrogen Peroxide in the Electrochemical Synthesis of Peroxyacetic acid

P18 p. 62

V. Perez-Herranz Modification of Porous Nickel Electrodes With Silver Nanoparticles for Hydrogen Production

P19 p. 63

M. Renzi Coupled System of Modified Membrane and Modified Cathode for Efficient PEM-FC

P20 p. 64

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M. Rodrigo Electro-bioremediation of Oxyfluorfen Polluted Soils with Periodic Polarity Reversal Strategy

P21 p. 65

M. Rodrigo Analysis of a RFB as Renewable Energy Storage System P22 p. 66

J. Rodriguez-Ruis Fabrication of a Sediment Microbial Fuel Cell using vermicomposting of urban green waste

P23 p. 67

S. Rondinini The Pseudo-Capacitive Reaction in Electrodeposited Highly Hydrated Amorphous Iridium Oxide by operando Energy Dispersive XAS Investigation

P24 p. 68

S. Sabatino Electrochemical abatement of organic pollutants in continuous using microfluidic reactors in series

P25 p. 69

C. Saez Development of Concentration Strategies for the Improved Removal of Pesticides

P26 p. 70

S. Salima Use of the Electrochemical Impedance in the Study of the Inhibition Corrosion of the carbon steel

P27 p. 71

A. Sanroman Soil Flushing by Application of Low Intensity Current: A Solution for in situ Remediation of Hydrocarbons Polluted Soils

P28 p. 72

A. Sanroman Evaluation of Cathode Material and Configuration to Enhance the Electro-Fenton Process

P29 p. 73

E. Sechi Preparation of Polyaniline/Porous Silicon Hybrids for photovoltaic applications

P30 p. 74

N. Sires Preparation, Characterization and Use of an IrO2-based DSA for the Electrochemical Removal of Dyes from Water

P31 p. 75

G. Sotgiu Nanostructured TiO2 Substrate: Influence on the Electrocatalytic Properties of Manganese Oxide Based Electrodes in the Anodic Oxidation of Organic Pollutants

P32 p. 76

A. Urtiaga Electrochemical Performance of an Innovate Water Treatment Technology in Aquaculture: ELOXIRAS

P33 p. 77

E. Valles New Electrochemical Medium for Synthesizing Highly Mesoporous Pt and CoPt3 Nanorods useful as Catalysts for Ethanol Electro-oxidation

P34 p. 78

A. Visibile Cavity Micro Electrodes (C-MEs) & SECM (Scanning ElectroChemical Microscopy) for the Investigation of Photoactive Semiconductor Materials and the Evaluation of Photodegradation Process during PEC_WS.

P35 p. 79

S. Zignani The Effect of Operating Temperature and Cell Configuration on the Performance of Ethanol Fuel Cells

P36 p. 80

P1 _____________________________________________________________________________________


Cost-effective Bifunctional Perovskite-Carbon Composite for the Oxygen Evolution and the Oxygen Reduction in Alkaline Environment

Cinthia Alegre, Esterina Modica, Antonino S. Aricò, Vincenzo Baglio

Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano” (CNR), Messina,

Italy, [email protected]

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are very important processes in different energy conversion devices such as fuel cells, electrolysers, unitized reversible fuel cells and metal-air batteries. In particular, in the latter two systems, both reactions occur on the same electrode during the charge and discharge processes. Such an electrode is called “bi-functional” oxygen electrode and should contain good electro-catalysts for both the oxidation and reduction reactions of oxygen. Furthermore, this electrode should be chemically stable over the wide range of potentials experienced during both processes. Although noble metal catalysts have proved to be effective as oxygen-electrode [1], the high costs and limited reserves in the world hinder their practical application. Recently developed perovskites have shown better activities for OER in alkaline medium of the catalysts based on noble metals. The ORR is the limiting step for this class of non-noble-metals [2–4].

In the present work, a perovskite, namely La0.6Sr0.4Fe0.8Co0.2O3 (LSFCO) was mixed with a carbon material and investigated for operation as both oxygen reduction (ORR) and oxygen evolution (OER) catalyst. The catalyst was investigated in half-cell by using a three-electrode configuration, in alkaline solution at ambient temperature, and compared to a Pd/C catalyst. LSFCO was less active for the ORR, while the performance for the OER was better compared to Pd. In order to get information on the stability, oxygen evolution polarizations were carried out up to 2 V vs. RHE. This may be considered an accelerated stress test since a high electrochemical potential promotes electrocatalyst degradation. The LSFCO-based catalyst showed a more stable behaviour compared to the noble metal catalyst. Acknowledgments The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2012-2015) under the call GC.NMP.2012-1; NECOBAUT Project n° 314159 and from the “Accordo di Programma CNR-MiSE, Gruppo tematico Sistema Elettrico Nazionale – Progetto: Sistemi elettrochimici per l’accumulo di energia” for the financial support”. References [1] C. Alegre, A. Stassi, E. Modica, C. Lo Vecchio, A.S. Aricò, V. Baglio, RSC Adv. 5, (2015), 25424–25427. [2] D. Chen, C. Chen, Z.M. Baiyee, Z. Shao, F. Ciucci, Chem. Rev., 115, (2015), 9869–921. [3] S. Hameer, J.L. van Niekerk, Int. J. Energy Res., 39, (2015), 1179–1195. [4] Z.-L. Wang, D. Xu, J.-J. Xu, X.-B. Zhang, Chem. Soc. Rev., 43, (2014), 7746–86.

P2 _____________________________________________________________________________________


Importance of the Cathodic Chamber Configuration in the Performance of Microbial Fuel Cells (MFC)

Yeray Asensio, Sara Mateo, Carmen M. Fernández-Marchante, Francisco J. Fernández,

Pablo Cañizares, Justo Lobato, Manuel.A. Rodrigo

University of Castilla-La Mancha, Department of Chemical Engineering, Faculty of Chemical Sciences and Technologies, Ciudad Real, Spain, [email protected]

In the recent years, Microbial fuel cells (MFC) have attracted special interest because of their promising application. Although the most exciting and widely studied reactions are those happening on the anode (because they involved microorganisms), the cathode of the MFC is also a very important component (despite being a simpler abiotic system) and it may help to obtain a good performance of the MFC device [1]. Taking into account this expected importance of the cathode, this work compares the performance of two MFC equipped with very different types of cathodes. These cells were prepared with the same anode materials and fed with the same fuel. One of the MFC was a conventional two-compartment cell divided using an ion-exchange membrane. In this device, the cathode compartment was connected to a water reservoir and a peristaltic pump was used to circulate a HCl solution (pH 3) from the reservoir to the cathode chamber, while a fishery compressor was connected to supply oxygen in this reservoir. The other cell was an air-breathing cell. This MFC used Toray carbon paper with a catalytic layer of 0,5 mg Pt cm-2 as cathode electrode. In this case, the cathodic chamber was open to the atmosphere so the oxygen employed was taken directly from air.

Results show that both cathodic configurations were suitable for organic matter removal and electricity production, although the air-breathing technology is able to achieve higher values of current density (5.4 A m-2) with respect to conventional MFC (4.5 A m-

2). Experiments were carried out during three months and both MFC showed operational stability, reflecting the robustness of the MFC technology regarding the cathode used. Acknowledgements Financial support from Spanish Ministry of Economy and Competitiveness (MINECO) through project SUNLIVINGENERGY (CTQ2013-49748-EXP, Explora Program) is gratefully acknowledged. In addition, financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is acknowledged. References [1] B.E. Logan, B. Hamelers, R. Rozendal, U. Schröder, J. Keller, S. Freguia, P. Aelterman, W. Verstraete, K. Rabaey, Environmental Science and Technology, 40, (2006), 5181-5192.

P3 _____________________________________________________________________________________


New Electroanalytical Approaches for Monitoring of Electroactive Dyes

Bakhta Bouzayania,c, Elvira Bocosa, Sourour Chaâbane Elaoudc, Elisa González-

Romerob, Marta Pazosa, M. Ángeles Sanromána aUniversity of Vigo, Department of Chemical Engineering, Vigo, Spain,

[email protected] b University of Vigo, Department of Analytical and Food Chemistry, Vigo, Spain,

c University of Sfax, Department of Chemical, Sfax, Tunisia.

Synthetic dyes are extensively used worldwide in a wide variety of applications. Approximately, 10,000 different types are produced annually, discharging a high percentage of this production into the water streams. These compounds pass unscathed through the aquatic environments given their high resistance to abrasion, chemical and bacterial attack. Once there, their presence entails an important risk for the welfare of living organisms, since they cause eutrophication and color and odor alteration. For instance, Reactive Black 5 is an electroactive compound derivate of H-acid, which cannot be effectively degraded by conventional or biological processes. During the last years, substantial research has been published with the objective of finding alternative treatment technologies. Among them, Electrochemical Advanced Oxidation Processes (EAOPs) have shown great ability to eliminate many kinds of hazardous pollutants like dyes. In these processes, highly reactive species such as •OH are generated and can quickly attack the saturated aromatic rings of organic compounds achieving their complete elimination. Among EAOPs, electro-Fenton technology, which involves the in situ electrogeneration of H2O2 and its reaction with Fe2+ to form •OH, is the most popular and has been used for the elimination of Reactive Black 5 [1]. Despite electro-Fenton technology is very effective on the elimination of a wide number of pollutants, monitoring and analysis take much time and usually it is difficult to follow the evolution of the degradation products produced during treatment. In this context, this work aims to evaluate the capacity of a new electroanalytical methodology on the monitoring of the elimination of Reactive Black 5 and its intermediates during electro-Fenton process. With this purpose, an original idea has arisen; the use of Screen-Printed electrodes as transducer in the in situ detection of reactants and intermediates by Linear Sweep Voltammetry (staircase mode). Likewise, the system was able to give selective information about the degradation of Reactive Black 5 and the evolution of the electroactive products generated in the treatment. Finally, the formation of aromatic/cyclic organic intermediates, and evolution of carboxylic acids, as well as the inorganic ions released during the treatment were monitored by GC/MS, HPLC, IC, respectively.

Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT, CTQ2015-71955-REDT and GRC 2013/003). The authors would like to thank to University of Sfax for the grant of B. Bouzayani and MINECO for financial support of E. Bocos under FPI program and M. Pazos under Ramón y Cajal program.

References [1] E. Bocos, et al., J. Chem.Technol. Biotech., 88, (2014),1235-42.

P4 _____________________________________________________________________________________


An Innovative Green Tri-material negative Electrode Based on Li3V1.95Ni0.05(PO4)3/C, Li4Ti5O12 and Activated Carbon

for Li-ion Supercapacitors

Silvia Calcaterraa,b, Marco Secchiarolia, Roberto Marassib, Margret Wohlfahrt-Mehrensa, Sonia Dsokea

aZentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg, Ulm, Germany, [email protected]

bCamerino University, School of Science and Technology, Chemistry Division, Camerino, Italy, [email protected]

Li-ion supercapacitors combine the high specific energy of Li-ion batteries (LiBs) with the high specific power of capacitors (EDLCs) to obtain a device with higher power densities than LiBs and higher energy densities than EDLCs [1,2,3]. Li4Ti5O12 (LTO) is a good candidate as negative electrode for this technology, but due to its low electronic conductivity (<10-13 S cm-1) and poor Li+ diffusion coefficient (between 10-8-10-13 cm2 s-1) its power ability is limited [4]. In order to diminish these intrinsic drawbacks of LTO, high amounts of activated carbon (AC) have to be added leading to a decrease of energy density in the final device. A valid solution to increase the energy density of LTO-AC bi-material negative electrode is to substitute a portion of AC with a high energy and high power Li-insertion-type material, like Li3V2(PO4)3/C (LVP/C) [5]. This study describes the development of a novel Na-alginate tri-material negative electrode consisting of Li3V1.95Ni0.05(PO4)3/C (LVNP/C) [6], LTO and AC for high energy and high power Li-ion supercapitors. This hybrid electrode exploits the advantage of using LVNP/C and LTO, which work at different potentials, between 1.5-3.0 V vs. Li+/Li, and exhibits excellent electrochemical performances thank to the high affinity between AC and Na-alginate [7]. Several compositions have been investigated and the most promising one, in terms of rate capability and cycling stability, is the electrode with a ratio LVNP/C:LTO:AC of 24:51:24. This composite electrode has been tested in a full cell with a Na-alginate-based AC positive electrode from 0.05 to 10 A g-1. The cell voltage, in LiPF6/EC:DMC (1:1) as electrolyte, is 2.6 V. The specific energy and specific power, together with the cycle life of this complete system have been compared with standard symmetric AC//AC, LTO//AC and LTO-AC//AC devices. References [1] G.G. Amatucci, F. Badway, A.D. Pasquier, T. Zheng, J. Electrochem. Soc., 148, (2001) ,A930–A939. [2] D. Cericola, P. Novák, A. Wokaun, R. Kötz, J. Power Sources, 196, (2011), 1035-10313. [3] H.S. Choi, J.H. Im, T. Kim, J.H. Park, C.R. Park, J. Mater. Chem., 22, (2012), 16986-16993. [4] N. Takami, K. Hoshina, H. Inagaki, J. Electrochem. Soc., 158, (2011), A725-A730. [5] X. Zhang, R.-S. Kühnel, M. Schroeder, A. Balducci, J. Mater. Chem. A, 2, (2014), 17906-17913. [6] M. Secchiaroli, G. Giuli, B. Fuchs, R. Marassi, M.Wohlfahrt-Mehrens, S. Dsoke, J. Material Chem. A, 3, (2015), 11807-11816. [7] M. Yamagata, S. Ikebe, K. Soeda, M.Ishikawa, RSC Adv., 3, (2013), 1037–1040.

P5 _____________________________________________________________________________________


Study of thermally regenerative ammonia-based batteries (TRABs)

Adriana D’Angelo, Simona Sabatino, Onofrio Scialdone, Alessandro Galia

aUniversità degli Studi di Palermo, Dipartimento di Ingegneria Chimica, Gestionale,

Informatica, Meccanica, Palermo, Italy e-mail: [email protected]

There are many different energy techniques such as solar, wind, hydroelectric but they have the main problem to transfer these forms of energy into usable electric batteries without losing energy as heat. It was recently proposed to create regenerating batteries that capture low-grade waste heat using ammonia [1,2]. In a typical TRAB, anode and cathode are constructed by copper metal immersed in a water solution separated by an anionic exchange membrane (fig. 1). Both compartments are filled with ammonia and copper nitrate. The only difference is the presence of NH3 in the anodic compartment (necessary for charge the battery). The battery works until the reaction uses up the ammonia needed for the complex formation in the anode compartment. The technology involves the distillation of ammonia with waste heat. In the next cycle the electrodic chamber are switched: the anode becomes the cathode and conversely.

Figure 1. Simple scheme of the cell used to study the thermally regenerative ammonia

batteries.

An investigation on the effect of numerous parameters (such as the concentration of ammonia, Cu(II), pH, cell geometry, nature of membrane) on the process was investigated. References [1] F. Zhang, J. Liu, W. Yang, B.E. Logan, Energy Environ. Sci, 8, (2015), 343-349. [2] F. Zhang, N. La Barge, W. Yang, J. Liu, B.E. Logan, ChemSusChem, 8, (2015), 1043-1048.

P6 _____________________________________________________________________________________


Advantages of Electro-Fenton Process over Current Trend Treatments in the Degradation of Emerging Pollutants

Aida Díez, Marta Pazos, Maria Angeles Sanromán

University of Vigo, Department of Chemical Engineering, Vigo, Spain, [email protected] The ionic liquids are salts with low melting points which are being using as an alternative to the traditional solvents due to their better qualities such as low volatility and high thermal and chemical stabilities. However, these characteristics make them an environmental problem, as ionic liquids are difficult to treat with the conventional degradation techniques. Advanced Oxidation Processes (AOPs) could be a solution, as they are reported as a promising way of mineralizing recalcitrant compounds [1]. The AOPs are based on the generation of powerful reactive species, capable of oxidizing a wide range of organic compounds [2]. Up to now, only few studies have reported the application of AOPs to the elimination of ionic liquid from water. In this study, the degradation of the ionic liquid, 1-butyl-2,3-dimethylimidazolium chloride (100 mg/L), was carried out under different AOPs such as Fenton, Photo-Fenton and Electro-Fenton processes. The removal of the ionic liquid was evaluated by liquid and ionic chromatography and the mineralization of the pollutant was followed by the measure of total organic carbon. The results demonstrated that Photo-Fenton and Electro-Fenton processes can achieved the total removal of the ionic liquid after 120 minutes. However, complete mineralization required a longer treatment time because after 6 hours only 84% of total organic carbon reduction was reached. Based on the economical point of view and the degradation levels, Electro-Fenton process seems to be the best technology for the treatment of ionic liquid. To determine the toxicity of the end solutions, ecotoxicity assays with the bacterium Vibrio fischeri were performed. Finally, mineralization pathways for the degradation of ionic liquid was proposed based on the identification of the degradation products and cations released along the different treatments and determined by GC/MS and ion-exclusion HPLC. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT and GRC 2013/003). The authors are grateful to MINECO for the financial support of Aida Díez under FPI program and Marta Pazos under Ramón y Cajal program. References [1] F. Lelario, M. Brienza, S.A. Bufo, L. Scrano. J. Photochem. Photobiol. A,. 321, (2016), 187-201. [2] E. Rosales, M. Pazos, M. A. Sanromán, M.A. Chem. Eng. Technol., 35, (2012), 609-617.

P7 _____________________________________________________________________________________


Mesoporous MnxNiyCo3-x-yO4 and Their Composites with Multiwalled Carbon Nanotubes as Anode Materials for Li-ion Batteries

Tarekegn Heliso Dolla, Patrick Ndungu

University of Johannesburg, Department of Applied Chemistry, Doornfontein,

Johannesburg, South Africa, [email protected]

This study aims at investigating crystal structure and electrochemical performance of MnxNiyCo3-x-yO4 and their composite with multi wall carbon nanotubes (MWCNTs) with different non-stochiometries (0≤x,y≤1) by varying x and y. Currently, MnxNiyCo3-

x-yO4 (0≤x,y≤1) with different non-stochiometries and their composites with MWCNT were synthesized using citric acid precursor method. The effects of substituting Co with different amounts of Mn and Ni on the crystal structure have been investigated to some extent and the effect on electrochemical performance will be investigated soon. The composites with multiwall carbon nanotubes have also been synthesized using the same method for MnxNiyCo3-x-yO4. The XRD pattern has shown that there is no siginifacnt change in the peak position of the mixed oxides due to the addition of the MWCNT. Detailed XRD, retiveld refinement, cyclic voltammetry and galvanostatic charging and discharging will be done to fully understand the crystal structure and electrochemical performance of the mixed oxides and their composite. References [1] Zhao, Hu, Lei Liu, Zhongbo Hu, Limei Sun, Songbai Han, Yuntao Liu, Dongfeng

Chen, Xiangfeng Liu, Materials Research Bulletin, 77, (2016), 265-270. [2] Song, Xiong, Qiang Ru, Yudi Mo, Lingyun Guo, Shejun Hu, Bonan An, J. Power

Sources, 269, (2014), 795-803. [3] Yuan, Changzhou, Hao Bin Wu, Yi Xie, and Xiong Wen David Lou, Angewandte

Chemie International Edition, 53, (2014), 1488-1504. [4] Wu, Fangfang, Jing Bai, Jinkui Feng, Shenglin Xiong, Nanoscale, 41, (2015),

17211-17230.

P8 _____________________________________________________________________________________


Electrochemical Characterization of Iron Based Photoelectrodes obtained by Anodization under Hydrodynamic Conditions

Bianca Lucas-Granados, Rita Sánchez-Tovar, Ramon M. Fernández-Domene, José

García-Antón

Universitat Politècnica de Valènci,a Ingeniería Electroquímica y Corrosión, Instituto Universitario de Seguridad Industrial, Radiofísica y Medioambiental, Valencia, Spain,

[email protected] Iron oxide has become an interesting material for obtaining nanostructures for being used as photocatalysts in different applications such as environmental processes and energy production [1, 2]. In this study, electrochemical anodization under different controlled hydrodynamic conditions (electrode rotation speeds) is carried out in order to obtain different nanostructures. The obtained nanostructures are characterized by different electrochemical techniques such as photocurrent density vs. potential measurements (photoelectrochemical water splitting), Mott-Schottky analysis and Electrochemical Impedance Spectroscopy. Fig. 1 shows the water splitting results for the different obtained nanostructures at electrode rotation speeds of 0, 1000, 2000 and 3000 rpm.

Figure 1. Photocurrent density vs. applied potential results obtained under chopped simulated light 1.5 AM illumination in 1 M KOH for the nanostructures synthesized at 0, 1000, 2000 and 3000 rpm. The results show that the nanostructure obtained with an electrode rotation speed of 1000 rpm during anodization achieves the best results in the photoelectrochemical water splitting measurements. This in turn implies that this nanostructure is an efficient photocatalyst for being used in applications such as environmental processes and energy production. Acknowledgments The authors thank for the financial support granted by Ministerio de Economía y Competitividad (Reference: BES-2014-068713, Project Code: CTQ2013-42494-R), for the co-finance by the European Social Fund and for the financial support from the Spanish excellence network E3TECH funded by the Ministerio de Economía y Competitividad (MINECO) under project CTQ2015-71650-RDT. References [1] T. Mushove, T. M. Breault, L. T. Thompson, Ind. Eng. Chemi. Res., 54, (2015), 4285-4292. [2] Z. Zhang, et al., Applied Catalysis B: Environmental, 95, (2010), 423-429.

P9 _____________________________________________________________________________________


Polycondensation of WO3 Nanostructures by Anodizing Tungsten in the Presence of Complexing Agents

Ramon M. Fernández-Domene, Rita Sánchez-Tovar, Bianca Lucas-Granados, José

García-Antón

Universitat Politècnica de València, Ingeniería Electroquímica y Corrosión, Instituto Universitario de Seguridad Industrial, Radiofísica y Medioambiental, Valencia, Spain

*[email protected]

Hydrogen is widely regarded as a potential future energy carrier that could be cleanly extracted from water and used subsequently for electricity production. Water photoelectrolysis, or water splitting, represents one of the most promising ways of solar hydrogen generation. WO3, synthesized in nanostructured form, is an attractive photoanode material due to its good properties. In this work, the influence of complexing agents (such as fluoride or oxalate ions) on the polycondensation of hydrated WO3 nanostructures has been investigated. Anodization of tungsten has been carried out in different acidic electrolytes, at 50 ºC for 4 hours, under controlled hydrodynamic conditions (375 rpm) by using a rotating electrode configuration. After anodization, samples were annealed at 400 ºC in presence of oxygen for 4 hours. Figure 1 shows two FE-SEM images of the nanostructures formed in the presence of fluoride anions (0.1 M and 0.25 M). It can be observed that regardless of the fluoride concentration, nanoplatelets arranged in a tree-like fashion are formed. However, at high concentrations (0.25 M), the density of nanoplatelets is significantly reduced (Figure 1b). This fact is a consequence of the ability of complexing ions to form bondings with tungsten of higher strength than O2- ions, hence reducing polycondensation of mono and polymeric tungsten species.

Figure 1. FE-SEM images of the WO3 nanoplatelets formed in the presence of 0.1 M NaF (a) and 0.25 M NaF.

Acknowledgments The authors thank for the financial support granted by Ministerio de Economía y Competitividad (Reference: BES-2014-068713, Project Code: CTQ2013-42494-R), for the co-finance by the European Social Fund and for the financial support from the Spanish excellence network E3TECH funded by the Ministerio de Economía y Competitividad (MINECO) under project CTQ2015-71650-RDT.

P10 _____________________________________________________________________________________


Preparation and Characterization of PtCo Alloys on Novel non Carbonaceous Support for Electrodes in High Temperature PEMFCs

Justo Lobato, María Millán, Hector Zamora, Pablo Cañizares, Manuel A. Rodrigo

University of Castilla-La Mancha Department of Chemical Engineering, Faculty of Chemical Sciences and Technologies, Ciudad Real, Spain, [email protected]

High temperature proton exchange membrane fuel cells (HT-PEMFCs) present certain advantages in face of common PEMFC such as incease of CO tolerance, decrease of thermal and water managment of the system and higher efficiencys because of the use of the produced vapor in CHP systems [1-3]. However, it is necessary to researh new materials which reduce costs, decrease the corrosion degree and improve the perfomance of the fuel cell without compromising the catalytic activity [4-6].

It reports the synthesis and physical-chemically and electrochemically characterization of PtCo catalysts supported on a novel non-carbonaceous support to be used as cathode catalysts in HT-PEMFCs based on PBI membranes doped with phosporic acid. PtCo catalyts with a 40 wt% of metal were shyntesized by an impregnation method using NaBH4 as a reducing agent [7]. H2PtCl6·6H2O and Cl2Co·6H2O were used as precursor salts. The synthesized catalysts were physical-chemically characterized by ICP-MS, XRD, TPR, SEM and TEM. Besides, cyclic voltammetries (CV), chronoamprometries curves and oxygen reduction reactions (ORRs) were carried out in a rotating disk electrode (RDE) to gain knowledge into the kinetis and mechanism of oxyen reduction reaction and the electrochemical surface area (ECSA). Electrodes with the novel materials were prepared and the electrochemical resistance in terms of the change of ECSA was evaluated in hot phosphoric acid.

It can be concluded that the PtCo catalysts were successfully synthesized by borohydride method. Moreover, the achieved results are very promising in terms of durability but further work is required to improve the performance. Acknowledgements: The authors thank the European Commission as this work was supported by the 7th Framework Programme through the project CISTEM (FCH-JU Grant Agreement Number 325262). Financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is also acknowledged. References [1] J. Lobato, et al., J. Membrane Science, 369, (2011), 105-111. [2] R. Zeis, Beilstein Journal of Nanotechnology, 6, (2015), 68-83. [3] Z. Liu, J.S. Wainright, M.H. Litt, R.F. Savinell, Electrochimica Acta, 51, (2006), 3914-3923. [4] S. Sharma, B.G. Pollet, J. Power Sources, 208, (2012), 96-119. [5] T. Yang, Y. Ma, Q. Huang, G. Cao, Nano Energy, 19, (2016), 257-268. [6] Y. Okada, et al., J. Electrochem. Soc., 162, (2015), F959-F964. [7] M.-S. Hyun, et al., Catalysis Today, 132, (2008), 138-145.

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Effect of Crystalline Faces Exposure on Na+ Uptake Mechanism in Anatase TiO2 Nanocrystals for Energy Storage

Gianluca Longonia,1, Riccardo Ruffoa,2, Claudio Maria Maria,3,

Rosita Lisette Peña Cabreraa

aUniversità degli Studi di Milano-Bicocca, Dipartimento di Scienza dei Materiali,

Milano, Italy, [email protected], [email protected],

[email protected] Mass production of Li-ion batteries casts a shadow on the future sustainability of this technology due to the progressive depletion of world’s lithium resources. In this scenario, taking into consideration a secondary battery technology based on a more abundant element would surely represent a forward-looking attitude. Sodium ion batteries (SIB) were being investigated for the first time in the 80s, when the study on Li-intercalating compounds knew its first bonanza. Nevertheless, due to better performances and ready marketability of lithium technology, sodium alternative was promptly discarded and not further investigated. Recently, SIBs have been proposed as a valuable energy storage alternative for those applications where the exploitation of larger volumes is not a major concern (stationary energy storage). Engineering of efficient anode and cathode materials for SIBs still represents an anything but simple challenge, and even the unveiling of sodium interaction with electrochemically active electrode materials lacks of understanding[1]. In the present contribute a low cost anode material, based on nanocrystals anatase-TiO2[2], has been chosen as a promising candidate for the systematic study on how sodium cations efficiently interact with different crystalline exposed facets. This aspect has being indeed proven to have a pivotal role in the occurring of capacity concurring mechanisms. By shape-controlling TiO2 crystals synthesis, we’ve been able to obtain the selective growth of specific crystalline facets. Through an extensive electrochemical characterization of different morphologies we then traced an early stage dependence between the relative exposure of different facets ((101) and (001)), characterized by different Ti and O surface densities and surface energies, and the specific capacities obtained by galvanostatic cycling of TiO2-based electrodes. A more in-depth electrochemical analysis (advanced cyclic voltammetry) oriented to unveil the mechanism accountable for TiO2 reversible capacity, has been performed as well, and preliminary results suggest that the so-called intercalation pseudocapacitance[3] might have a considerable role. Together with mechanistic studies on bare TiO2 crystals, TiO2-rGO (reduced graphene oxide) composite has been prepared and studied in order to propose a high performing Na-ion battery anode with improved stability over cycling. This material showed interesting properties yielding to a reversible capacity of 150 mAh g-1 at 50 mA g-1 charge/discharge current, lasting for more than 600 cycles, with coulombing efficiencies close to 100 %. [1] L. Wu, et al., Adv. Energy Mater. (2014), 1–11. [2] M.N., Tahir, et al., Adv. Energy Mater., 2015 [3] V. Augustyn, et al., Nat. Mater., 12, (2013), 518–522.

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Influence of the Anodic Material in the Performance of a Microbial Fuel Cell

Sara Mateo, Pablo Cañizares, Manuel Rodrigo, Francisco J. Fernández-Morales

University of Castilla-La Mancha, Chem. Eng. Dept., Ciudad Real, Spain,

[email protected]

Microbial Fuel Cells (MFC) could be used for energy recovery from biodegradable substrates contained in the wastewater at the same time that the wastewater is stabilized. Nowadays, one of the main limitations of this technology is its low efficiency. In this work, in order to achieve high efficiency at low cost, different anodic carbonaceous materials were used in an air-breathing MFCs with small electrode areas and volumes. The experimental set-up used consisted of five MFCs working simultaneously with the following characteristics: 0.87 cm2 and 0.69 cm3 of anodic electrode area and volume respectively. Anode and cathode were separated by a Nafion proton exchange membrane. Carbon Toray paper with 10% of Teflon and 0.5 mg Pt cm-2 was used at the air-breathing cathode. The electrical external circuit was closed by means of a resistance of 120 Ω. The MFC was feed at a flow rate of 3 ml min-1 and the sludge age of the suspended cells was fixed 7.5 days. Regarding to the anode, five carbonaceous materials were studied: paper, cloth, felt and foam of 30 ppi and 80 ppi. The main results obtained when comparing the anodic materials are shown in Figure 1.

Figure 1. Evolution of the current density with different anodic materials: () Carbon Felt; () Carbon foam 80 ppi; (∆) Carbon cloth; (*) Carbon foam 30 ppi; (x) Carbon paper. After approximately 40 days of operation, carbon felt showed the best performance: an output current of 15 A m-2 was achieved, maximum power density of 3.98 W m-2 and a coulombic efficiency of 39.2 %. This best behavior could be related to the high porosity of this material which allows to the growth of a good biofilm in its surface. The main conclusion that can be obtained from this work is that the direct electron discharge play a significant role in the performance of the MFC. Therefore, more attention should be pay to characteristics, mainly porosity, of the carbon used as anodic electrode.

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Graphene-based Materials as Electrode Constituents of Energy Storage Devices

Jijeesh R. Nair, Francesca Colò, Federico Bella, Giuseppina Meligrana, Claudio Gerbaldi

Politecnico di Torino, GAME Lab, CHENERGY Group, Department of Applied Science and Technology - DISAT, Torino, Italy,

[email protected]; [email protected]

Energy production and storage have become key issues due to the ever-increasing demand of electricity in modern days. Rechargeable batteries are recognized as the primary power sources for applications from portable electronic devices to electric vehicles. Recently, there has been a growing interest in investigating graphene nanocomposite materials for various energy storage applications, such as electrode constituents in Li-based batteries (LiBs). With its unique structural, mechanical, and electrical properties, graphene can be a critical component in nanostructured electrode materials with improved capacity and cyclability, enabling the development of advanced batteries and new battery technologies to cover the increasing demand for high energy/power demanding applications.

Fig. 1. a) Sketched illustration of CNW deposition over Cu foil and arrangement of graphitic carbon flakes in the vertical direction; b) constant current long-term cycling of the CNW/LiFePO4 cell at 310 mA cm-2.

This contribution reviews the recent achievements in graphene utilization in negative electrodes for LiBs and introduces the latest progress of flexible graphene-based LiBs. In this respect, the application of vertically arranged multilayered graphene carbon nanowalls as high power LiB anode will be detailed as well as the novel spray-drying procedure towards hybrid 3D/2D Cu/Ni mixed oxide composite microspheres with graphene nanosheets. The superior cycling behaviour of the newly elaborated electrodes is demonstrated in lab-scale Li metal and Li-ion cells (LiFePO4 cathode and, eventually, polymer electrolyte separators) capable of very stable and prolonged reversible cycling with excellent durability exceeding thousands of cycles, good specific capacity and capacity retention when subjected to ultrafast current regimes. A survey of the scientific advances achieved thanks to the use of graphene in the so called “beyond Li-ion” technologies, namely Na-ion and Li-sulphur batteries, will be also envisaged.

Acknowledgements: EU Graphene Flagship support is gratefully acknowledged.

References

[1] J.R. Nair, et al., Electrochim. Acta, 182, (2015), 500–506.

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Electrochemical Treatment of Real Textile Wastewater: Tricromy Procion HEXL

Francisco Orts, Ana Isabel del Río, Javier Molina, José Bonastre, Francisco Cases

Universitat Politècnica de València, Departamento de Ingeniería Textil y Papelera,

Escuela Politécnica Superior de Alcoy, Alcoy, Spain, [email protected]

This work is aimed to the study of the degradation and electrochemical behaviour of bifunctional reactive dyes, tricromy Procion HEXL, their structure is mainly characterized by the presence of two azo groups as chromophore group and two monochlorotriazinic groups as reactive groups. The study consisted of three different dyeing processes performed with three solutions containing each dye separately and a fourth dyeing process with a solution containing the three dyes of this tricromy HEXL. After dyeing, different electrolyses were accomplished with the solutions obtained. From previous investigations [1], [2], the oxido-reduction process at 125mA cm-2 using a filter press reactor was found to give the best results in terms of degradation and decolourisation. Therefore, this working conditions were also chosen in this study. The degradation and decolourization degree was evaluated by means of Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD) measures. The combination of these results also allowed us to know the Average Oxidation State (AOS) at the end of the electrolyses and the efficiency of the processes in terms of the Carbon Oxidation State (COS) and the Average Current Efficiency (ACE). The decolourisation kinetics and the presence of the intermediates generated as a result of the electrochemical treatment was studied by High Performance Liquid Chromatography (HPLC) and these results were also completed with UV-Visible Spectroscopy studies. In all cases, a decrease in TOC and COD was obtained after the electrochemical treatment and the AOS and COS data corroborated the presence of oxidized intermediates in solution after the electrolyses. According to the ACE and COS results, the efficiency of these processes was confirmed as well. The decolourisation process followed a pseudo-first order kinetics. After the electrolyses a complete decolourisation was obtained and this result was also supported by the disappearance of the bands attributed to the chromophore groups. References [1] A.I. del Río, J. Molina, J. Bonastre, F. Cases, Chemosphere, 75, (2009), 1329–1337, 2009. [2] A. I. del Río, J. Fernández, J. Molina, J. Bonastre, F. Cases, Desalination, 273, (2011), 428–435.

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Electrochemical Oxidation of Synthetic Dyes Using BDD Anode With Solid Polymer Electrolyte

Marco Panizza, Antonio Barbucci, Maria Paola Carpanese, Davide Clematis, Marina

Delucchi, Alice Giuliano, Giacomo Cerisola

University of Genoa, Department of Civil, Chemical and Environmental Engineering, , Genova, Italy, [email protected]

Residual dyestuffs, although only present in small amounts, are sources of esthetic pollution and eutrophication of water bodies and thereby have to be removed from wastewater before it is discharged. In this field, electrochemical oxidation of refractory effluents has received a great deal of attention and it has been demonstrated that the complete mineralization of synthetic dyes can be obtained with high current efficiency by electrooxidation using only high-oxygen-overvoltage anodes such as BDD [1-3] anodes. However, most of experiments have been performed in aqueous solution containing supporting electrolyte and with high conductivity in order to reduce energy consumption, and only few papers deals with the treatment of water with low conductivity [4]. In this study, the degradation of Safranin T, a synthetic dye chose as model compound, has been investigated by anodic oxidation in galvanostatic condition. The electrolyses have been performed in a beacker with a BDD anode on Niobium expanded metal substrate, a Ti/RuO2 cathode sandwiched on a Nafion 324 ion exchange membrane that serves as solid polymer electrolyte. The synthetic dyes was dissolved in distilled water with a conductivity of 0.02 mS/cm or in a tap water with a conductivity of 0.02 mS/cm 0.27 mS/cm or in water with low amount of Na2SO4. The effect of operating conditions such as applied current, stirring rate, water conductivity and temperature has been studied. The experimental results showed that Safranin T was completely removed by the reaction with •OH radicals generated from water electrolysis, and the decay kinetics always follow a pseudo-first-order reaction. The oxidation was under mass-transport control and it was almost independent on temperature. Furthermore, it was observed that the increase of the conductivity of the solution decreased the removal rate. References [1] C.A. Martinez-Huitle, E. Brillas, Appl. Cat. B: Environ., 87, (2009), 105–145. [2] I. Sirés, E. Brillas, M.A. Oturan, M.A. Rodrigo, M. Panizza, Environ. Sci. Pollut. Res. 21, (2014), 8336–8367. [3] L. Labiadh, A. Barbucci, M.P. Carpanese, A. Gadri, S. Ammar, M. Panizza, J. Electroanal. Chem., 766, (2016) 94–99. [4] A.Kraft, M. Stadelmann, M. Wunsche, M. Blaschke, Electrochem. Commun. 8, (2006) 155–158.

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Regeneration and Recovery of Adsorbents by Electrochemical Advanced Oxidation Process

Imen Ouiriemmia,b, Salah Ammarb, Abdellatif Gadrib, Emilio Rosalesa, Marta Pazosa,

M. Angeles Sanromána

aUniversity of Vigo, Department of Chemical Engineering, Vigo, Spain, [email protected]

bUniversity of Gabes, Department of Chemistry, Faculty of Sciences of Gabes, Gabes, Tunisia.

Adsorption is a very promising method for the removal of several organic and inorganic pollutants from wastewater. By application of this method a rapid response is possible to handle catastrophic environmental problems but the pollution is only transported from wastewater to adsorbent. For this reason, the main drawbacks of this process are the expensive cost of the typical adsorbents and the disposal of the end products. Therefore, the recovery of adsorbent, its subsequent regeneration and reuse are important issues from an economical and environmental point of view. The effective regeneration can reduce the need of new adsorbent and also can diminish the problem of disposal of used adsorbent. Although, several regeneration techniques like thermal, electrochemical, ultrasonic, chemical methods are reported for regeneration, this area of investigation needs to be explored in depth [1]. For this reason, in this study, natural bentonite clay (aluminium phyllosilicate clay) from Tunisia was used as adsorbent. Initially, the physical-chemical characterization of this natural material was performed. Its potential for Methylene blue dye adsorption from aqueous solutions was evaluated. The dye adsorption was evaluated with a Colorimeter PCE-CSM 10 by color change using as reference the initial material without dye. Kinetics and isotherm studies were carried out to evaluate the effect of contact time, initial concentration, pH, and the desorption characteristics of bentonite. After the adsorption of dye on bentonite, comparative studies using Fenton and the electro-Fenton process were performed for the degradation of the adsorbed dye in the clay and the treated clay was used in successive adsorption processes. The electro-Fenton results showed the best performance. However, it was necessary to control the pH of the process due to the high buffering capacity of bentonite which increases the pH of the bulk media reducing the efficiency of oxidation process. To control the pH, citric acid was added which permitted the control of pH in acid environment and increased the iron solubility. Operating in this way, the total removal of dye adsorbed on bentonite was possible and the material could be used in successive adsorption-degradation process without any operational problem. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT and GRC 2013/003). The authors would like to thank to University of Gabes for the grant of I. Ouiriemmi and MINECO for financial support of M. Pazos and E. Rosales under Ramón y Cajal and Juan de la Cierva programs, respectively. References [1] K.S. Rao, et al., Internat. J. Eng. Sci.Technol., 2, (2010), 81-103.

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Comprehensive Solution for the Treatment of Wastewater: Combined Electro-Fenton and Adsorption Process

Jessica Meijide, Sandra Rodríguez, M. Angeles Sanromán, Marta Pazos

University of Vigo, Department of Chemical Engineering, Vigo, Spain,

[email protected]

In recent times, the use of Advance Oxidation Processes (AOP) has attracted the attention of the scientific community because their efficacy for the treatment of wastewater containing synthetic organic compounds. Among the different AOP, electro-Fenton has become a very interesting approach in which the powerful oxidants, hydroxyl radicals, are generated by the combination of Fenton’s reaction and electrochemical process. In this technique, the Fenton’s reagents, H2O2 and iron, are continuously generated and regenerated, respectively by the electric field action. Recently, several investigations have carried out in order to optimize the operational parameters as well as the reactor design to achieve the mineralization of organic compounds by the Electro-Fenton process [1]. However, the toxicity of the effluent after the treatment was not completely reduced because the presence of inorganic ions and organics of low molecular weight such as carboxylic acids. Thus, a subsequent treatment is required to achieve the total remediation of the water streams. In this work, a combined treatment Electro-Fenton and adsorption process was developed for a remediation of a simulated wastewater containing the pesticide acetamiprid. Initially, the development of heterogeneous catalyst was performed by the manufacture of iron-base-hydrogel catalysts. The catalytic activity and physical resistance of the different iron-base-hydrogels were assessed at different operational conditions and the catalyst that provided the best performance was a mixture of PVA-alginate-goethite. After that, catalyst dosage and working pH were evaluated to increase the degradation rate of the pesticide. In these assays the generation of ionic species as NH4

+, Cl- and NO3- as well as carboxylic acids was taken into account. In the optimized

conditions, the treatment of the water stream generated after the Electro-Fenton process was accomplished using fixed-bed adsorption filter containing activated carbon. For this end, the simulation tool Fast 2.0 was used and the breakthroughs were modelled using the homogenous surface diffusion model. The obtained results of this study permit to conclude that a combined treatment of Electro-Fenton and adsorption process can be an appropriate approach for the comprehensive remediation of water streams. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness, Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT and GRC 2013/003). The authors would like to thank to MINECO for financial support of M. Pazos under Ramón y Cajal program. References [1] J. Meijide, J. Gómez, M. Pazos, A. Sanromán, J. Hazard. Mater. (2016), doi:10.1016/j.jhazmat.2016.02.064

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The Role of Hydrogen Peroxide in the Electrochemical Synthesis of Peroxyacetic acid

I. Moraleda, José F. Pérez, Javier Llanos, Cristina Sáez, Pablo Cañizares, Manuel A.

Rodrigo

University of Castilla-La Mancha, Department of Chemical Engineering, Facultad de Ciencias y Tecnologías Químicas, Ciudad Real, Spain, [email protected]

One of the most important organic peroxides is peroxyacetic acid (PAA), which is also known as peracetic acid, which the carboxylic group or acetic acid (-COOOH). Depending on operation conditions, PAA can present bleaching and delignification properties, it may be used in industrial synthesis of epoxides. The most important use of PAA in industry is in water treatment, because it is an effective oxidant and a more potent antimicrobial agent than hydrogen peroxide, being rapidly active at low concentrations against a wide spectrum of micro-organisms. Thus, it has been found than hydrogen peroxide required much larger doses than PAA for the same level of disinfection. PAA can be found commercially in equilibrium with hydrogen peroxide, acetic acid and water.

CH3COOH + H2O2 → CH3COOOH + H2O

Recently, electrochemical oxidation with diamond anodes have become one of the most promising technologies in the treatment of industrial waste pollutions whit organics and in the electrosynthesis of oxidants. Compared with other electrode materials, boron doped diamond anodes have higher chemical and electrochemical stability, as well as higher current efficiency. In addition, the high overpotential for water electrolysis is one of the most important properties of conductive-diamond. These advantageous properties have led to great improvements (in both efficiency and electrode stability) in the use of conductive diamond in the electrosynthesis of many types of oxidants.

With this background, the goal of the work described here was to investigate the feasibility of generating peroxoacetic acid and its salts by electrolyses with conductive-diamond electrodes. To do this, bench-scale electrolysis assays of concentrated solutions of different raw material solutions were carried out in order to characterize the mechanism of the process and to clarify the role of the most significant process parameters (pH, current density, presence of H2O2).

Acknowledgments The authors acknowledge funding support from the Regional Government (Project PEII-2014-039) and the excellence network E3TECH funded by Ministry of Economy and Competitiveness (MINECO) through the project CTQ2015-71650-RDT.

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Modification of Porous Nickel Electrodes With Silver Nanoparticles for Hydrogen Production

Valentin Pérez-Herranza, Ramiro Medinab, Cristina González-Bucha, Emma Maria

Ortegaa, Guadalupe. Sánchez-Loredob

a Universitat Politècnica de València, Departamento de Ingeniería Química y Nuclear,

E.T.S.I. Industriales, Valencia, Spain, [email protected] b UASLP, Instituto de Metalurgia/Facultad de Ingeniería, México

In the present work macroporous Ni electrodes by electrodeposition at high current densities, modified with Ag nanoparticles (NPs), for the enhancement of the catalytic activity for the HER have been developed. Ag nanoparticles were electrodeposited on the surface of the Ni macroporous electrode at a current density of 100 µA/cm2 for one minute. The presence of the Ag NPs has been confirmed by means of FE-SEM microscopy and EDX analysis. The electrocatalytic behaviour towards the HER was assessed by pseudo-steady-state polarization curves, electrochemical impendance spectroscopy and hydrogen discharge curves in alkaline media. Fig. 1 shows the FE-SEM images where a typical Ni sponge-like macrostructure with spherical holes with diameters ranging between 100 and 200 µm, as previously reported, was obtained [1]. Ag nanoparticles homogeneously distributed on top of Ni macrostructure can be distinguished as white spots. Fig. 2 shows the polarization curves recorded in KOH 30 wt.% on macroporous Ni and Ni-Ag NPs. Polarization curves showed a classical Tafelian behavior and can be described by using the Tafel equation. Similar values of the Tafel slope (around 120 mV/dec) and the charge transfer coefficient (around 0.5) are obtained for the two electrodes. However, the macroporous Ni electrode modified with Ag NPs shows the highest exchange current density, i0 (3.41·10-3 v.s. 3.98·10-4 A/cm2) and the lowest values of the overpotential at a fixed current density of -100 mA/cm2, η100 (0.202 v.s. 0.289 V), showing the highest overall catalytic activity. Acknowledgments The authors thank the Spanish Ministry of Economy and Competitiveness for the financial support under the projects CTQ2015-65202-C2-1-R (MINECO/FEDER) and network E3TECH CTQ2015-71650-RDT (MINECO). References [1] I. Herraiz-Cardona, et al., Int. J. Hydrogen Energy, 37, (2012), 2147-2156.

Fig. 1. FE-SEM images of Macroporous Ni-Ag nanoparticles electrode.

Fig. 2. Linear Tafel polarization curves recorded on the investigated electrocatalytic coatings in 30 wt.%

KOH solution.

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Coupled System of Modified Membrane and Modified Cathode for Efficient PEM-FC

Marco Renzia, Maria Assunta. Navarrab, Roberto Marassia, Francesco Nobilia

a University of Camerino, School of Science and Technology, Chemistry Division, Camerino, Italy, [email protected]

b University “La Sapienza”, Department of Chemistry, Roma, Italy

A coupled system formed by polyoxometalate (POM)-modified ultra-low Pt loading cathode and sulphated titania (S-TiO2)-doped Nafion membrane is evaluated in a proton exchange membrane (PEM) fuel cell (FC). Modification of fuel cell cathode is performed using Kegging-type polyoxometalate and low Pt loading, in order to enhance active area and mesoporosity [1]. Commercial Nafion is modified with superacidic sulphated titanium oxide nanoparticles, in order to improve the proton transfer and the hydration level in the membrane-electrode assembly (MEA) [2,3]. The cell performance is studied at different relative humidity with polarization dependence and electrochemical impedance spectroscopy at high and low current density. Analysis of cell performance shows that the catalytic and transport properties are improved, with respect to unmodified commercial materials, using the coupled system, despite the ultra-low Pt loading used, thanks to rich proton environment provided from both cathode and membrane.

References [1] S. Dsoke, a. Moretti, G. Giuli, R. Marassi, International Journal of Hydrogen Energy 36, (2011), 8098 [2] M.A. Navarra, C. Abbati, F. Croce, B. Scrosati, Fuel Cell, 09, (2009), 222–225. [3] I. Nicotera, V. Kosma, C. Simari, G.A. Ranieri, M. Sgambetterra, S. Panero, M.A. Navarra, International Journal of Hydrogen Energy, 40, (2015), 14651-14660.

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Electro-bioremediation of Oxyfluorfen Polluted Soils with Periodic Polarity Reversal Strategy

Silvia Barbaa, José Villaseñora, Pablo Cañizaresb, Manuel A. Rodrigob

aUniversity of Castilla-La Mancha, Department of Chemical Engineering, Institute of Chemical & Environmental Technologies, Ciudad Real, Spain. [email protected] bUniversity of Castilla-La Mancha Department of Chemical Engineering, Faculty of

Chemical Sciences & Technologies, Ciudad Real, Spain

Electro-bioremediation is a technology based on the combination of electrokinetic and biological technique for in-situ the treatment of polluted soils. This alternative is focused on clayey soils characterized by low permeability where conventional pump and treat methods are not effective to move the underground water, pollutants, nutrients or microorganims. Electrokinetic transport mechanisms in soil get contacting the microorganisms and contaminants, something that improves de removal of pollutants, such as oxyfluorfen. This work shows an in-situ alternative for oxyfluorfen polluted soil remediation, using an acclimated pollutant-degrading microbial consortium distributed in the soil. The variable under study is the periodic change in the polarity of the electric field, in order to avoid the extreme values of pH which can affected the microorganisms negatively. Several polarity reversal frequency values have been tested (1, 2, 3 and 6 d-

1). All the experiments were carried out at 1 Vcm-1 during two weeks, using a lab-scale setup, and the concentration of oxyfluorfen in the soil was 200 mg/kg. From the results obtained it can be extracted these conclusions:

- In any case, the temperature and pH working conditions are adequate for the development of microorganisms and their functions.

- It was observed that the highest percentage of oxyfluorfen removal (15%) was achieved by using a polarity change with a frequency of 12 hours (2 d-1), while lower values were obtained using 2 d-1 (14%), 1 d-1(10%), and 6 d-1 (6%). This results offers an optimum value in the polarity reversal frequency and, according to the past experience of the authors [1], higher removal efficiencies are expected to be reached when using higher retention times. Acknowledgements Financial support from the Sapanish Minister of Economy and Competitivity through the project CTM2013-45612-R is gratefully acknowledged. In addition, financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is acknowledged. References [1] M. A. Rodrigo, E. Mena, C. Ruiz, C. Risco, J. Villaseñor, C. Saéz, V. Navarro, P. Cañizares, Chem. Eng. Trans., 41, (2014), 109-114.

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Analysis of a RFB as Renewable Energy Storage System

Justo Lobato, Esperanza Mena, Rubén López-Vizcaíno, Pablo Cañizares, Manuel A. Rodrigo.

University of Castilla-La Mancha, Department of Chemical Engineering, Faculty of Chemical Sciences & Technologies, Ciudad Real, Spain

[email protected]

The use of renewable energy sources has a great number of advantages such as the possibility of using them inexhaustibly. However, there are also some disadvantages related to the use of them (e.g. instability, unpredictability and fluctuations due to changes in the weather). Because this, the use of energy storage systems is required in order to be able to maintain an uninterruptable electricity supply as it is the required for houses, hospitals or official facilities. In the recent years a great number of studies have been published about a new electrochemical technology for the efficient storage of energy: Redox Flow Batteries. A flow battery consists of two usually aqueous electrolytes that contain two redox couples and are pumped through an electrochemical cell in which chemical energy is converted to electricity. Among the different redox systems, the all vanadium redox flow batteries (VRFB) are receiving a great attention by the researchers recently. This type of batteries was proposed in the mid-1980s by Professor Skyllas-Kazacos’s group [1], obtaining patent in 1986 (AU Patent 575247-1986). Since then, the development of this technology, even for the industrial application, has been spread world-wide. In this work, authors show the accumulated and delivered charge capacities and the coulombic, voltage and energy efficiencies obtained during the start-up of a bench scale VRFB used as solar or windy energy storage system. In this way, charge procedures were carried out applying variable current densities according to the solar radiation or wind speed profiles obtained in three winter days in Ciudad Real, Spain. Results show that the application of a non constant current (typical one from a renewable energy like solar) does not make to the VRFB performs in a worst way, reaching similar efficiencies and charge/discharge capacities than the one operating under constant current (31%, 38% and 39% were the energy efficiencies obtained in the constant, solar and wind profile procedures, respectively). However, further work is required to improve these laboratory results that are considerably different to that reported in the literature [2]. Anyhow, authors are in a position to affirm that VRFBs are suitable as energy storage systems for renewable energy sources. References [1] M. Skyllas-Kazacos, M. Rychcik, R.G. Robins, A.G. Fane, J. Electrochem. Soc., 133, (1986), 1057-1058. [2] M.J. Watt-Smith, P. Ridley, R.G.A. Wills, A.A. Shah, F.C. Walsh, J. Chem. Technol. Biot., 88, (2013), 126-138. Acknowledgements Financial support from the Spanish Minister of Economy and Competitivity is gratefully acknowledged (Project CTM2013-45612-R). In addition, financial support from the Spanish excellence network E3TECH funded by the Ministry of Economy and Competitiveness (MINECO) under project CTQ2015-71650-RDT is acknowledged.

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Fabrication of a Sediment Microbial Fuel Cell using vermicomposting of urban green waste

Jesus Rodríguez, D. Díaz, Roberto Campana., M. Sánchez, G. Sevilla, Lourdes

Rodriguez

Centro Nacional del Hidrógeno (CNH2) Puertollano (C. Real), Spain, [email protected]

Over the last decades, rural, industrial and urban green wastes have emerged as an important source of organic pollution., and most of treatment methods currently used to reduce that pollution involve high costs, time and, in some cases, greenhouses gases emissions (GHG’s). In contrast with them, vermicomposting represents a sustainable, rapid and cost-effective alternative method which leads to a substrate that is rich of nutrients and suitable for plant growth [1]. Differently to other composting processes, vermicomposting detritivorous worms fragment the waste substrate and accelerate the rate of the organic matter decomposition with a very low GHG’s emissions [1, 2]. Microbial Fuel Cells (MFC) are biolectrochemical devices that utilize the metabolic activity of exoelectrogenic bacteria to catalyze redox reactions on the anode to the cathode for direct current harvesting [3]. The Sediment Microbial Fuel Cells (a subgroup of MFC) use the electrons released by the microbial oxidation of organic matter in natural sediments or even less engineering management (e.g., artificial wetland). One of the most successful applications of this technology is wastewater treatment, which allows the reduction of the organic pollutants concentration as well as the energy harvesting (electrogenic wetlands). However, to the best of our knowledge, up to now, there is not reference of using this technology for solid waste management. Therefore, in this work we present a novel strategy for fabrication of sediment microbial fuel cells obtained by vermicomposted urban green waste.

Figure 1. Proposed methodology for Sediment Microbial Fuel Cell fabrication from vermicomposting References [1] P. Garg, A. Gupta, S. Satya, Bioresource Technol, 97. (2006), 391-396. [2] Y.C. Chan, R. K. Sinha, W. Wang, Waste Manage Res, 29, (2011), 540-548. [3] T. Huggins, H. Wang, J. Kearns, P. Jenkins, Z. J. Ren, 157, (2014), 114-119.

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The Pseudo-Capacitive Reaction in Electrodeposited Highly Hydrated Amorphous Iridium Oxide by operando Energy Dispersive XAS

Investigation

Sandra Rondininiabe, Cristina Locatelliab, Alessandro Minguzziab, Elisabetta Achillic, Paolo Ghignac, Alberto Vertovaabe

a Università degli Studi di Milano, Dipartimento di Chimica, 20133 Milano, Italy,

[email protected] b INSTM Milano Unit, Milano, Italy

c Università di Pavia, Dipartimento di Chimica, Pavia, Italy e associate to C.N.R. – I.S.T.M., Milano, Italy

Understanding the chemical phenomena occurring at the electrode/electrolyte interface is one of the highest challenges for a better design of electrodes in all fields of electrochemistry. This becomes particularly critical when inner sphere, electrocatalytic reactions are considered. Coupling electrochemistry with a complementary spectroscopy results in a spectroelectrochemical method that represents one of the most complete tool for collecting new insights on the mechanisms of electrochemical reactions. In the present communication we report our advanced studies on the dynamics of the charge accumulation in highly hydrated IrOx, a system of high relevancy in water electrolyzers [1], and specifically for its stability and high performances in both water oxidation [2]. This study is based on operando time-resolved Energy Dispersive X-Ray Absorption Spectroscopy (EDXAS) at the Ir LIII edge, performed at the ESRF beamline ID24 [3]. The potential steps are selected in order to drive the electron and charge transfers into the Ir(III) Ir(IV) and Ir(IV) Ir(V) transition domains. The adoption of sodium hydroxide aqueous solutions provides the best conditions for the potentiostatic control of the iridium oxidation states, as evidenced by the two well-separated, symmetric peaks observed in cyclic voltammetry. The combined treatment of electrochemical and XAS signals mutually supports the working hypothesis of full complementarity between the two techniques, that allow observing the pseudocapacitive reactions and its time evolution even in the presence of possible parasitic side-processes, and highlights the XAS features to be used as effective kinetic parameters. References [1] A. Minguzzi, O. Lugaresi, E. Achilli, C. Locatelli, A. Vertova, P. Ghigna and S. Rondinini, Chem. Sci., 5, (2014), 3591–3597. [2] A. Minguzzi, O. Lugaresi, C. Locatelli, S. Rondinini, F. D’Acapito, E. Achilli, , Anal. Chem., 85, (2013), 7009–7013. [3] I. Kantor, J.-C. Labiche, E. Collet, L. Siron, J.-J. Thevenin, C. Ponchut, J. Borrel, T. Mairs, C. Marini, C. Strohm, O. Mathon, S. Pascarelli, J. Synchrotron Rad., 21, (2014), 1240-1246.

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Electrochemical abatement of organic pollutants in continuous using microfluidic reactors in series

Simona Sabatino, Adriana D’Angelo, Alessandro Galia, Onofrio Scialdone

Università degli Studi di Palermo, Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Palermo, Italy, [email protected]

The removal of organic pollutants resistant to conventional biological processes from water often requires the adoption of advanced oxidation processes (AOPs). These processes involve chemical, photochemical or electrochemical techniques to allow chemical degradation of organic pollutants. Electrochemical methods are considered to be among the more efficient AOPs and can offer new sustainable routes for the abatement of toxic and bio-refractory organic pollutants [1-4]. These methods use a clean reagent, the electron, and mild operative conditions (room temperature and atmospheric pressure) with limited operative costs [1-2]. The microfluidic reactors (i.e. cells with a distance between the cathode and the anode of tens or hundreds of micrometers) can improve the electrochemical processes for the treatment of wastewaters contaminated by recalcitrant pollutants [2-4], allowing to operate with lower cell voltages and without supporting electrolyte), and on the other side to intensify the mass transport of the reagents towards electrodes surfaces. The utilization of micro devices may present the drawback of a more easy fouling but also other potential advantages such as an easier scale-up procedure through simple parallelization of many small units [4]. In this work, the possible utilization of various electrochemical oxidation methods for the treatment of aqueous solutions of Acid Orange 7 (AO7) chosen as a model compound (namely, direct electrochemical oxidation, indirect oxidation with active chlorine and electro-Fenton) used alone or in a combined way was studied for the sake of comparison of various electrochemical approaches. The abatement of AO7 was performed successfully in the micro reactors under a single-pass mode without supporting electrolyte at low cell voltages. A very high conversion for passage can be achieved, allowing to operate the process under a continuous mode and to achieve a fast screening of the effect of operative parameters due to very short times of treatment. The utilization of more micro reactors in series open interesting new perspectives, including the opportunity to modulate the current density among the reactors, in order to optimize the figures of merit of the process. Both electro-Fenton (EF) with cheap compact graphite cathode and electrochemical oxidation (EO) at boron doped diamond (BDD) anodes were used. Very different operating conditions were set for EF and EO to optimize their performances. The effect of current density, flow rate and initial concentration of AO7 on the process was investigated. References [1] C. A. Martınez-Huitle, E. Brillas, Applied Catalysis B: Environmental, 87, (2009),

105–145. [2] O. Scialdone, A. Galia, S. Sabatino, Applied Catalysis B: Environmental, 148-149,

(2014), 473– 483. [3] O. Scialdone, A. Galia, C. Guarisco, S. La Mantia, Chemical Engineering Journal,

229, (2012), 189– 190. [4] S. Sabatino, O. Scialdone, A. Galia, ChemElectroChem, 1, (2016), 83-90.

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Development of Concentration Strategies for the Improved Removal of Pesticides

Cristina Sáez, Alexandra Raschitor, Javier Llanos, Manuel A. Rodrigo, Pablo Cañizares

University of Castilla-La Mancha, Department of Chemical Engineering, Facultad de

Ciencias y Tecnologías Químicas, Ciudad Real, Spain, [email protected]

Within the last years, a great effort has been devoted to the development of

degradation techniques for the removal of hazardous organic pollutants. Among them, pesticides has attracted a special attention because they present bio-recalcitrant properties, high toxicity, and persist in the environment [1]. Among the technologies studied to remove or concentrate herbicides from polluted water, it is worth mentioning biological or membrane processes, adsorption, advanced oxidation technologies, electrochemical processes and combined technologies.

For the case of electrochemical-based depletion technologies, anodic oxidation have demonstrated a high ability to completely mineralize a wide range of organic pollutants [2]. One of the drawbacks of this technology is the limited efficiency of the process for the treatment of low concentrated effluents, due to the appearance of mass transfer control, which limits the maximum rate of the process [3].

In this context, the present work deals with the development of integrated processes for the enhanced removal of pesticides. These processes combine a stage of concentration and a step of pesticide degradation by anodic oxidation. In this way, it is possible to overcome mass transfer limitations characteristic of electrochemical degradation processes. In a first approach, concentration of ionic pesticides is integrated with anodic oxidation using DSA anode in the same electrochemical cell. It has been observed that the removal efficiency, in terms of applied electric charge, is increased by the simultaneous degradation and concentration of the target pesticide in a single electrochemical cell. DSA Registered trademark of Industrie De Nora Spa

Acknowledgments

The authors acknowledge funding support from the through the MINECO Project CTM2013-45612-R and the excellence network E3TECH (project CTQ2015-71650-RDT). References [1] R.D. Wilson, J. Geronimo, J.A. Armbruster, 2,4-D dissipation in field soils after applications of 2,4-D dimethylamine salt and 2,4-D 2-ethylhexyl ester, Environmental Toxicology and Chemistry, 16, (1997), 1239-1246. [2] C.A. Martínez-Huitle, E. Brillas, Decontamination of wastewaters containing synthetic organic dyes by electrochemical methods: A general review, Applied Catalysis B: Environmental, 87, (2009), 105-145. [3] Rodrigo, M., Michaud, P., Duo, I., Panizza, M., Cerisola, G., Comninellis, C. Oxidation of 4-chlorophenol at boron-doped diamond electrode for wastewater treatment, J. Electrochem. Soc. 148, (2001), D60-D64.

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Use of the Electrochemical Impedance in the Study of the Inhibition Corrosion of the carbon steel

Saker. Salimaa;b, Hammache. Houaa, Aliouane. Nabilaa

a Université de Béjaia, Laboratoire d’Electrochimie, Corrosion et de Valorisation

Energétique, Département de Génie des Procédés, Faculté de la technologie, Béjaia, Algeria, [email protected]

b Université de Béjaia, Département de Tronc Commun des Sciences de la Nature et de la Vie, Faculté des Sciences de la Nature et de la Vie, Béjaia, Algeria

. Electrochemical behaviour and corrosion layers of carbon steel electrode, in the absence and presence of a synthesized tetra-phosphonic acid (TPA), namely (methylenbis(2-hydroxy-5,1 phenylene)) phosphonic acid in 3% NaCl medium were investigated by electrochemical impedance spectroscopy and The morphology of the thin film formed on the inhibited surface of carbon steel was examined using the scanning electron microscope. The addition of phosphonic acid leads to growth in diameter and size of the capacitive semicircle (figure1), which probably reflects physical blocking of the metal surface which indicates the formation of a thicker protective film and therefore reduced corrosion [1]. SEM image in the presence TPA (Figure 3) shows a large area free of corrosion products and reveals the formation of an inhibitor layer. The results show that the inhibitor has the ability of reducing the corrosion rate of ordinary steel in 3% NaCl.

Figure 1: Impedance spectra of carbon steel in 3% NaCl medium in the absence and the

presence of different concentrations of ATP.

Reference [1] H. Hammache, L Makhloufi, B Saidani Corrosion Science, 45, (2003) 2031.

0 100 200 300 400 500 6000

100

200

300

400

à blanc 5.10-5mol/l 10-4mol/l 5.10-4mol/l 10-3mol/l

100 KHz

0,01 Hz

0,6 Hz

-Im

g (Z

) (O

hm.c

m²)

Re (Z) (Ohm.cm²)

Figure 2 : SEM image of carbon steel immersed in 3% NaCl.

Figure 3: SEM of carbon steel immersed in 3% NaCl containing 10−3 M of ATP

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Soil Flushing by Application of Low Intensity Current: A Solution for in situ Remediation of Hydrocarbons Polluted Soils

Ciprian Sandua,b, Marius Popescua,b, Emilio Rosalesa, Marta Pazosa, Gabriel Lazarb,

Maria Angeles Sanromána

aUniversity of Vigo, Department of Chemical Engineering, Vigo, Spain,

[email protected] b University of Bacau, Faculty of Engineering, “Vasile Alecsandri”, Bacau, Romania

The persistence of pollutants which are strongly sorbed into the soils is causing important environmental problems. Nowadays, the variety of complex mixtures of hydrocarbons depends upon manufacturer, geographic location, and seasonal use. For this reason, it is known that the compositions of these products are made up of hundred hydrocarbon compounds which are accumulated in environmental media, mainly in soil. Among the different available treatments, the in situ technologies are preferred since they are not invasive treatments. In this context, it is important to highlight that by application of a low intensity current it is possible to promote several phenomena into the soil that provoke the movement of the pollutants and flushing solutions [1]. In addition, chemical oxidation typically involves reduction/oxidation reactions that transform chemically hazardous contaminants into non-hazardous or less toxic, mobile or inert compounds. Therefore, by combination of both techniques could be possible the degradation of pollutants in a soil with low-permeability in which is not possible the application of conventional flushing technology. In this study, the in situ degradation of pollutants by the inclusion into the soil of oxidant reagents and by application of low intensity current was developed. Due to the variety of hydrocarbons (C10-C40) of a historically contaminated soil collected from an elevated industrial activity area in the nearby of Bacau (Romania), it was decided to treat this soil by different oxidant agents. The results showed that the removal of organic contaminants was achieved by the generation of oxidant species permitting the in situ oxidation/destruction. Thus, by addition of H2O2 the Fenton’s reaction took place by reaction with the iron present into the soil achieving degradation levels around 60%. Similar remediation levels were obtained when permanganate or persulfate were used. These results allow concluding that flushing process generated by low intensity current is a feasible way to fulfill the in situ remediation of a soil polluted with persistent contaminants as hydrocarbons. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT and GRC 2013/003). The authors would like to thank to the European Union for the financial support of Ciprian Sandu and Marius Popescu under the Erasmus+ program and to MINECO for the financial support of E. Rosales and Marta Pazos under Ramón y Cajal and Juan de la Cierva programs, respectively. References [1] M. Pazos, E. Rosales, T. Alcántara, J. Gómez, M.A. Sanromán, J. Hazard. Mater., 177, (2010), 1-11.

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Evaluation of Cathode Material and Configuration to Enhance the Electro-Fenton Process

Marius Popescua,b, Ciprian Sandua,b, Emilio Rosalesa, Marta Pazosa, Gabriel Lazarb,

Maria Angeles Sanromána

aUniversity of Vigo, Department of Chemical Engineering, Vigo, Spain, [email protected]

b University of Bacau, Faculty of Engineering, “Vasile Alecsandri”, Bacau, Romania

The worldwide production and application of pesticides have increased progressively. They are used for controlling, repelling, preventing or eradicating pests. However, their compositions often pose a threat against humans and the environment [1]. In addition, their high solubility in water increase the potential to leach into groundwater and transport to other water sources. One of the bottlenecks often faced on the field of environmental remediation is focused on the design of efficient processes. Consequently, to solve this environmental issue caused due to agricultural activities several conventional treatments have been studied with limited results. Therefore, the hunt for efficient alternatives is a concern to be tackled in order to improve the low efficiency of conventional techniques. Among the new technologies, the application of electrochemical advanced oxidation process (EAOP) has proved to be a powerful oxidative technique for degrading several organic pollutants such as pesticides [1]. It is considered that electro-Fenton is the most effective EAOP [3]. This process is based on the oxidation of ferrous iron to ferric iron by hydrogen peroxide which has been electrogenerated on cathode, releasing hydroxyl radicals with the capacity to oxidize a huge amount of pollutants. In addition, the electric current permits the catalytic cycle due to ferric iron species revert to ferrous iron, reducing the problem of iron sludge. To increase the efficiency of this technology, several key variables, can be studied such as the cathode material and configuration, initial pH or Fenton's reagents dosage. The main objective of this study was to enhance the electro-Fenton process by optimization of the cathode material and its configuration. For this purpose, different materials were used (nickel foam, carbon felt and carbon fiber) and they were tested in cylindrical and brush configurations. The cathodes were characterized and the hydrogen peroxide production recorded. After that, the effect of these electrodes on degradation process was evaluated using as model pollutant a pesticide, pyrimethanil. Finally, the degradation products were identified by GC-MS and a plausible degradation pathway was proposed. Acknowledgments This research has been funded by the Spanish Ministry of Economy and Competitiveness (MINECO), Xunta de Galicia and ERDF Funds (Projects CTM2014-52471-R, CTQ2015-71650-REDT and GRC 2013/003). The authors would like to thank to the European Union for the financial support of Ciprian Sandu and Marius Popescu under the Erasmus+ program and to MINECO for the financial support of E. Rosales and Marta Pazos under Ramón y Cajal and Juan de la Cierva programs, respectively. References [1] O. Iglesias, et al., Appl. Catal. B Environ. 144, (2013), 416-424. [2] E. Brillas, I. Sirés I, M.A. Oturan, Chem Rev. 109, (2009), 6570-631.

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Preparation of Polyaniline/Porous Silicon Hybrids for photovoltaic applications

Elisa Sechia, Annalisa Vaccaa, Maria Vitalia Tiddiab, Guido Mulab, Michele Masciaa,

Simonetta Palmasa, Simona Corgiolua, Pablo Ampudiaa, a Università degli Studi di Cagliari, Dipartimento di Ingegneria Meccanica, Chimica, e

dei Materiali, Cagliari, Italy. [email protected] b Università degli Studi di Cagliari, Dipartimento di Fisica, Monserrato(Ca), Italy

Over the last few years, hybrid nanocomposite materials have been studied for improving electrical and optoelectronic properties of several kind of devices, e.g. light emitting devices, solar cell, sensor and biosensor. The properties of the hybrid materials are related to the properties of the single constituents but also to the interface between the two materials especially when porous structures are used. In this work the preparation of nanostructured porous silicon (PSi) modified with polyaniline (PANI) have been studied ant the hybrid material has been test for photocurrent generation. The coupling of (PSi) with (PANI) has been realized by electrochemical polymerization of aniline on PSi. Before the impregnation, the inner PSi pores surface was functionalized by the electroreduction of 4-nitrobenzene diazonium salt (NBD) in order to obtain a covalent grafting of nitrophenyl layer onto silicon surfaces. The nitro group has been electrochemically reduced to amino group allowing to obtain a aniline layer already grafted prior to the polymerization. Cyclic voltammetries in acetonitrile solution containing perchloric acid (0.1 M) and aniline (0.1 M) have been used for the PANI polymerization: different values of the scan rate and number of cycles of polymerization have been tested. As a comparison, also samples obtained electropolymerising PANI directly on PSi without the aminophenyl layer have been prepared. Every sample was covered with a sputtered gold semitransparent contact and illuminated with a tungsten lamp. The photocurrent measurements were performed using a series of long-pass filters. The results indicate that the PANI/PSi prepared with the aminophenyl under-layer show higher increase of the photocurrent. Moreover, the covalent grafting of PANI on PSi improves the light absorption in the visible range compared to the empty porous silicon. This work was partially funded by Regione Autonoma della Sardegna, Fundamental Research Programme, L.R. 7/2007 ``Promotion of the scientific research and technological innovation in Sardinia'' under grant agreement CRP- 59886 AMBROSIA Project.

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Preparation, Characterization and Use of an IrO2-based DSA for the Electrochemical Removal of Dyes from Water

Zaira G. Aguilara, Mercedes Salazara, José L. Navaa, Enric Brillasb, Ignasi Sirésb

a Universidad de Guanajuato ,Departamento de Ingeniería Geomática e Hidráulica,

Guanajuato, Mexico, [email protected], [email protected], [email protected] b Universitat de Barcelona, Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Barcelona, Spain,

[email protected], [email protected] The textile industry today is the second largest polluter of clean water after agriculture due to the large consumption and complexity of its effluents. In particular, azo dyes are the most used compounds to color fabrics. They tend to be transformed into toxic aromatic amines which cannot be degraded by sunlight or by conventional processes, becoming very persistent in water. Nevertheless, some electrochemical advanced oxidation processes like electro-oxidation (EO) with high oxidation power anodes have shown outstanding oxidation ability [1]. Dimensional stable anodes (DSA) are of special interest owing to their low cost and high robustness. Usually, such anodes are composed of catalytic metal oxide layers (based on Ir, Ru, Sb and Sn) deposited onto a metallic substrate like Ti or Nb [2]. In the present work, a DSA composed of an IrO2-SnO2–Sb2O5 mixture was prepared following a specific protocol. Surface analysis was carried out by SEM-EDS and XDR to know the characteristics and composition of the electrode. Its ability to produce hydroxyl radicals (•OH) was assessed by indirect electron spin resonance (ESR) with DMPO as spin trap. Its performance to decolorize and mineralize synthetic dyes by EO was been tested using a flow system with a filter-press reactor equipped with the DSA and a stainless steel cathode of 20 cm2 area. Solutions of 2.5 L of Acid Yellow 36 azo dye at natural pH were electrolyzed in different aqueous media, including Na2SO4, NaClO4 and NaCl + Na2SO4. The effect of flow rate, current density, UVA light, Fe2+ content and initial dye concentration on decolorization efficiency and total organic carbon removal was thoroughly studied. The presence of chloride ions allowed the faster disappearance of the dye and its colored intermediates due to the action of active chlorine, which also led to a gradual mineralization at high applied current. The main reaction products have been identified by reversed-phase HPLC, GC/MS and ion chromatography. DSA Registered trademark of Industrie De Nora Spa

Acknowledgments Financial support from project CTQ2013-48897-C2-1-R (MINECO/FEDER, EU), as well as from excellence network E3TECH under project CTQ2015-71650-RDT (MINECO, Spain) is acknowledged. The authors would also like to thank financial support under project 240522 (CONACYT, Mexico) and project 869/2016 (University of Guanajuato, Mexico). Z. Aguilar thanks her PhD grant (CONACYT, Mexico).

References [1] M.I. León, Z.G. Aguilar, J.L. Nava, J. Electrochem. Sci. Eng., 4, (2014), 247-258. [2] Ch. Comninellis, Electrochim. Acta, 39, (1994), 1857-1862.

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Nanostructured TiO2 Substrate: Influence on the Electrocatalytic Properties of Manganese Oxide Based

Electrodes in the Anodic Oxidation of Organic Pollutants

Giovanni Sotgiua, Daniele Montanarob, Monica Orsinia, Elisabetta Petruccib

a University of Roma Tre, Department of Engineering, Rome, Italy, [email protected]

b Sapienza University of Rome, Department of Chemical Engineering Materials & Environment, Rome, Italy

Although manganese oxide-based (MnOx) electrodes exhibit promising electrocatalytic activity, a reduced electrogeneration of chlorinated by-products in the presence of chlorides and low cost, they have been little explored in the anodic oxidation of recalcitrant pollutants. This is partially due to their limited durability caused by a low adherence of the oxides to the investigated substrates. Nonetheless, the peculiar characteristics of these materials encourage further studies to improve both stability and durability by adopting more efficient preparation techniques. In previous research, by comparing the performance of MnOx films grown on both untreated and microstructured substrates we have verified that the morphological and electrochemical properties of the electrodes are improved by a surface texturization [1]. Recently, a new approach for the production of anode materials has been developed and applied. The method involves the oxide deposition on substrates modified at a nano-scale with significant increase in the life time of the electrode without impacting the electrocatalytic properties [2]. The enhanced performance can be attributed either to the increase in the electrode surface area or to the improved inclusion of the oxide particles inside the nanostructures. The present work investigates the possibility to prepare a new manganese-based electrode by deposition of the oxide on a TiO2 nanostructured substrate. In particular, ordered structures of TiO2 nanotubes have been obtained by anodizing titanium foils in the presence of pitting agents, using different organic electrolytes. The obtained electrodes have been characterized in terms of chemical, morphological and electrochemical properties by scanning electron microscopy (SEM), profilometry, cyclic voltammetry (CV). The nanostructured substrates have been coated with an interlayer and a thin film of MnOx by thermal decomposition of hydroalcoholic solutions. Preliminary results on the applicability of the obtained materials as the anodes in the oxidation of aqueous solutions of recalcitrant compounds are also presented. The electrolysis experiments have been conducted under galvanostatic conditions in a free membrane cell. In particular, the influence of the oxides thickness (RuOx interlayer and MnOx, active layer) have been correlated with the morphological and electrochemical performances of the electrodes.

References

[1] G. Sotgiu, L. Tortora, E. Petrucci, J. Appl. Electrochem., 45, (2015), 787-797. [2] H. An, H. Cui, W. Zhang, J. Zhai, Y. Qian, X. Xie, Q. Li, Chemical Engineering Journal, 209, (2012), 86-93.

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Electrochemical Performance of an Innovate Water Treatment Technology in Aquaculture: ELOXIRAS

P. Gómeza, A. Arrutia, J. Pinedoa, E. Santosa, R. Ibáñezb, I. Ortizb, A. Urtiagab

a APRIA Systems S.L., Centro de Empresas Municipal de Camargo, Revilla de

Camargo, Cantabria, Spain, [email protected] b University of Cantabria, Department of Chemical and Biomolecular Engineering,

Santander, Cantabria, Spain, [email protected] Aquaculture industry fulfils the increasing global demand of marine fish species without spoiling the natural resources. Recirculating Aquaculture Systems (RAS) are emerging as an advantageous technology to raise biomass production, but entails the accumulation of harmful compounds (ammonia, nitrite, nitrate, organic matter and pathogens) for the fish farming. Current water treatment are mainly based on biofilters, that are useful to reduce the amount of contaminant but present several limitations in the process performance. ELOXIRAS [1] is an innovative water treatment concept, based on electrochemical oxidation, specially developed to improve the productivity and to reduce the environmental impact of marine RAS. The major differences among biolfiters and ELOXIRAS lie in:

• Number of contaminants removed: Biofilter technology is able to partially remove total ammonium nitrogen (TAN) and nitrites, having no effect against bacteria and viruses. ELOXIRAS is able to completely remove the harmful contaminants present in aquaculture recirculating water circuits: TAN, nitrites, bacteria and viruses.

• Process efficacy: Biofilters have an average TAN and nitrite elimination rates typically between 50%-60%, while ELOXIRAS reaches efficiencies above 99%.

• Operating conditions: Biofilters require start-up and adaption periods when variations in the wastewater composition and volume occur, while ELOXIRAS offers an instantaneous response to these changes.

Besides, ELOXIRAS presents several features that makes it different from numerous electrochemical processes. In most cases electrochemical oxidation is applied to treat low volumes of water with high concentration of contaminants. The challenge of ELOXIRAS is the treatment of large water volumes posing low contaminant concentrations in a cost-efficient way. Additionally, ELOXIRAS presents a continuous monitoring system to automatically adjust the treatment capacity to the volume and composition of water, also monitoring and managing the presence of any by-product. Acknowledgement ELOXIRAS is a project co-funded by the European Union under H2020 SME Instrument. Support from the Spanish excellence network E3TECH (CTQ2015-71650-RDT) and project CTM2013-44081-R, MINECO, is also acknowledged.

References [1] ELOXIRAS, 2016. http://www.eloxiras.com/

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New Electrochemical Medium for Synthesizing Highly Mesoporous Pt and CoPt3 Nanorods useful as Catalysts for Ethanol Electro-oxidation

Elisa Vallésa, Albert Serràa, Elvira Gómeza, Manuel Montielb

aUniv. Barcelona, Ge-CPN, Dpt. Ciència de Materials i Química Física, and Institut de

Nanociència i Nanotecnologia (IN2UB), Barcelona, Spain, [email protected] b Universidad Autónoma de Madrid, Dpt. Química Física Aplicada, Madrid, Spain

The electrodeposition of Pt or CoPt in the interior of polycarbonate membranes using IL/W microemulsions of ionic liquid (bmimPF6) in aqueous solution of Pt(IV) or Pt(IV)+Co(II) allows us to obtain uniform mesoporous nanorods (NRs) of 3-4 µm of length, 100-110 nm of diameter and pores in the 3-4 nm range (Fig. 1). The electrochemically active surface areas (ECSAs) of the nanorods is very high (228 and 235 m2 g-1 for Pt and CoPt3), due to the high porosity of the nanostructures, which show around 15 times as much surface area as compact nanorods. The electrocatalytic activity of the mesoporous nanorods respect of the ethanol electro-oxidation in alkaline medium has been studied and compared with that of compact nanorods or PtRu nanoparticles/C substrates: Fig. 2 shows that the CoPt3 mesoporous NRs present significantly higher mass-normalized oxidation peaks than compact ones or commercial PtRu nanoparticles (NPs). Moreover, the synthesized NRs show excellent stability in aggressive acidic or alkaline media, being good catalysts for ethanol fuel cells.

Acknowledgements Financial support from EU ERDF (FEDER) funds and from the Spanish Ministry of Economy and Competitiveness (MINECO) for the TEC2014-51940-C2-2-R grant and the excellence network E3TECH funded under project CTQ2015-71650-RDT is acknowledged.

Fig. 2. Cyclic voltammograms at 50 mV s-1 for ethanol oxidation in 1 M NaOH of A) compact

CoPt3 NRs, B) commercial Pt-RuNPs/C, C) CoPt3 mesoporous NRs

Fig. 1. TEM image of a CoPt3 mesoporous NR electrochemically synthesized in the IL/W microemulsion

P35 _____________________________________________________________________________________


Cavity Micro Electrodes (C-MEs) & SECM (Scanning ElectroChemical Microscopy) for the Investigation of Photoactive Semiconductor Materials and the Evaluation of Photodegradation

Process during PEC_WS.

Alberto Visibile,a Alessandro Minguzzi,a Alberto Vertova,a,b Sandra Rondinini. a,b

aUniversità degli Studi di Milano, Department of Chemistry, Milano, Italy,

[email protected] bAssociate to C.N.R. – I.S.T.M., Milano, Italy

Photoelectrochemical water splitting using semiconducting materials is an interesting route to produce hydrogen (or other chemicals, e.g. oxygen) using solar energy. However, these materials might exhibit poor stability under photoexcitation and degrade in aqueous solution leading to a progressive loss of efficiency. Our work aimed to set up and validate a simple and fast method for screening libraries of materials and identifying their efficiency in H2 (or O2) production respect to side reactions or photocorrosion. The proposed method is applicable to any semiconductor powder for a fast, preliminary evaluation of the material, in the absence of any effect of the supporting material (i.e. the current collector, FTO). Here, scanning electrochemical microscopy (SECM) in tip generation /substrate collection (TG/SC) [1] mode in combination with cavity microelectrodes [2-3] were used to characterize the behaviour of different powder materials: CuO/Cu2O coreshell NP [4], NiO, CuI and TiO2. The preliminary feasibility was confirmed by the use of Pt/Vulcan XC-72 (28.6% w/w) powder as standard material. The influence of different wavelength light on the whole system was evaluated too [5]. References [1] S. Morandi, A. Minguzzi Electrochemistry Communications, 59, (2015), 100–103. [2] A. Minguzzi, C. Locatelli, O. Lugaresi, A. Vertova, S. Rondinini, Electrochimica Acta 114, (2013), 637-642. [3] C. Locatelli, A. Minguzzi, A. Vertova, P. Cava, S. Rondinini, Analytical Chemistry, 83, 7, (2011), 2819-2823. [4] T. Baran, A. Visibile, S. Wojtyła, M. Scavini, F. Malara, A. Naldoni, A. Minguzzi, Reverse Type I core/shell CuxO@CuI: versatile heterostructure for photoelectrochemical applications (in preparation). [5] V. V. Yakushev, A. M. Skundin, V. S. Bagotskii, Electrokhimiya, 20, (1982), 99-104.

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The Effect of Operating Temperature and Cell Configuration on the Performance of Ethanol Fuel Cells

Sabrina C. Zignani, Massimiliano Lo Faro, Stefano Trocino, Vincenzo Baglio, Antonino S. Aricò

Institute of Advanced Energy Technologies (ITAE) of National Research Council

(CNR), Messina, Italy, [email protected]

A large number of investigations have been devoted to low temperature direct ethanol fuel cells (DEFCs), and several efforts have been addressed to overcome their limitations related to the low performance achievable and to the rapid deactivation of anodic catalyst [1]. Nevertheless, limitation in power density produced by a low temperature fuel cell is yet an open issue. The alternative is the use of ethanol as fuel for high temperature solid oxide fuel cells (SOFCs). However, also in this case some issues are object of investigations. At the present, in fact, the direct use of ethanol in traditional SOFCs based on nickel/yttria stabilized zirconia (Ni/YSZ) anodes leads to a fast deactivation due to carbon formation as well as poisoning of catalytic sites by the sulphur impurities. A possible approach is provided by the use of a protective layer deposited on the outermost side of the supporting anode of a state-of-the-art SOFC. This can mitigate the effects of degradation caused by the use of ethanol [2]. We report the results obtained in the study of anodic catalyst for low temperature fuel cells (DEFC) and high temperature fuel cells (SOFC) with the aim to mitigate the degradation mechanisms occurring on both technologies during the utilization of ethanol.

References [1] S.C. Zignani, V. Baglio, J.J. Linares, G. Monforte, E.R. Gonzalez, A.S. Aricò, Electrochim. Acta, 70, (2012), 255-265. [2] M. Lo Faro, R.M. Reis, G.G.A. Saglietti, A.G. Sato, E.A. Ticianelli, S.C. Zignani, A.S. Aricò, ChemElectroChem, 1, (2014), 1395-1402.

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List of Speakers

Alegre C. P1 p. 45

Ania C. O17 p.24

Asensio Y. O1 p.2 - P2 p. 46

Baran T. O29 p.38

Benedetto M. K1 p.12

Bocos E. O18 p.25 - P3 p. 47

Bouzek K. K2 p.13

Calcaterra S. P4 p. 48

CHEMICAL NEWTECH S.p.a. - Titanium Anodes O6 p.7

D'angelo A. O2 p.3 - P5 p. 49

Diez A. O20 p.27 - P6 p. 50

Dolla T. P7 p. 51

ENGITEC S.p.a. O7 p.8

Feliu J. O13 p.20

Fernandez Domene R.M. P8 p. 52 - P9 p. 53

Geneste F. O16 p.23

ITELCOND S.r.l. O8 p.9

La Mantia F. K3 p.14

Lapicque F. K4 p.15

Lo Faro M. O11 p.17

Lobato J. O10 p.16 - P10 p. 54

Longoni G. P11 p. 55

Mais L. O22 p.31

Mateo S. P12 p. 56

Musiani M. O30 p.39

Nair J. P13 p. 57

NANOMATERIALS.IT S.r.l O9 p.10

Orts F. P14 p. 58

Panizza M. P15 p. 59

Pazos M. P16 p. 60 - P17 p. 61

Perez J. O14 p.21

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Perez J.F. P18 p. 62

Perez V. O28 p.37

Perez-Herranz V. P19 p. 63

Petrucci E. O19 p.26

Renzi M. P20 p. 64

Ridruejo C. O23 p.32

Rodrigo M. P21 p. 65 - P22 p. 66

Rodriguez-Ruis J. P23 p. 67

Rondinini S. P24 p. 68

Sabatino S. O24 p.33 - P25 p. 69

Saez A. O3 p.4

Saez C. O12 p.18 - P26 p. 70

Salima S. P27 p. 71

Sanroman A. P28 p. 72 - P29 p. 73

Sechi E. O15 p.22 - P30 p. 74

Sires N. P31 p. 75

Soavi F. O4 p.5

Soler S. O21 p.30

Soriano A. O25 p.34

Sotgiu G. P32 p. 76

Steter J. O26 p.35

Tsurumaki A. O27 p.36

Urtiaga A. P33 p. 77

Valles E. P34 p. 78

Visibile A. P35 p. 79

Zaffou R. O5 p.6

Zignani S. P36 p. 80

Gargnano (Garda Lake) – Italy 14-16 September 2016 PROGRAMME · Xosé Ramón Nóvoa, Universidad...

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