PROGRAM & ABSTRACTSgso/documents/2018... · 2018-08-20 · 5 7:00PM – 9:00PM Symposium Mixer Sgt...

27th AnnualGraduate Research Symposium

August 15-16, 2018

Davidson School of Chemical EngineeringPROGRAM & ABSTRACTS

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Preface........................................................................................................ 2

2018 - 2019 GSO Officers ......................................................................... 3

2018 Symposium Coordinators ................................................................ 4

Schedule of Events .................................................................................... 5

Keynote Speaker ....................................................................................... 7

Student Research Seminar Schedule

Morning Session ................................................................................ 8

Afternoon Session ........................................................................... 10

Student Speaker Abstracts ..................................................................... 13

Poster Showcase Map ............................................................................. 36

Poster Showcase Guide .......................................................................... 37

Acknowledgements ................................................................................. 38

Table of Contents

2 Chemical Engineering GSO Research Symposium 2018

Preface

It is with great pleasure that I welcome you to the Davidson School of Chemical Engineering for the 27th Annual Graduate Research Symposium. This event has a long history of strengthening the relationships between our department and industry, and your attendance today continues this tradition. Our senior graduate students benefit greatly from the feedback they receive from our industrial partners and become better prepared for the hiring process as a result.

Furthermore, your financial contributions help to support the Graduate Student Organization’s mission of building a flourishing and enriching community for our students. With your support, we are able to host a variety of professional development, service, and social events, ranging from teaching local third graders after-school science lessons to hosting swing dance lessons in the atrium.

We hope you take this opportunity to listen to the oral presentations from our graduate students and help them with the important transition from academia to industry. We also encourage you to spend some time at the poster session to become more familiar with the research of our rising graduate students.

I would like to personally extend my sincere gratitude to all in attendance today. Your continued support is greatly appreciated by the student body, and we look forward to a continued partnership in the years to come.

David RokkePresident, Graduate Student Organization2018-2019

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David Rokke ……........................................................................... President

Vinny Pizzuti …….................................................................... Vice President

Jessica Torres ..................................................... First-Year Representative

Mihit Parekh ……….............................................. First-Year Representative

Kaustabh Sarkar ................................................ Student Advocacy Officer

Blake Finkenauer ……........................................................... PGSG Senator

Tony Mathew ...................................................... Publications Chairperson

Ayse Eren ....................................................................... Social Chairperson

Kyle Weideman ............................................................ Sports Chairperson

Aidan Coffey …....................................... Outreach Committee Chairperson

Aditi Khot ……..…................................. Co-curricular Activities Chairperson

Akriti Akriti ..................................... Sustainability Committee Chairperson

Kai Jin ........................................................ Safety Committee Chairperson

2018-2019 GSO Officers


David Rokke ..................................... Symposium Committee Chairperson

Tony Mathew ....................................................... Publications Coordinator

Ayse Eren ………….…….......................................... Publications Coordinator

Bev Johnson .......................................................... Scheduling Coordinator

Blake Finkenauer ……............................................ Scheduling Coordinator

Jessica Torres ........................................................ Scheduling Coordinator

Aditi Khot …………..…........................................ Poster Session Coordinator

Mihit Parekh ………….................................................... Judging Coordinator

Aidan Coffey …………..................................... Industrial Packet Coordinator

Kai Jin ............................................... Refreshment & Catering Coordinator

Akriti Akriti ........................................ Refreshment & Catering Coordinator

Vinny Pizzuti ........................................................... Industrial Liaison Head

Kyle Weideman ............................................................... Industrial Liaison

Kaustabh Sarkar ............................................................ Industrial Liaison

2018 Symposium Coordinators

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7:00PM – 9:00PM Symposium Mixer Sgt Preston’s Purdue Room 14 N 2nd St, Lafayette

Thursday, August 16th, 2018

7:30AM – 8:30AM Breakfast & Welcome Davidson School of Chemical Engineering Henson Atrium

8:30AM – 9:30AM Student Research Seminars Davidson School of Chemical Engineering Session A – Room G124 Session B – Room B124

9:30AM – 9:45AM Break

9:45AM – 10:45AM Keynote Address Dr. Peter T. Kissinger - Bioanalytical Systems, Inc. Davidson School of Chemical Engineering FRNY G140

10:45AM – 11:00AM Break

11:00AM – 12:00PM Student Research Seminars Forney Hall of Chemical Engineering Session A – Room G124 Session B – Room B124

12:00PM – 12:45PM Lunch Davidson School of Chemical Engineering Henson Atrium

Schedule of Events Wednesday, August 15th, 2018


Schedule of Events Thursday, August 16th, 2018 (continued)

12:45PM – 2:00PM Poster Showcase Davidson School of Chemical Engineering Henson Atrium

2:00PM – 3:00PM Student Research Seminars Davidson School of Chemical Engineering Session A – Room G124 Session B – Room B124

3:00 PM – 3:15PM Break

3:15PM – 4:15PM Student Research Seminars Davidson School of Chemical Engineering Session A – Room G124 Session B – Room B124

4:15 PM – 4:30PM Closing and Vote of Thanks

7:00PM – 9:00PM Awards Banquet Midtowne Oven--Columbia Room 625 Columbia Street, Lafayette

Keynote Speaker

Dr. Kissinger received a B.S. in Chemistry (1966) from Union College, Schenectady, N.Y. and a Ph.D. in Analytical Chemistry (1970) from the University of North Carolina in Chapel Hill. Prior to joining the faculty at Purdue in 1975, Kissinger was a Research Associate at the University of Kansas (1970-1972) and an Assistant Professor at Michigan State University (1972-1975). Headquartered in West Lafayette, Indiana, BASi also has operations in Evansville, Indiana and St. Louis, Missouri. The company manufactures instrumentation and develops software for pharmaceutical research, and carries out contract bioanalytical, pharmacological and toxicological research for pharmaceutical and biotechnology companies. Dr.Kissinger’s academic research has involved the study of electroanalytical chemistry, modern liquid chromatography techniques, and in vivo methodology for drug metabolism and the neurosciences. Dr. Kissinger has published more than 250 scientific papers and is a Fellow of the American Association of Pharmaceutical Scientists and the American Association for the Advancement of Science. In 2005, he became the Chairman of Prosolia, which markets mass spectrometry innovations for life science, industrial and homeland security applications. In 2007, he and Candice Kissinger founded Phlebotics, Inc., a medical device company focused on diagnostic information for intensive care medicine. He is a columnist for the trade publication Drug Discovery News and serves on several boards, including Chembio Diagnostic Systems (CEMI) in Medford, New York. Kissinger advises startup firms including bioVidria, AniDyn, and Tymora while continuing to be active with BASi, Prosolia, Inc. and Phlebotics, Inc. On the Purdue campus he enjoys interactions with several faculty in ChemE and Industrial Engineering with the goal of using engineering principles to improve care of hospitalized patients. He has long supported entrepreneurship programs on campus from before they were born, including formation of the first business incubator in the Purdue Research Park in the late 1980's, now among the largest in the country.

Peter T. Kissinger

Founder of Bioanalytical Systems, Inc. (BASi)

Professor of Chemistry at Purdue University

[email protected]

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Student Research Seminar Schedule Session A - Morning (FRNY G124)

8:30 AM − 8:50 AM CeO2 Supported Ni-based Catalysts Prepared by Solution Combustion Synthesis for H2 Generation from N2H4∙H2O Wooram Kang Dr. Arvind Varma

8:50 AM − 9:10 AM Catalytic Consequences of Spatial Distribution, Mobility, and Solvation of Active Sites on Ammonia Selective Catalytic Reduction of Nitric Oxide over Cu-Zeolites Ishant Khurana Dr. Fabio Ribeiro

9:10 AM − 9:30 AM Density Functional Theory Studies of Atomic Layer Deposition on LiMn2O4 Lithium Ion Battery Cathodes Robert Warburton Dr. Jeffrey Greeley

9:45 AM – 10:45 AM Keynote Address Dr. Peter Kissinger - FRNY G140

11:00 AM − 11:20 AM Nature of SO2-poisoning on ZCuOH and Z2Cu sites in Cu-SSZ-13 during the NH3 Selective Catalytic Reduction (SCR) of NOx Arthur Shih Dr. Fabio Ribeiro

11:20 AM − 11:40 AM Pt-Co Catalysts for Alkane Dehydrogenation: Structural Effects on Selectivity Laryssa Goncalves Caesar Dr. Jeffrey T. Miller

11:40 AM − 12:00 PM Influence of Confining Environment Polarity on Ethanol Dehydration Catalysis by Lewis Acid Zeolites Jason Bates Dr. Rajamani Gounder

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Student Research Seminar Schedule Session B - Morning (FRNY B124)

8:30 AM − 8:50 AM Manipulating Energy Transfer between a Photoexcited Conjugated Polymer and Open-Shell Small Molecules Daniel Wilcox Dr. Bryan Boudouris

8:50 AM − 9:10 AM Synthesis and Evaluation of Novel Thin-Film Solar Cell Materials: A Case Study of Cu3AsS4 Scott McClary Dr. Rakesh Agrawal

9:10 AM − 9:30 AM Temperature Dependent Electrochemical Performance and Safety Aspects of Graphite Anodes for K-ion and Li-ion Batteries Ryan Adams Dr. Arvind Varma and Dr. Vilas Pol

9:45 AM – 10:45 AM Keynote Address Dr. Peter Kissinger - FRNY G140

11:00 AM − 11:20 AM Constant-Pattern Design Method for Separating Ternary Mixtures of Rare Earth Elements Using Ligand-Assisted Displacement Chromatography Hoon Choi Dr. Nien-Hwa Linda Wang

11:20 AM − 11:40 AM Interfacial Tension and Phase Behavior of Oil-Aqueous Systems with Applications to Enhanced Oil Recovery Jaeyub Chung Dr. Elias I. Franses and Dr. Bryan Boudouris

11:40 AM − 12:00 PM Approaching the Nature of Glass Transition as Probed by Dynamic Mechanical Analysis of Polymers Yelin Ni Dr. James Caruthers


Student Research Seminar Schedule Session A - Afternoon (FRNY G124)

2:00 PM − 2:20 PM Articular Cartilage Defect Repair with a Collagen Type I and II Blend Hydrogel in vitro and in vivo Need Claire Kilmer Dr. Julie Liu

2:20 PM − 2:40 PM Deciphering the Molecular Mechanisms Involved in the Transport of Volatile Organic Compounds in the Epicuticle of Plant Epidermal Cells Shaunak (Rick) Ray Dr. John Morgan

2:40PM – 3:00 PM A Modeling Framework to Individualize Hydroxyurea Based Treatment of Sickle Cell Patients Akancha Pandey Dr. Doraiswami Ramkrishna

Break

3:15 PM − 3:35 PM Structural Effect of PdZn Surfaces on CO and Propylene Adsorption Cory Milligan Dr. Fabio Ribeiro

3:35 PM − 3:55 PM Controlled Heteroatom Insertion into Zeolite Framework Vacancy Defects and Catalytic Consequences for Glucose Isomerization Juan Carlos Vega-Vila Dr. Rajamani Gounder

3:55 PM − 4:15 PM First Principles Modeling of Site Interconversion in Lewis Acid Zeolites for Ethanol Dehydration Brandon Bukowski Dr. Jeffrey Greeley

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Student Research Seminar Schedule Session B - Afternoon (FRNY B124)

2:00 PM − 2:20 PM Coffee Eye Effect: the Formation of Stagnation Points during Drop Evaporation and the Influence on Particle Deposition Lihui Wang Dr. Mike Harris

2:20 PM − 2:40 PM The Effect of Scale-Up on Mixing Efficiency in Oscillatory Flow Reactors Using Principal Component Image Analysis as a Novel Noninvasive Residence Time Distribution Measurement Tool Joseph Oliva Dr. Zoltan Nagy

2:40PM – 3:00 PM Advancing Smart Manufacturing in Continuous Processing of Oral Solid Doses Sudarshan Ganesh Dr. Gintaras Reklaitis and Dr. Zoltan Nagy

Break

3:15 PM − 3:35 PM Dropwise Additive Manufacturing for Pharmaceutical Products utilizing non-Brownian Suspensions Andrew Radcliffe Dr. Gintaras Reklaitis and Dr. Zoltan Nagy

3:35 PM − 3:55 PM Process Intensification and Control in Pharmaceutical ManufacturingKanjakha Pal Dr. Zoltan Nagy


Student Research Abstracts

The abstracts for the presentations of the section "Student Research Seminar Schedule" appear on the following pages.

Abstracts are listed in order of presentation, with simultaneous talks shown on opposing pages.

8:30 AM – 8:50 AM SESSION A ROOM G124

CeO2 Supported Ni-based Catalysts Prepared by Solution Combustion Synthesis for H2 Generation from N2H4∙H2O

Wooram Kang Prof. Arvind Varma

Hydrous hydrazine (N2H4·H2O) is a promising hydrogen carrier for proton exchange membrane (PEM) fuel cell vehicles, owing to its high hydrogen content (8.0 wt.% for hydrazine monohydrate), stable liquid state at ambient temperature, moderate reaction temperature (20-80 °C), and benign byproduct (only nitrogen) via complete decomposition reaction. Since the catalytic decomposition of hydrous hydrazine proceeds by two different pathways [complete decomposition (N2H4 → N2+2H2) and incomplete decomposition (3N2H4 → 4NH3+N2)], and even small ammonia amount is poison for PEM fuel cells, the development of cost-effective catalysts with high activity and 100% selectivity towards hydrogen generation under mild conditions is a significant challenge for its practical use.

In this study, CeO2 supported Ni-based nanopowders as noble metal free catalysts were prepared by solution combustion synthesis (SCS), which is a rapid and simple method to fabricate a variety of metal and metal oxide materials with uniform composition and porous structure.1,2 By varying the SCS synthesis parameters such as ratio of precursor oxidizers (nickel nitrate and ammonium cerium nitrate), fuel-to-oxidizer ratio (ϕ) and fuel type (hydrous hydrazine and glycine), the correlation between combustion characteristics, physicochemical and catalytic properties was investigated in detail. The tailored Ni/CeO2 catalysts with the optimized synthesis condition exhibited 100% H2 selectivity in the temperature range 30-70 °C and the highest catalytic activity among all prior reported catalysts containing Ni alone, owing to its highly porous structure and the enhanced strong metal-support interaction (e.g., formation of oxygen vacancy in CeO2 lattice).3 In addition, CeO2 supported Ni-Cu, Ni-Fe and Ni-Co bimetallic catalysts were synthesized using SCS. The synergistic effect to enhance activity for the reaction was found for the NiCu/CeO2 catalysts. Its turnover frequency at 50 °C was 5.4-fold higher as compared to that of the monometallic Ni/CeO2 and H2 selectivity remained at 100%. Detailed characterization revealed the reasons for the synergistic effect observed for the NiCu/CeO2 catalysts.

References:

[1] Varma, A.; Mukasyan, A.S.; Rogachev, A.S.; Manukyan K.V. Chem. Rev. 2016, 116, 14493.

[2] Kang, W.; Ozgur, D.O.; Varma, A. ACS Nano Mater. 2018, 1, 675.

[3] Kang, W.; Varma, A. Appl. Catal. B 2018, 220, 409.

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8:30 AM – 8:50 AM SESSION B ROOM B124

Manipulating Energy Transfer between a Photoexcited Conjugated Polymer and Open-Shell Small Molecules

Daniel A. Wilcox Prof. Bryan W. Boudouris

Organic electronic materials and devices are offering new perspectives on the modern energy conversion and storage landscape. The commercialization of organic light-emitting devices (OLEDs) and the potential associated with the low-cost production of other electronic devices (e.g., batteries, sensors, and photovoltaics) has resulted in significant interest in these materials.1 To date, most organic electronic devices utilize molecules with extensive π-conjugation, which allows for charge conduction through the stabilization of ionized states on the molecule. Due to the significant research investments in this initial wave of organic electronics research, molecular design rules for closed-shell conjugated polymers as well as the interactions between different conjugated species are relatively well understood. However, this same methodology has not been extended to open-shell (i.e., radical-containing) organic electronic systems, which conduct charge through electron self-exchange reactions between individual localized radical sites. This is despite the promising performance that many of these materials have shown in organic batteries and spintronics applications, as well as in active interfacial layers and dopants in other organic electronic devices.2 While radical-based materials are now being used in conjunction with conjugated polymers, the fundamental interactions and energy transfer events in these hybrid composites must be fully deciphered to better establish the potential application space of these novel materials.

Specifically, the behavior of the excited states in conjugated polymer systems can be understood by evaluating their fluorescent behavior. In a system of two different molecular species, the quenching (or extinguishing) of fluorescence is a direct reflection of their intermolecular interactions. Here, for the specific conjugated polymer poly(3-hexylthiophene) (P3HT), which has served as an oft-used material in many organic electronic applications, we demonstrate that Förster Resonance Energy Transfer (FRET) is the primary mechanism by which the fluorescence quenching occurs for radical species that absorb light strongly within the visible range, and that radical species with low optical density do not show significant quenching behavior. While quenching behavior has been reported for non-absorbing radicals that were covalently linked to their respective fluorophore,3 this work establishes a means by which energy transfer between these two classes of materials can occur at a greater distance. Thus, the results shown have significant implications in the strategic development of coupled closed-shell conjugated polymer-radical molecule systems, enabling a much wider material space to be explored for various applications.

References: [1] Meller, G.; Grasser, T. Organic Electronics; Springer: Heidelberg/New York, 2010.

[2] Wilcox, D. A.; Agarkar, V.; Mukherjee, S.; Boudouris, B. W. Stable Radical Materials for Energy Applications. Annu. Rev. Chem. Biomol. Eng. 2018.

[3] Green, S. A.; Simpson, D. J.; Zhou, G.; Ho, P. S.; Blough, N. V. Intramolecular Quenching of Excited Singlet States by Stable Nitroxyl Radicals. J. Am. Chem. Soc. 1990, 112 (20), 7337–7346.

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Catalytic Consequences of Spatial Distribution, Mobility, and Solvation of Active Sites on Ammonia Selective Catalytic Reduction of Nitric Oxide over Cu-Zeolites Ishant Khurana Prof. Fabio H. Ribeiro

NOx selective catalytic reduction (SCR) using NH3 as a reductant over Cu-SSZ-13 zeolites is a commercial technology used to meet emissions targets in lean-burn and diesel exhaust. In order to optimize the catalyst design parameters, detailed molecular level understanding of structurally different active Cu sites, reaction kinetics, and mechanism is essential. In addition, these Cu sites are required to retain SCR performance after both exposures to hydrothermal conditions (T > 923 K and ~7% H2O (v/v)) and sulfur poisoning. We have demonstrated that Cu in Cu-SSZ-13 speciates as two distinct sites viz. divalent Cu(II) and monovalent [Cu(II)(OH)] complexes exchanged at paired Al and isolated Al sites, respectively, with a preferential population of divalent Cu(II) sites. This was proven over a wide range of zeolite chemical composition by employing synthetic, spectroscopic (Infrared and X-ray absorption) and titrimetric analysis of Cu sites under ex situ conditions and in situ and operando SCR conditions. These structurally different Cu sites have different susceptibilities to H2 and He reductions but have been found to catalyze NOx SCR reaction at similar turnover rates (per Cu2+; 473 K) via. Cu(II)/Cu(I) redox cycle, as their structurally different identity is masked by NH3 solvation during reaction. [1]

Figure 1: Proposed low temperature SCR catalytic cycle

Molecular level insights on low temperature standard SCR (473 K) Cu(I)/Cu(II) redox mechanism have been gained with the help of experiments performed in-situ and operando coupled with theoretical calculations (Figure 1). Evidence has been provided to show that O2-oxidation during standard SCR Cu(I)/Cu(II) redox cycle requires two Cu(I)(NH3)2 sites, which is enabled by NH3 solvation conferring mobility to isolated Cu(I) sites, allowing dynamic interaction between two Cu(I)(NH3)2 species. As a result, standard SCR rates depend on Cu cation spatial distribution in Cu-SSZ-13 zeolites when Cu(I) oxidation steps are kinetically-relevant, but are independent of Cu spatial distribution otherwise. [2]

References:

[1] Paolucci, C; Parekh, A; Khurana, I. et al. J. Am. Chem. Soc., 138, 6028–6048 (2016)

[2] Paolucci, C; Khurana, I. et al., Science 357, 898–903 (2017)


Synthesis and Evaluation of Novel Thin-Film Solar Cell Materials: A Case Study of Cu3AsS4 Need spacing for uniformity

Scott McClary Prof. Rakesh Agrawal

The ubiquity of solar radiation makes it an ideal candidate to perpetually supply humankind’s energy needs for the foreseeable future. Thin-film solar cells (TFSCs) convert sunlight directly into electricity and are heavily researched due to high efficiencies, usage in flexible configurations, and amenability to solution processing. Cadmium telluride and copper indium gallium diselenide currently dominate the TFSC market, but the low abundance of elements In and Te suggest that substantial production of such devices cannot be maintained indefinitely. Copper zinc tin sulfoselenide (CZTSSe), which is comprised of abundant elements, was initially promising for TFSC applications, but its efficiencies have saturated primarily due to Cu-on-Zn and Zn-on-Cu antisite defects, which form readily due to the similar sizes of Cu and Zn.

As such, it is imperative to develop new TFSC materials that consist of earth abundant elements, have excellent optoelectronic properties, and are relatively defect-free. Many groups have used density functional theory (DFT) to rapidly screen materials and identify those that are promising for TFSCs.1,2 One of the most attractive compounds is Cu3AsS4 in the orthorhombic enargite (ENG) crystal structure. Previous works have predicted band gaps between 1.3 and 1.4 eV, absorption coefficients exceeding 105 cm-1, and a low concentration of defects due to the dissimilar ionic radii of Cu+, As5+, and S2-. However, experimental confirmation of the DFT calculations and prototype TFSCs have not yet been reported.

This talk will first detail the synthesis of the first ENG thin films and their incorporation into TFSCs.3 Through a novel method involving sintering of Cu3AsS4 nanoparticles in an As2S5 atmosphere, thin films with micron-sized dense grains were formed, likely due to the presence of a liquid consisting primarily of As and S. These films were incorporated into TFSCs with efficiencies of 0.35%, a promising result considering the presence of a carbonaceous secondary phase and poor band alignment at the pn junction.

The second portion of the talk will evaluate the long-term potential of Cu3AsS4. To avoid repeating the development path of CZTSSe (i.e. investing significant research funding only to discover inherent material limitations), fundamental properties of Cu3AsS4 were measured. Characteristics such as mobilities, carrier lifetimes, and defect concentrations were estimated using techniques like Hall effect measurements, time-resolved photoluminescence, and photoluminescence. The results suggest that Cu3AsS4 can achieve high efficiencies, so continued research is fully justified. Additionally, the methods used to evaluate Cu3AsS4 can be extended to other novel materials to identify promising candidates for future TFSCs.

References:

[1] L. Yu, R. S. Kokenyesi, D. A. Keszler and A. Zunger, Adv. Energy Mater., 2013, 3, 43–48.

[2] T. Shi, W.-J. Yin, M. Al-Jassim and Y. Yan, Appl. Phys. Lett., 2013, 103, 152105.

[3] S. A. McClary, J. Andler, C. A. Handwerker and R. Agrawal, J. Mater. Chem. C, 2017, 5, 6913–6916.

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Density Functional Theory Studies of Atomic Layer Deposition on LiMn2O4 Lithium Ion Battery Cathodes Need spacing

Robert Warburton Prof. Jeffrey Greeley

Despite the development of many promising lithium ion battery (LIB) electrode materials in recent years, scientific and technological bottlenecks remain that must be solved for many of these materials to realize their full potential. As an example, undesired side reactions between the electrode and the electrolyte lead to significant performance degradation upon extended cycling. Understanding and controlling these reactions is therefore a critical step towards the development of LIBs with enhanced chemical stability. In particular, transition metal (TM) dissolution is a capacity fade process that is widespread among various cathode materials. To address this shortcoming, protective surface coatings have been shown to enhance capacity retention through mitigated TM dissolution, although there remains a lack of understanding regarding the fundamental nature of their efficacy.

In this work, first principles density functional theory (DFT) calculations are used to evaluate the mechanism of protective film growth by atomic layer deposition (ALD) on spinel LiMn2O4 (LMO), a cathode for which the problem of Mn dissolution is well-documented. The prototypical reaction sequence of alternating trimethylaluminum (TMA) and H2O half-reactions for Al2O3 film growth is used as a model ALD reaction. DFT calculations and in-situ experiments suggest significant decomposition of the TMA precursor in early ALD cycles, leading to site blocking and sub-monolayer coverages of the Al2O3 coating. These partial coating show enhanced performance in comparison to uncoated LMO as well as fully conformal films obtained through further ALD cycles.1 Further DFT calculations are performed on the thermodynamically stable2 low-index (001) and (111) terraces, in addition to (511) steps, demonstrating structure-sensitive precursor decomposition to the more reducible step and defect sites on LMO. These results suggest film nucleation is likely to proceed at the more reducible features on LMO electrode particles, which are also more susceptible to Mn dissolution. These trends help provide an explanation for enhanced cycling performance with only 1-2 ALD cycles. We will address how the trends outlined for the TMA/H2O system can be extended to control the onset of film growth based on precursor selection.

Acknowledgements: The Center for Electrochemical Energy Science, an Energy Frontier Research Center; Purdue Research Computing; Center for Nanoscale Materials; Laboratory Computing Resource Center; National Energy Research Scientific Computing Center.

References:

[1] Chen, L.; Warburton, R. E.; Chen, K.-S.; Liberia, J. A.; Johnson, C.; Yang, Z.; Hersam, M. C.; Greeley, J. P.; Elam, J. W.; Mechanism for Al2O3 Atomic Layer Deposition on LiMn2O4 Studied by in-situ Measurement and Density Functional Theory Calculations. Chem 2018 (in press).

[2] Warburton, R. E.; Iddir, H.; Curtiss, L. A.; Greeley, J. P.; Thermodynamic Stability of Low- and High-Index Spinel LiMn2O4 Surface Terminations. ACS Appl. Mater. Interfaces 2016, 8 (17), 11108-11121.

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Temperature Dependent Electrochemical Performance and Safety Aspects of Graphite Anodes for K-ion and Li-ion Batteries

Ryan A. Adams Prof. Arvind Varma, Prof. Vilas G. Pol

Rechargeable lithium-ion batteries (LIBs) are currently the dominant electrical energy storage technology with widespread usage in portable electronics and electric vehicles due to their high energy density and reasonable lifetime. However, the scarcity and poor distribution of Li resources limits the scalability of this technology in the future, especially for large scale applications such as grid storage of renewable energy (e.g. solar and wind). Thus, researchers have become interested in alternative alkali metal-ion chemistries, replacing Li with Na, and more recently K, for applications where kWh $-1 is more important than energy density.[1] These batteries operate with an analogous mechanism to LIBs, with intercalation storage between cathode and anode in a non-aqueous electrolyte. Despite the larger size of the cation, potassium has some key advantages over sodium, with a higher operating voltage, increased mobility in electrolyte due to its weaker Lewis acidity, and a working graphite anode.[2]

With K-ion battery (KIB) research still in its infancy, there remain many challenges to address. For example, the effect of operating temperature on KIBs remains completely unexplored. It is known that operating temperature plays a significant role in the electrochemical performance of LIBs, cell lifetime, and safety.[3] At low temperatures, reduced power capability results from the sluggish kinetics, and safety concerns arise from possible Li plating and dendrite formation. At elevated temperatures, accelerated battery aging occurs due to irreversible growth of the solid electrolyte interphase (SEI) layer. Thermal runaway can also occur at elevated temperatures, due to the exothermic degradation of SEI and metastable electrodes in the presence of the flammable organic electrolyte.

Motivated by these concerns, we evaluate and compare the effect of operating temperature on electrochemical performance for graphite anode for Li-ion and K-ion chemistries. Investigations into cell aging, polarization, rate capability, and safety are carried out over the operating temperature range of 0°C - 40°C, with kinetic parameters determined for solid-state diffusion, charge-transfer resistance, and SEI layer resistance. A full cell system comprising Prussian blue cathode and graphite anode is tested to evaluate the performance of a practical battery, removing the issues of the K metal counter electrode. These results provide insight into the energetics of K+ intercalation in graphite for the emerging K-ion battery chemistry, and the influence of the intercalation cation on electrochemical behavior.

References:

[1] Eftekhari, A. et al. ACS Appl. Mater. Interfaces 2017, 9, 4404–4419.

[2] Komaba, S. et al. Electrochem. commun. 2015, 60, 172-175.

[3] M.-T.F. Rodrigues, M.-T.F. et al. Nat. Energy. 2017, 2, 17108.

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Nature of SO2-poisoning on ZCuOH and Z2Cu sites in Cu-SSZ-13 during the NH3 Selective Catalytic Reduction (SCR) of NOx

Arthur J. Shih Prof. Fabio H. Ribeiro

Reduction of NOx emissions from diesel engine exhaust is an environmental issue driven by increasingly stringent regulations. Cu-SSZ-13 catalysts are used commercially for this application. Although their hydrothermal stability is better than other zeolite catalysts, they are still susceptible to deactivation by SOx formed from the combustion of ppm levels of sulfur present in diesel fuel. We report on the effects of SO2-poisoning on the two active sites responsible for selective catalytic reduction, Cu2+ and CuOH [1,2].

Two Cu-SSZ-13 catalysts, one with only Cu2+ active sites (3.8 Cu wt%, 100% Cu2+) and another with primarily [CuOH]1+ active sites (1.5 Cu wt%, 80% CuOH) were synthesized [3]. Our model Cu2+ and [CuOH]1+ catalysts were sulfated with dry SO2 at 200°C until 5 times as many moles of SO2 than moles of Cu was flown through, resulting in molar S:Cu ratios of 0.3 and 0.7, respectively. Consistent with the measure of higher affinity of sulfur to [CuOH]1+, density functional theory (DFT) calculations indicate that the binding energy of SO2 on Cu2+ and [CuOH]1+ are -30 and -90 kJ mol-1, respectively. Sulfation decreased the SCR rate (300 ppm NO, 300 ppm NH3, 60% O2, 2% H2O, 8% CO2, balance N2, 200°C normalized per total moles Cu) by 26% for the Cu2+ catalyst and 64% for the [CuOH]1+ catalyst. Reaction rates are constant when normalized to the number of non-poisoned Cu sites (moles Cu – moles S) for all samples collected under the same reduction-limited regime (Eapparent = 65 ± 5 kJ mol-1), which indicates that sulfur deactivates Cu sites at a 1:1 S:Cu molar ratio on both Cu2+ and [CuOH]1+ active sites. The coordination environment probed by UV-Visible indicate that sulfur-Cu interactions were observed on [CuOH]1+but not on Cu2+. Thus, though sulfur poisons both Cu2+ and [CuOH]1+ sites at a 1:1 molar ratio, we spectroscopically observe that sulfur interacts directly with [CuOH]1+ but not with Cu2+.

Cu2+ sites are preferred over [CuOH]1+ sites as SO2-resistant sites for SCR because it has less affinity for SO2 as evidenced by theoretical DFT calculations and experimental elemental analysis. Reaction kinetics indicate that each SO2 poison binds to only one Cu site while all other non-poisoned Cu sites continue to turn over normally. These results predict that synthesizing catalysts with higher fractions of Cu2+ sites will lead to improved emission control catalysts for commercial applications.

References:

[1] Jangjou, Y.; Do, Q.; Gu, Y.; Lim, L.-G.; Sun, H.; Wang, D.;Kumar, A.; Li, J.; Grabow, L.C.; Epling, W.S. ACS Catal. 2018, 8, 2.

[2] Luo, J.; Wang, D.; Kumar, A.; Li, J.; Kamasamudram, K.; Currier, N.; Yezerets, A. Catal. Today 2016, 267, 3.

[3] Paolucci, C.; Parekh, A.A.; Khurana, I.; Di Iorio, J.R.; Li, H.; Albarracin Caballero, J.D.; Shih, A.J.; Anggara, T.; Delgass, W.N.; Miller, J.T.; Ribeiro, F.H.; Gounder, R.; Schneider, W.F. J. Am. Chem. Soc. 2016, 138, 18.

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Constant-Pattern Design Method for Separating Ternary Mixtures of Rare Earth Elements Using Ligand-Assisted Displacement Chromatography

Hoon Choi Prof. Nien-Hwa Linda Wang

The rare earth elements (REEs) consist of the 15 elements of the lanthanide series, yttrium, and scandium. REEs are important components of many high-tech products, and as a result, the demand for REEs is growing. Traditionally, REEs are mined from ores that contain a mixture of several different elements. For most applications, high purity of a single REE is required, so the ores must be separated and purified. However, since REEs have similar physicochemical properties, the separation and purification is a challenging and expensive process. Ligand-assisted displacement chromatography (LAD) was developed to separate REEs in the 1950s and 1960s using commercially available ion exchange sorbents and ligands. While previous studies have demonstrated the feasibility of LAD for separating REEs with high purity (>99%) and high ligand efficiency, the productivity for these experiments were very low. Without a systematic process to design and optimize LAD systems with mass transfer effects, LAD systems were designed using a trial and error approach.

In this study, a constant-pattern design method is developed to separate REEs with high purity and high productivity for a given target yield. When the mixed band regions in a LAD system reach a constant pattern state, the yields of high purity products will be maximized. A general map was developed to show the relationship between the minimum column length to reach a constant pattern state and key dimensionless groups, which include selectivity, loading fraction, cut, and overall mass transfer coefficients. Given a target yield, intrinsic parameters, and material properties, operating conditions were calculated using the general map without trial and error. The design method was verified experimentally for different target components, yields, ligand concentrations, and feed compositions. The yields of the target components were within 3% of the expected values, demonstrating the robustness of the design method. High purity (>99%) of REEs were obtained from experiments with two orders of magnitude (x800) higher productivity than literature results. In cases with a minimum required yield, the component with the lowest feed concentration can be the limiting component, even in cases where it does not have the lowest selectivity.

References:

[1] H. Choi, D. Harvey, D. Yi, N.L. Wang, Key parameters controlling the development of constant-pattern isotachic trains of two rare earth elements in ligand-assisted displacement chromatography, Journal of Chromatography A. 1563 (2018) 47–61

[2] H. Choi, D. Harvey, D. Yi, N.L. Wang, Constant-pattern design method for the separation of three rare earth elements using ligand-assisted displacement chromatography. Journal of Chromatography A, (under review: JCA-18-1167)

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Pt-Co Catalysts for Alkane Dehydrogenation: Structural Effects on Selectivity Need spacing for uniformity

Laryssa G. Cesar Prof. Jeff T. Miller

The demand for light olefins has increased in the last years, due to its role in industry as chemical building blocks for polymers production. Allied to this, the boom in shale gas exploitation motivated the development of new on-purpose technologies, such as propane dehydrogenation (PDH). In this process, Pt-based catalysts are commonly used, due to their higher selectivity and lower coke formation compared to other active transition metals [1]. These properties are enhanced by the formation of bimetallic catalysts with non-active metals, as Sn and In [2]. It’s believed that the increase in selectivity is due to the change in the catalyst crystalline structure, showing the influence of the geometric effect over propylene selectivity. Evidence shows that these bimetallic catalysts form intermetallic compounds, i.e. ordered alloy phases, and the Pt3M phase is the most common among these catalysts. This same phase can be achieved with Pt and active metals such as Co and Fe [2,3].

Therefore, the goal of this research is to study the performance of Pt-Co catalysts for PDH. The experiments were performed by synthetizing a series of bimetallic Pt-Co catalysts, with different Co loadings. The catalysts were screened for catalytic activity and characterized using X-Ray Diffraction and X-Ray Absorption Spectroscopy, at Argonne National Lab.

The results showed that, despite being an active metal, Co promoted the Pt active sites by increasing the activity to over 90% among all different loadings at 20% conversion. These catalysts are believed to have formed both the Pt3Co and PtCo alloy phases, with Pt-Pt Coordination numbers between 5 and 7, at 2.7 Å bond distance. Therefore, this enhanced behavior in selectivity is consistent with the Co atoms acting as a non-active promoter upon alloying, in similar way as other promoters previously reported [2,3].

References:

[1] Sattler, J. J. H. B et al. Catalytic Dehydrogenation of Light Alkanes on Metals and Metal Oxides. Chem. Rev. 114, 10613–10653 (2014).

[2] Wu, Z. et al. Pd–In intermetallic alloy nanoparticles: highly selective ethane dehydrogenation catalysts. Catal. Sci. Technol. 6, 6965–6976 (2016)

[3] Wegener, E. C. et al. Structure and reactivity of Pt-In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenation. Catal. Today (2016).

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Interfacial Tension and Phase Behavior of Oil-Aqueous Systems with Applications to Enhanced Oil Recovery Need spacing

Jaeyub Chung Prof. Bryan W. Boudouris, Prof. Elias I. Franses

In order to facilitate the mobilization of trapped oil in porous reservoirs by injecting a surfactant solution for enhanced oil recovery (EOR), it is critical to have low or ultralow (< 10-2 mN·m-1) interfacial tension (IFT) values between a crude oil and the surfactant aqueous solution before and after significant interphase mass transfer has occurred. We report on the surface tension (ST) and IFT of un-pre-equilibrated mixtures of aqueous surfactant solutions and a crude oil, and the IFT and phase behavior of pre-equilibrated mixtures. The surfactant used here is a commercial anionic surfactant, PETROSTEP S-13D HA, which is a single-extended-isopropoxylated-chain sodium sulfate salt. The synthetic brine used is similar to the one present in an actual oil reservoir. It primarily contains 9,700 ppm of NaCl.1 The crude oil samples used were obtained from an actual oil reservoir and were purified slightly with centrifugation and filtration. The dynamic and equilibrium STs have a simpler adsorption mechanism than the dynamic IFTs (DIFTs), involving diffusion from the aqueous phase and adsorption/desorption. The results suggest that the tension equilibrations with a commercial surfactant were associated with the typical adsorbed soluble monolayers at the interfaces with negligible solubilization effects.1 For pre-mixed systems, the apparent phase behavior at 22 ± 2 °C, and the IFTs were found to depend strongly on the mixing methods and on the water-to-oil volume ratio (WOR) used.2 For all systems, two phases were observed for all mixing methods: (a) mild mixing, (b) magnetic stirring, and (c) shaking vigorously by hand. With water, the equilibrium IFTs (EIFTs) between the pre-equilibrated phases were similar to the un-pre-equilibrated EIFT. However, with brine solutions, there was significant surfactant transfer from the aqueous phase to the oil phase with the method (c) relative to the other methods. Moreover, as the WOR was varied from 2.33 to 0.43, the pre-equilibrated EIFTs increased. The surfactant concentration at the aqueous layer decreased significantly from the original values. The results indicate that changes in the relative concentrations of the various components in both phases lead to significant changes in mixtures, and hence, to major EIFT changes.2 These results have significant implications for screening surfactants for use in EOR processes. A spectrum of EIFTs, rather than a single IFT value, characterizes a certain formulation. As the aqueous solution that is injected into a reservoir undergoes potential phase equilibration the effective WOR decreases. Then, the IFT and the partitioning of the various components in the various phases change. These phenomena should be considered in designing EOR processes. In simulations of EOR processes and interpretation of core flood and field test results, one should consider the effect of wide variation of the IFT and the surfactant partitioning in the oil phase on the surfactant losses and the overall recovery efficiency.

References [1] Chung, J.; Boudouris, B. W.; Franses, E. I. Colloids Surfaces A Physicochem. Eng. Asp. 2018, 537, 163–172. [2] Chung, J.; Yang, Y.-J.; Tang, H.; Santagata, M.; Franses, E. I.; Boudouris, B. W. Colloids Surfaces A Physicochem. Eng. Asp. 2018, 554, 60-73.

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11:40 AM – 12:00 PM SESSION A ROOM G124

23

Influence of Confining Environment Polarity on Ethanol Dehydration Catalysis by Lewis Acid Zeolites

Jason Bates Prof. Rajamani Gounder

Lewis acidic Sn-Beta zeolites containing different silanol defect density and framework metal site coordination (open: (HO)-Sn-(OSi≡)3, closed: Sn-(OSi≡)4) have been recognized to behave catalytically different in reactions of oxygenated compounds. In aqueous-phase glucose isomerization, titration and quantification of sites in Sn-Beta zeolites using pyridine and CD3CN [1], together with theoretical estimates of 1,2-intramolecular hydride shift activation barriers [2], indicate that open sites are the dominant active sites. Furthermore, glucose isomerization initial rate constants (373 K, per open Sn) are >10× higher for open sites confined within Sn-Beta-F (fluoride-mediated, low-defect) than Sn-Beta-OH (hydroxide-mediated, high-defect) [1], which has been ascribed to the presence of extended hydrogen-bonded water structures that increase activation free energies in high-defect pores. Here, we employ gas-phase ethanol dehydration as a probe reaction to clarify the kinetic consequences of defect density in the absence of bulk solvent effects, and assess the influence of reaction conditions on active Sn site coordination.

Sn sites in open and closed configurations, quantified from infrared spectra of adsorbed CD3CN before and after reaction, convert to structurally similar intermediates during ethanol dehydration catalysis (404 K) and revert to their initial configurations after regenerative oxidation treatments (21% O2, 803 K).Dehydration rate data (404 K, 0.5–35 kPa C2H5OH, 0.1–50 kPa H2O) measured on ten low-defect (Sn-Beta-F) and high-defect (Sn-Beta-OH) zeolites were described by a rate equation that was derived frommechanisms identified previously by density functional theory calculations and simplified using microkinetic modeling to identify kinetically-relevant pathways and intermediates. Polar hydroxyl defect groups located in the microporous environments that confine Sn sites preferentially stabilize reactive (ethanol-ethanol) and inhibitory (ethanol-water) dimeric intermediates over monomeric ethanol intermediates. As a result, equilibrium constants (404 K) for ethanol-water and ethanol-ethanol dimer formation are 3–4× higher on Sn-Beta-OH than on Sn-Beta-F, consistent with insights from single-component (302 K) and two-component (303 K, 403 K) ethanol and water adsorption measurements. Intrinsic dehydration rate constants (404 K) were identical, within error, among Sn-Beta-OH and Sn-Beta-F zeolites; thus, measured differences in dehydration turnover rates solely reflect differences in prevalent surface coverages of inhibitory and reactive dimeric intermediates at active Sn sites. The confinement of Lewis acidic binding sites within secondary microporous environments of different defect density confers the ability to discriminate surface intermediates on the basis of polarity, providing a design strategy to accelerate turnover rates and suppress inhibition by water.

References:

[1] Harris et al., J. Catal. 335 (2016) 141–154.

[2] Bermejo-Deval et al., Proc. Natl. Acad. Sci. 109 (2012) 9727–9732.

11:40 AM – 12:00 PM SESSION B ROOM B124

Approaching the Nature of Glass Transition as Probed by Dynamic Mechanical Analysis of Polymers Need spacing

Yelin Ni Prof. James Caruthers

Glass has ancient origins but a high-tech future. Yet the nature of glass and the glass transition remains an unsolved problem in solid state physics. Most apparently, there is a contradiction between two basic facts about the glass:

• The microstructure of a glass is indistinguishable from that of a liquid (i.e. no long-range order).• The shear modulus of a glass is that of a solid under the conventional rates of deformation.

As a representative material, polymeric glass is researched in this project with designed chemical structure and convenient test conditions. The most straightforward way to quantify glass transition is by measuring the change in mechanical properties such as modulus. As compared to transient tests (e.g., stress-strain behaviors under a constant strain-rate loading), dynamic mechanical analysis (DMA) is more sensitive and informative. In a strain-controlled DMA experiment, a sinusoid signal of strain is applied to the specimen. The corresponding stress signal will be measured, typically showing a phase shift with regards to the input strain signal. The in-phase and out-of-phase part each reveals storage modulus G’ and loss modulus G”.

Prediction of both G’ and G” simultaneously can be a challenge for any constitutive model, even in its simplest case, i.e., in the linear viscoelastic range where stress and strain are proportional. With generalized Maxwell model and Tikhonov regularization, the G’ and G” dataset can be fit and the corresponding relaxation spectrum near and above glass transition region (defined as “α+ region”) is reveals. Conventionally, the glass transition (also called “α relaxation”) is described as a continuous process characterized by a single-broad peak. Here I’m going to show that with finer discretization in my model, the spectrum evolves from a single-broad peak or a convoluted shoulder on α peak to one or more clearly separated, single-relaxation-time Debye peaks. The presence of discrete Debye processes in α+ region is also observed for a variety of materials, including polymers and small-molecular glass formers. After ruling out several plausible mechanisms, the hypothesis being currently investigated is that (i) the relaxation processes in α+ region is an extension of glass transition, (ii) in a unified α+ and α regions the relaxation processes are discrete.

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2:00 PM – 2:20 PM SESSION A ROOM G124

Articular Cartilage Defect Repair with a Collagen Type I and II Blend Hydrogel in vitro and in vivo Need spacing

Claire Kilmer Prof. Julie C. Liu and Prof. Alyssa Panitch

Osteoarthritis (OA) is a debilitating condition that affects over 27 million people in the United States alone and is defined by degradation in articular cartilage extracellular matrix (ECM). Although there is no cure for OA, there are many treatment options including osteochondral grafting and autologous chondrocyte implantation. However, these options promote the growth of fibrocartilage, which is inferior to the mechanical properties of native, hyaline cartilage. Tissue engineering seeks to repair damaged cartilage by introducing an optimized combination of cells, scaffold, and bioactive factors that can be transplanted into a patient. Collagen hydrogels are an attractive option for tissue engineered scaffolds since collagen is biocompatible and can take on any desired defect shape. Collagen type I (Col I) continues to be the most utilized type of collagen in tissue engineered scaffolds even though collagen type II (Col II), which is the most abundant type of collagen produced by chondrocytes, is considered to be the ideal environment for culturing chondrocytes. Col II has been shown to promote the secretion of ECM molecules specific to cartilage and induce cartilage repair. However, when compared to Col I, Col II exhibits poor mechanical properties when forming a hydrogel without chemical crosslinking.

This study aimed to investigate the chondrogenic differentiation potential of bone marrow-derived MSCs embedded within a 3:1 collagen type I to II blend hydrogel (Col I/II) or an all collagen type I hydrogel (Col I) in vitro. A DMMB assay for glycosaminoglycans (GAGs) revealed that there was a statistical increase inthe GAG production in the Col I/II hydrogels as compared to high-throughput pellets cultured in chondrogenic media (CM), suggesting that the addition of collagen type II promotes GAG production. At each time point, the Col I/II hydrogels had statistically less AP activity as compared to the pellets cultured in CM, and statistically less AP activity than the Col I hydrogel at Day 14 and Day 21, suggesting that Col I/II hydrogels provide a less hypertrophic environment and do not allow differentiation into early bone. The ability of MSCs to undergo chondrogenesis when encapsulated in a collagen type I and II blend gel was investigated in vivo. Two defects were created in the femur of New Zealand White rabbits and filled with either a Col I/II or Col I hydrogel scaffold embedded with autologous bone marrow-derived MSCs. After 13 weeks, histochemical staining suggests that the Col I/II blend hydrogel provides favorable conditions for cartilage repair. Histological scoring, using the O’Driscoll scoring system, revealed a statistically higher cartilage repair score for the Col I/II hydrogels as compared to the Col I hydrogels and the empty defect controls in both locations investigated. Results from this study suggest that there is a clinical value in the cartilage repair capabilities of our Col I/II hydrogel with encapsulated MSCs.

References:

[1] Lu, Z.; Doulabi, B. Z.; Huang; C., Bank, R. A; and Helder, M. N. Tissue Eng. Part A. 2010, 16, 81.

[2] Vazquez-Portalatin, N.; Kilmer, C. E.; Panitch, A.; and Liu, J. C. Biomacromolecules. 2016, 17, 314.

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2:00 PM – 2:20 PM SESSION B ROOM B124

Coffee Eye Effect: the Formation of Stagnation Points during Drop Evaporation and the Influence on Particle Deposition

Lihui Wang Prof. Michael T. Harris

Particle deposition in drop evaporation happens in many industrial applications including spray coating, inkjet printing, fabrication of functional nanomaterials and disease diagnosis. The deposition is a self-assembly process affected by various reasons, one of which is the microfluidic flow. Understanding the fluid mechanics of this process is crucial to elucidating and controlling deposition patterns of these applications.

Unlike the ubiquitous “coffee ring” effect, a “coffee eye” pattern was obtained in the experiments of nanoparticle deposition in water drop evaporation. The “coffee ring” is named to describe the ring-like pattern left by a spill of coffee after it evaporates. The “coffee eye” is a combination pattern of a thick central stain and a thin outer ring.

While the cause of a coffee ring is the capillary flow in the direction of the periphery of the evaporating droplet, the coffee eye pattern indicates a different flow pattern: beside the outward capillary flow, there also exists an inward Marangoni flow. This Marangoni flow results from the surface tension change caused by evaporative cooling. The two kinds of flow in opposite directions form a stagnation point in between. The stagnation point was also observed by the track of nanoparticles under microscopy.

The numerical results of the finite element method simulation gave a clear view of the development of the flow pattern with stagnation points. The stagnation point emerges near the contact line at the late stage of evaporation. The position of the stagnation point from the numerical results agreed with that of the experimentally observed stagnation point. The simulation was further validated by the lubrication theory, showing that the stagnation point was produced by the competing effects of the capillary flow and the Marangoni flow. The competing effects give a better explanation to the formation of the “coffee eye” deposition pattern.

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Deciphering the Molecular Mechanisms Involved in the Transport of Volatile Organic Compounds in the Epicuticle of Plant Epidermal Cells

Shaunak Ray Prof. John Morgan

Plants produce a wide diversity of volatile organic compounds (VOCs) that serve roles in the attraction of pollinators and seed dispersers, defense against pathogens and herbivores, and in plant-plant signaling. While research on volatiles has traditionally focused on the biosynthetic pathways and their individual function, how these compounds translocate through subcellular tissue is less established. One significant barrier to the transport of plant volatiles is the cuticle, the outermost layer of the plant epidermis. Transport of volatiles through the cuticle is solely reliant on diffusion, and is thus dependent on the cuticle physicochemical properties. Biologically synthesized wax compounds are exported from epidermal cells into the cuticular matrix where they self-assemble into a multiphase system of crystalline and amorphous regions, with their relative amounts and arrangements governing the diffusivity of volatiles.

We hypothesize that the relative composition of various wax compounds has a measurable impact on both the cuticle ultrastructure and volatile emission rates. To test these hypotheses in planta, we modify the floral waxes of Petunia hybrida by two separate approaches: (i) we overexpress an Arabidopsis thaliana transcription factor AtMYB106 known to regulate cuticle biosynthetic pathways [1], and (ii) down-regulate PhABCG12 encoding for a plasma membrane-bound ATP-binding cassette (ABC) transporter known to export waxes and lipids from epidermal cells [2]. Cuticles of these Petunia mutants were isolated and analyzed for wax content and composition, and compared to wild-type flowers. Screened mutant petal cuticle ultrastructures were subsequently characterized using Fourier-transform infrared spectroscopy (FTIR) and X-Ray diffraction (XRD) to identify changes in molecular arrangements and crystallinity. Dynamic headspace collections of volatiles revealed that the generated Petunia mutants have perturbed emission rates, correlating to changes in floral wax composition. By using a combination of metabolic engineering with physical and analytical chemistry, this study provides insight into the role petal cuticles serve in floral emissions of flowering plant species.

References:

[1] Oshima, Y., Shikata, M., Koyama, T., Ohtsubo, N., Mitsuda, N., Ohme-Takagi, M. (2013) MIXTA-like transcription factors and WAX INDUCER1/SHINE1 coordinately regulate cuticle development in Arabidopsis and Torenia fournieri. Plant Cell 25: 1609-1624

[2] McFarlane H.E., Shin, JJ., Bird D.A., Samuels, A.L. (2010) Arabidopsis ABCG transporters, which are required for export of diverse cuticular lipids, dimerize in different combinations. Plant Cell 22, 3066-3075

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The Effect of Scale-Up on Mixing Efficiency in Oscillatory Flow Reactors Using Principal Component Image Analysis as a Novel Noninvasive Residence Time Distribution Measurement ToolJoseph Oliva Prof. Zoltan K. Nagy

Oscillatory flow strategies through baffled tubular reactors provide an efficient approach in improving process kinetics through enhanced micromixing and heat transfer1. Known to have high surface area to volume ratios, oscillatory flow baffled reactors (OFBR) generate turbulence by superimposing piston driven oscillatory flow onto the net flow generated by a pump. By tuning the oscillating parameters (amplitude and frequency), one can tailor the residence time distribution of the system for a variety of multiphase applications2,3. Using a microscope camera, principal component image analysis, and pulse tracer injections, a novel noninvasive approach has been developed to experimentally estimate dispersion coefficients in two geometrically different systems (DN6 and DN15, Alconbury Weston Ltd.). Similarly, a comprehensive experimental investigation of the effect of oscillation parameters on the residence time distributions (RTD) is discussed in both systems. The oscillation amplitude was found to have a significant positive correlation with the dispersion coefficient with 1 mm providing the least amount of dispersion in either system. Oscillation frequency had a less significant impact on the dispersion coefficient, but optimal operation was found to occur at 1.5 Hz for the DN6 and 1.0Hz for the DN15. Until now, OFBR literature has not distinguished between piston and pump driven flow. Pump driven flow was found to be ideal for both systems as it minimizes the measured dispersion coefficient. However, piston driven turbulence is essential for avoiding particle settling in two phase (solid-liquid) systems and should be considered in two phase applications such as crystallization.

To further understand how operating parameters affect system flow conditions, a computational fluid dynamics model was developed. Found to have good agreement with experimental validation, the CFD model further explains how system geometry and oscillation conditions drastically affect the size and shape of eddies generated, ultimately impacting the measured dispersion coefficient. The CFD model also sheds light on how the RTD of the system is (indirectly) dependent on temperature and mass diffusivity. Using a combined experimental and computational approach, optimal operating conditions were determined for each system.

References:

[1] Stonestreet, P., & Harvey, A. P. (2002). A Mixing-Based Design Methodology for Continuous Oscillatory Flow Reactors. Chemical Engineering Research and Design, 80(January), 31–44.

[2] Kacker, R., Regensburg, S. I., & Kramer, H. J. M. (2017). Residence time distribution of dispersed liquid and solid phase in a continuous oscillatory flow baffled crystallizer. Chemical Engineering Journal, 317, 413–423.

[3] Ni, X., & Pereira, N. E. (2000). Parameters Affecting Fluid Dispersion in a Continuous Oscillatory Baffled Tube. AIChE Journal, 46(1), 37–45.

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1

A Modeling Framework to Individualize Hydroxyurea Based Treatment of Sickle Cell Patients

Akancha Pandey Prof. Doraiswami Ramkrishna, Prof. Sangtae Kim

Hydroxyurea (HU) is the current FDA approved drug for sickle cell disease treatment. Though several studies have indicated that the drug is effective in ameliorating disease pathophysiology, its use is limited due to myelosuppression and uncertainties associated with its long-term safety. Use of hydroxyurea presents major challenges to clinicians in terms of wide interpatient variability in pharmacokinetic-pharmacodynamic (PK-PD) profiles, cytotoxicity, lack of an effective biomarker to predict treatment efficacy and consequently lack of optimal dosing regimen for individual patients.

A pharmacokinetic model is developed that describes drug concentration in the gastrointestinal tract, plasma, and tissue where the drug gets metabolized into nitric oxide and its derivatives. The model explains the trend of hydroxyurea in plasma in agreement with literature [1-3]. Fetal hemoglobin (HbF) and mean cell volume (MCV) of red blood cells (RBCs) have been used clinically as biomarkers to indicate treatment efficacy. A preliminary signaling model that captures fetal hemoglobin dynamics is formulated based on the hypothesis that HU activates HbF through NO-cGMP pathway. The model incorporates species varying on different timescales. To quantify toxicity, leukopoiesis process is modeled where stem cells undergo biochemical and morphological changes to produce fully functional leukocytes in the blood circulation. The PK model is integrated with the signaling model and the hematopoiesis model to characterize kinetics with both efficacy and toxicity. Through integrated PK-PD model, we seek to predict the individual patient PK-PD trajectory and answer questions such as why some of the patients do not respond, why some of the patients respond well for the same amount of dose. Another major issue which plagues the entire treatment process is non-adherence where patients do not take the drug. It is difficult to differentiate non-adherence from treatment inefficacy, as non-adherent patients might mislead clinicians into believing that treatment at the current dose level is insufficient. In this case, the dose might be increased but once the patient starts adhering to the dose, the excess dose might prove to be harmful. Non-adherent patients are modeled where the patients are missing dose on certain days and its effect on dynamics of hydroxyurea present in the plasma, its metabolites and fetal hemoglobin is studied and compared with adherent patients’ PK-PD trajectory. This will facilitate in formulating a strategy to differentiate non-adherence and treatment inefficacy.

References:

[1] Rodriguez, G. I. et al. A bioavailability and pharmacokinetic study of oral and intravenous hydroxyurea. Blood 91, 1533–1541 (1998).

[2] Ware, R. E. et al. Pharmacokinetics, pharmacodynamics, and pharmacogenetics of hydroxyurea treatment for children with sickle cell anemia. Blood 118, 4985–4991 (2011).

[3] Gwilt, P. R. et al. Pharmacokinetics of hydroxyurea in plasma and cerebrospinal fluid of HIV-1-infected patients. J. Clin. Pharmacol. 43, 1003–1007 (2003).


Advancing smart manufacturing in continuous processing of oral solid doses

Sudarshan Ganesh Prof. Gintaras Reklaitis and Prof. Zoltan Nagy

Continuous manufacturing of drug product is the outcome of systematic integration of product and process knowledge, instrumentation and automation systems, quality control protocols and real-time process management for a solids processing system handling pharmaceutical materials. The highly instrumented process equipment along with PAT tools have facilitated real-time product quality monitoring, improved process understanding and the advancement towards plant-wide automation. This progress has promoted the advance towards smart manufacturing for oral solid doses to leverage the advancements in integrated systems and knowledge management for optimal utilization of plant assets and achieve operational excellence via model-based automation, multivariate data analytics, and predictive and preventive maintenance.

Success in smart manufacturing for sustainable process operations and quality risk assessment necessitate reliable and accurate measurements from field devices combined with good quality estimates of unmeasured process variables [1]. Overcoming the challenges in the implementation of PAT tools for sustainable operations require the integration of process models through the application of data reconciliation and gross error detection for superior real-time data accuracy. In addition, the integration of process equipment, sensors and analytics platform with the control system requires a setup in accordance with automation standards for ensuring operational excellence.

This presentation discusses an integrated framework, consisting of the sensor network and the implementation considerations for smart manufacturing in continuous pharmaceutical process operations. A dry granulation based continuous tableting processes is first characterized for feasibility in continuous process operations. Inline measurements from a continuous dry granulation process are used to demonstrate the implementation of data reconciliation and gross error detection for model-based validation and improved monitoring accuracy [2]. The case studies are performed in an ISA-95 structured pilot plant at Purdue University. Finally, the concept of quality-by-control [3] is demonstrated as the integrated platform to advance smart manufacturing in pharmaceutical systems.

References:

[1] Bagajewicz MJ. Smart Process Plants: Software and Hardware Solutions for Accurate Data and Profitable Operations. McGraw-Hill, 2009

[2] S. Ganesh, M. Moreno, J. Liu, M. Gonzalez, Z. Nagy, G. Reklaitis. Sensor Network for Continuous Tablet Manufacturing. Comp. Aided. Chem. Engg., Proceedings of the 13th International Symposium on Process Systems Engineering – PSE 2018, San Diego, CA 2018.

[3] Q. Su, M. Moreno, A. Giridhar, G. Reklaitis, Z. Nagy. A Systematic Framework for Process Control Design and Risk Analysis in Continuous Pharmaceutical Solid-Dosage Manufacturing. J Pharm Innov. 2017

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31

Structural Effect of PdZn Surfaces on CO and Propylene Adsorption Need spacing for uniformity in line spacing

Cory Milligan Prof. Fabio Ribeiro

Due to the shale gas boom, propane dehydrogenation (PDH) is poised to be one of the most important reactions of the 21st century. [1] One of the more promising industrially relevant class of catalysts are intermetallic compounds where a highly active but poorly selective metal is alloyed with an inactive metal to improve both stability and selectivity, for instance palladium and zinc. [2] In order to obtain a more detailed level of understanding of these types of catalysts, five structurally distinct intermetallic PdZn model surfaces were prepared and analyzed using a variety of surface sensitive techniques. The techniques used include scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS).

The model surfaces were prepared using a chemical vapor deposition (CVD) approach exposing Pd(111) and Pd(100) single crystals to 450 L of diethylzinc (DEZ) with the substrate held in a temperature range of 373K – 473K. Further annealing of the surfaces in ultra-high vacuum (UHV) lead to clean and well-ordered intermetallic surfaces. Three of these surfaces directly correspond to low index planes of the β1-PdZn crystal structure which has been identified as the crystal structure of the supported PDH catalysts. [2]

Chemical properties towards CO adsorption were compared for different PdZn surface structures at 130 K. On the Pd(111) surface, CO adsorbs on 3-fold, 2-fold bridge and linear positions. On the Pd(100) surface, 2-fold bridge COads was detected. On PdZn alloy surfaces, CO was found only on the zig-zag and β1-PdZn(010) structures. On the zig-zag surface, adsorption sites of COads are similar to those on Pd(111). On the other hand, only linear COads was observed on β1-PdZn(010) surface. CO adsorption was completely suppressed on FCC-p(2×1), β1-PdZn(111) and β1-PdZn(001) structures. These results match those seen on the supported technical catalysts where CO adsorption is strongly destabilized and almost exclusively adsorbs in the linear binding position. [2]

The adsorption properties of propylene, the desired product of PDH, were also investigated on different PdZn surface structures at 130 K. Propylene is known to adsorb on palladium surface through the π complex. On the other hand, propylene adsorption is strongly destabilized on the PdZn alloy surfaces: hydrocarbon fragments were found only on one of the five model surfaces, the zig-zag surface. These results give potential insights to the enhanced catalytic properties of the intermetallic class of PDH catalysts.

References:

[1] Q. Wang, X. Chen, A. N. Jha, H. Rogers, Renew. Sust. Energ. Rev. 30, 1-28 (2014).

[2] J. R. Gallagher, D. J. Childers, H. Y. Zhao, R. E. Winans, R. J. Meyer, J. T. Miller, Physical Chemistry Chemical Physics 17, 28144-28153 (2015).


Dropwise Additive Manufacturing for Pharmaceutical Products utilizing non-Brownian Suspensions Need spacing

Andrew J. Radcliffe Prof. Zoltan K. Nagy, Prof. Gintaras V. Reklaitis

In recent years, a changing business environment, regulatory encouragement, and novel contributions from academic/industrial researchers have spurred the pharmaceutical industry toward realization of improvements in manufacturing efficiency and product quality through implementation of on-line process analytical technologies, predictive process models and advanced production methods. As part of this transition, adaptations of drop-on-demand inkjet printing technology, which rely on material jetting to deposit individual droplets, have been the focus of much academic and industrial research for the extent of control of drug product properties enabled by precision dispensing of small volumes of active ingredient or excipient. As inherently flexible processes, these methods present advantages in a variety of applications related to production of low dose drugs, creation of novel drug formulations and integration with continuous or semi-continuous manufacturing strategies.

Recent works from academic and industrial researchers have demonstrated the utility of dropwise additive manufacturing processes for production of oral solid doses using printing materials based on drug solutions and eutectic melts. As an alternative to solutions or melts, we present the use of a dropwise additive manufacturing system for dispensing of micrometer-size (1-250μm) particle suspensions, thereby enabling the process to serve as a flexible method for dosing of active pharmaceutical ingredient powders produced by conventional crystallization or milling operations. In support of this, we present a framework for drop printing with non-Brownian particle suspensions in which the effects of non-ideal particle properties, suspension formulation and process conditions on performance metrics are quantified through a set of experiments that investigate aspects of the drop formation dynamics using high-speed photography and image analysis [1, 2]. With feasible conditions identified, oral solid doses are produced and analyzed for the mass/composition uniformity and for the extent of preservation of particle size through the process [2]. Thereafter, we discuss the development of methods to address sources of uncertainty introduced to the process/products by particle suspensions and provide a preview of future works [3].

References:

[1] A.J. Radcliffe, G.V. Reklaitis, Dropwise Additive Manufacturing using Particulate Suspensions: Feasible Operating Space and Throughput, Computer Aided Chemical Engineering, Proc. of the 27th European Symposium on Computer Aided Process Engineering (ESCAPE), Vol. 40, 1207-1212, 2017.

[2] A.J. Radcliffe, J.L. Hilden, Z.K. Nagy, G.V. Reklaitis, Dropwise Additive Manufacturing of Pharmaceutical Products using Particle Suspensions, Journal of Pharmaceutical Sciences, (In review).

[3] A.J. Radcliffe, G.V. Reklaitis, Bayesian Estimation of Product Attributes from On-line Measurements in a Dropwise Additive Manufacturing System, Computer Aided Chemical Engineering, Proc. of the 28th ESCAPE , Vol. 43, p 1243-1248, 2018.

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Controlled Heteroatom Insertion into Zeolite Framework Vacancy Defects and Catalytic Consequences for Glucose Isomerization

Juan Carlos Vega-Vila Prof. Rajamani Gounder

Alternative synthesis routes to hydrothermal crystallization of Sn-Beta zeolites have focused on the post-synthetic incorporation of stannic precursors within framework vacancy defects in dealuminated supports via vapor-phase deposition [1], solid-state ion exchange [2], and liquid-phase grafting under isopropanol reflux [3], each with different consequences for the density and coordination of framework Sn atoms and density of residual silanol defects. Moreover, glucose-to-fructose isomerization rates (per total Sn, 373 K) measured on post-synthetic Sn-Beta samples decrease systematically with increasing Sn content, which has been rationalized by intrazeolite transport limitations [3], T-site specific reactivity [3], or different open ((HO)-Sn-(OSi)3) and closed (Sn(OSi)4) site densities [4].

We report that grafting Sn heteroatoms in dichloromethane solvent (333 K) enables preparing Sn-Beta zeolites comprising higher framework Sn densities (Si/Sn = 30-144) [5] than reported for liquid-phase grafting procedures performed in isopropanol reflux (Si/Sn > 120) [3], because Sn incorporation is limited during isopropanol reflux (383 K) by competitive adsorption of isopropanol at vacancy defects, consistent with IR and TPD evidence [5]. As a result, dichloromethane-assisted grafting of stannic chloride into vacancy defects provides a route to prepare Sn-Beta zeolites with controlled densities of framework Sn and residual vacancy defects. IR spectra of Sn-Beta samples titrated with CD3CN (303 K) was used to quantify the distribution of Sn heteroatoms in an open and closed configuration [6], providing evidence that open Sn sites are formed preferentially at low Sn framework densities. Thus, first-order glucose-to-fructose isomerization rate constants (373 K) decreased systematically with increasing Sn content when normalized to the total number of Sn atoms. Isomerization rate constants (373 K) normalized to open Sn sites, however, were invariant (within 2x) among Sn-Beta samples prepared via liquid-phase grafting in dichloromethane reflux (333 K), highlighting the single-site behavior of open framework Sn sites in post-synthetically prepared Sn-Beta for glucose isomerization [5]. Vapor-phase CH3OH adsorption isotherms (293 K) of Sn-Beta zeolites of varied Sn content and residual density of vacancy defects suggest that removing internal hydrophilic binding sites may increase glucose-to-fructose isomerization rate constants (per open Sn, 373 K) for post-synthetically prepared solid Lewis acids. These findings clarify the effect of reflux solvents on grafting procedures and highlight the need to quantify active sites in order to rigorously normalize rate data prior to kinetic or mechanistic interpretation. References: [1] P. Li et al., J. Phys. Chem. C 115 (2011) 3663-3670. [2] C. Hammond et al., Angew. Chem. Int. Ed. 51 (2012) 11736-11739. [3] J. Dijkmans et al., J. Catal. 330 (2015) 545-557. [4] W.N.P. van der Graaff et al., ChemCatChem 7 (2015) 1152-1160. [5] J.C. Vega-Vila et al., J. Catal. 344 (2016) 108-120. [6] J.W. Harris et al., J. Catal. 335 (2016) 141-154.

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Process Intensification and Control in Pharmaceutical Manufacturing Need spacing for uniformity in title length

Pal Kanjakha Prof. Zoltan K. Nagy

Pharmaceutical Manufacturing of solid oral dosage forms is done mostly in batch mode as a sequence of discrete unit operations carried out sequentially. With increasing costs of drugs, there is a consensus that the manufacturing costs need to be reduced to brings down the price of the marketed drugs. Process Intensification combines a number of unit operations by lumping some of the fundamental rate processes occurring in different unit operations into a single unit operation. This leads to decreased capital and operating costs which ultimately brings down the cost of manufacturing the drugs.

The typical sequence of unit operations in pharmaceutical manufacturing involves crystallization, filtration, drying, milling, granulation, blending followed by tablet press. In this research endeavor, the idea has been to delete three energy-consuming steps in manufacturing – milling, granulation and blending and carry out the four manufacturing stages in a single stage – the Spherical Agglomeration stage. A combined approach of experimentation along with in-silico design was used to get mechanistic insights into the process. Process Analytical Technologies were also used to get understanding of the fundamental rate processes of nucleation, growth and agglomeration to demystify the complex mechanism of Spherical Agglomeration. After the correct mechanistic in-silico model was identified, a framework was designed to precisely estimate the model parameters by reducing the volume of the uncertainty ellipsoid in which the parameters lie – the goal was to extract maximum amount of information from each experiment and reduce the number of experiments needed to get the optimal parameters.

Maintaining the product quality within very tight bounds is vital to the pharmaceutical industry since drug dosages are critical for the in-vivo efficacy of the drug. A major drawback of batch manufacturing is the inconsistency between two batches which ultimately leads to the rejection of many batches; the ultimate price is paid by the patients who end up paying more for the drugs. In any industrial process uncertainties are always present which come from unmodeled disturbances or plant-model mismatch. A Model Predictive Control Algorithm was designed which controls the final drug product quality within very precise bounds even in the presence of unmodeled disturbances.

Summarily, a Process Intensification unit operation was designed which reduces the cost of pharmaceutical manufacturing and makes the process development faster, more efficient and robust.

References:

[1] Pitt et al., Particle Design via Spherical Agglomeration : A critical review of controlling parameters, rate processes and modeling, Powder Technology, 326(2018), 327-343

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First Principles Modeling of Site Interconversion in Lewis Acid Zeolites for Ethanol Dehydration Need spacing

Brandon C. Bukowski Prof. Jeffrey P. Greeley

The structure of active sites in microporous Lewis acid zeolites is investigated using first principles DFT and microkinetic modeling to quantify the mechanism and abundant surface intermediates for ethanol dehydration reactions to form diethyl ether1. One complexity to elucidating reaction mechanisms in Lewis acid zeolites is the speciation of heteroatoms, which comprise the catalytic active site, between closed (tetravalent coordination to the framework) and so-called “open” (addition or replacement of Sn-framework bonds with a hydroxyl ligand) sites2. These open sites are proposed to be the active site for a variety of oxygenate chemistries3. Gas phase reactions, such as ethanol dehydration, provide a more direct approach to the structure and abundance of active sites in the absence of liquid solvent. The presence of which obscures intrinsic kinetics and introduces additional complexity in the generation of computational models. The structural complexities of confining pore environments are distinct from supported metal nanoparticles, necessitating accurate techniques to consider the entropic contributions of reactive intermediates. When exploring a reaction network, the large number of parallel reactions and side products complicate the accurate calculation of entropies. Thus, a tiered algorithm using sensitivity criteria is applied to a microkinetic model allowing the identification of key reactive intermediates and transitions states. These key intermediates can then be refined with more accurate entropy estimates. The reaction orders and rates calculated from the model compare well to experimentally measured kinetics at the same conditions. The modeling results quantify the surface coverages of key intermediates, inaccessible to experimental measurements, allowing for the derivation of an analytic rate expression.

Modeling results show that the formation of open sites is quasi-equilibrated under reaction conditions, and the equilibrium coverage of these sites is less than one percent. The sole kinetically relevant pathway is through closed Sn sites which form ethanol dimers with favorable hydrogen bonding. The bimolecular dehydration transition state adopts an SN2 mechanism where the angle of attack expected from classical SN2 reactions is strained by the confining pore environment. Inhibition by water is found to proceed through stable ethanol-water dimer species which form on closed Sn sites. Results from ethanol dehydration are then used to begin mapping out a reaction network for butadiene synthesis using design principles based on similar tiered modeling approaches.

References:

[1] Bukowski, B.C.; Bates, J.S.; Gounder, R.; Greeley, J. J. Catal. 2018.

[2] Boronat, M.; Concepcion, P.; Corma, A.; Renz, M.; Valencia, S. J. Catal. 2005.

[3] Luo, H.Y.; Consoli, D.F.; Gunther, W.R.; Roman-Leshkov, T., J. Catal 2014.

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36

Poster Showcase Guide

No Title Authors

1 Conducting Radical Polymers for Organic Electronics Siddhartha Akkiraju, Varad Agarkar, Daniel Wilcox, Yongho Joo, Kuluni Perera, Xikang Zao and Bryan Boudouris

2 Constant Pattern Design of Ligand-Assisted Displacement Chromatography for the Separation of Rare Earth Elements

David Harvey, Hoon Choi, Yi Ding, and Nien-Hwa Linda Wang

3 Optimal Mapping Scheme for Bottom-Up Coarse-Graining Methods Aditi Khot, Stephen B. Shiring, and Brett M. Savoie

4 Prospecting for New Polymers: Combining Physics-based and Empirical Model towards Accelerating Discovery

Nicolae Iovanac, Brett M. Savoie

5 Higher Capacity Composite Anodes for Safer Rechargeable Lithium ion Batteries Mihit Parekh, Vihang Parikh, Patrick Kim, Shikhar Misra, Haiyan Wang, and Vilas G Pol

6 Macromolecular Transport through Nanoporous Membranes Noelia Almodovar, Bryan Boudouris and David Corti

7 Sustainable Electrode Materials for Next Generation Energy Storage Devices Ryan Adams, Vihang P. Parikh, Palanisamy Manikandan, Vilas G. Pol

8 Chondrogenic Differentiation of Mesenchymal Stem Cells in Collagen Blend Hydrogels

Claire Kilmer, Abigail Durkes, Gert J. Breur, Alyssa Panitch, and Julie C. Liu

9 Formulation Design of a Protein-Based Surgical Sealant Jessica Torres, Sydney Hollingshead, and Julie Liu

10 Radiation-Controlled Chemotherapeutic Release Formulations for Intratumoral Chemo-Radio Combination Therapy for Locally Advanced Head and Neck Tumors

Kaustabh Sarkar, Rahul Misra, Vincenzo Pizzuti, You Yeon Won

11 Enhanced aromatic amino acid production using cyanobacteria Arnav Deshpande, Jeremiah Vue and John Morgan

12 A Redox-Sensitive Kinetic Model of the Calvin Cycle in Synechocystis sp. PCC 6803 Nathaphon Yu King Hing, John Morgan

13 Population Balance Model for Cooling Crystallization of Carbamazepine Claire Y. Liu, David Acevedo, Xiaochuan Yang, Wei-lee Wu, Eleazar Wong, Sean Naimi, Naresh Pavurala, Celia Cruz, Thomas O'Connor, and Zoltan K. Nagy

14 Advancing smart manufacturing in pharmaceutical systems Sudarshan Ganesh, Mariana Moreno, Yash Shah, Qinglin Su, Marcial Gonzalez, Zoltan K. Nagy, and Rex Reklaitis

15 MiniPharm: A Miniaturized Pharmaceutical Manufacturing Platform for Process Development

Jaron Mackey, Ahmad Mufti,Edward Barks, Andy Koswara, and Zoltan K. Nagy

16 Process Intensification and Control in Pharmaceutical Manufacturing Kanjakha Pal, Zoltan K. Nagy

17 Vesicle Dynamics Under Complex Flows Charlie Lin, Vivek Narsimhan

18 Dynamics of Multicomponent Suspensions in Viscoelastic Fluids Cheng-Wei Tai, Vivek Narsimhan

19 Hydrodynamic singularities in free surface flows Brayden Wagoner, Vishrut Garg, Hansol Wee, Pritish Kamat, and Christopher Anthon and Osman Basaran

20 Interfacial Tension, and Phase Behavior of Oil/Aqueous Systems with Applications to Enhanced Oil Recovery

Jaeyub Chung, Yung-Jih Yang, Huiling Tang, Marika Santagata

21 Are membranes always more energy efficient than distillation? Jose Adrian Chavez Velasco, and Rakesh Agrawal

22 DistOpt: A Software for Optimal Multicomponent Distillation Column Sequencing Parham Mobed, Tony Joseph Mathew, Rakesh Agrawal, and Mohit Tawarmalani

23 Sustainable coproduction of food and solar power to relax land use constraints Yiru Li, Caleb Miskin, Allison Perna, Ryan Ellis, Elizabeth Grubbs, Peter Bermel and Rakesh Agrawal

24 Solution–Processed Thin-film Photovoltaics via Nanocrystal Inks and Molecular Solutions for Scalable, Low-Cost Manufacturing

David Rokke, Kyle Weideman, Swapnil Deshmukh, Ryan Ellis, Joseph Andler, Scott McClary, Essam AlRuqobah, Xianyi Hu, and Rakesh Agrawal

25 Process Synthesis for Light Alkane Transformation to Liquid Fuel Peter Oladipupo, Zewei Chen, Jeffrey J. Sirola, and Rakesh Agrawal

26 Facilitating the Revitalization of the U.S Petrochemical and Fuels Industries: Basic Research Aimed at Sustainable Development of America’s Light Hydrocarbon Resources

Rakesh Agrawal, W. Nicholas Delgass, Rajamani Gounder, Jeffrey Greeley, Jeffrey Miller, Fabio Ribeiro, Jeffrey Siirola, and Arvind Varma

27 Center for the Innovative and Strategic Transformation of Alkane Resources. Fabio Ribeiro, Monica Cardella, Michael Harris, Peter Keeling, and Adrian Thomas

28 Mechanistic details of Ethylene Dimerization catalyzed by Nickel cations Ravi Joshi, Guanghui Zhang, Jeffrey Miller and Rajamani Gounder

29 Catalytic Consequences of Spatial Distribution, Mobility, and Solvation of Active Sites on NOx Selective Catalytic Reduction (SCR) with NH3 over Cu-Zeolites

Ishant Khurana, Atish A. Parekh, Arthur J. Shih, Christopher Paolucci, Jonatan D. Albarracin-Caballero, W. Nicholas Delgass, Aleksey Yezerets, Jeffrey T. Miller, William F. Schneider, Rajamani Gounder,and Fabio H. Ribeiro

30 The Formation of Pt3Cr Intermetallic Alloys Nicole LiBretto, Jeff Miller

31 Catalysis at Metal/Oxide Interfaces: Pt/MgO for Water Gas Shift Reaction Pushkar G. Ghanekar, Jeffrey P. Greeley

32 Direct Oxidative Conversion of Methane to Liquid Oxygenates over Bimetallic Pt-Cu Catalysts

Rexonni B. Lagare, Yang Xiao, and Arvind Varma

33 The Dominant Role of Entropy in Stabilizing Sugar Isomerization Transition States within Hydrophobic Zeolite Pores

Michael J. Cordon, James W. Harris, Juan Carlos Vega-Vila, Jason S. Bates, Sukhdeep Kaur, Mohit Gupta, Megan E. Witzke, Even C. Wegener, Jeffrey T. Miller, David W. Flaherty, David D. Hibbitts, and Rajamani Gounder

The names of the presenters are highlighted in bold. The presenters for poster no 26 and 27 are Taufik Ridha and Stephen Purdy.37

Acknowledgments

The Graduate Student Organization would like to thank the following

companies for their financial support and attendance at the 27th Annual Graduate Research Symposium. Without their support, this

event would not have been possible:

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39

Notes

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Notes

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