1st International Symposium on Energy Chemistry & Materials, Oct. 29‒31 2015, Fudan University, Shanghai, China

Selective Aldol Condensation of Biomass-Derived Levulinic Acid and

Furfural in Aqueous Phase

Guanfeng Liang, Aiqin Wang*, Tao Zhang*

aState Key Laboratory of Catalysis, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese

Academy of Sciences, Dalian, 116023, China.

*Correspondence to: aqwang@dicp.ac.cn, taozhang@dicp.ac.cn

ABSTRACT

Utilization of lignocellulosic biomass for production of fuels and chemicals is of great importance to decreasing the dependence on fossil resources and minimizing CO2 emissions. In the past ten years, various approaches have been developed towards the efficient utilization of biomass. Among others, the production of diesel or jet fuel range long-chain alkanes via the C-C bond coupling of biomass-derived platform molecules and the subsequent hydrodeoxygenation (HDO) reactions has attracted great attention. In particular, the C-C bond coupling step is not only the key reaction to provide precursors with extended carbon chains for biofuel, it can also directly produce high value-added chemicals from biomass feedstock. In this presentation, we for the first time report the aldol condensation of furfural with levulinic acid in aqueous phase over MgO and ZnO solid catalysts. Two isomeric condensation products, β- and δ- furfurylidenelevulinic acid (β- and δ-FDLA) were produced, but the selectivity was strongly dependent on the nature of the solid catalysts. MgO showed the highest activity for aldol condensation, reaching 70.6 % yield of δ-FDLA. In contrast, β-FDLA was obtained as major product on ZnO (75.5% yield with 95.8% conversion). The aldol reactions on MgO and ZnO were supposed to proceed via two fundamentally different mechanisms. The formation of δ-FDLA on MgO followed typical base-catalyzed mechanism, while the formation of β-FDLA on ZnO followed the acid-catalyzed mechanism. In-depth investigations revealed that exposed surface hydroxyl groups on ZnO worked as active sites for aldol reaction.

P1-1

Hydrogenolysis of glycerol to 1,3-propanediol under low H2 pressure: a

good use of H2 over highly isolated Pt/WOx catalyst

Xiaochen Zhaoa, Jia Wanga, Aiqin Wang*a, Tao Zhang*a

a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese

Academy of Sciences, Dalian 116023,PR China. aqwang@dicp.ac.cn

taozhang@dicp.ac.cn;

ABSTRACT

Glycerol, the byproduct of biodiesel and soap, is available in surplus amounts and calls for efficient valorization to high value-added chemicals.1 Owing to its high oxygen content (C/O=1), selective hydrogenolysis, whereby C-O bonds is cleaved or undergo “lysis” by hydrogen, is considered an atom economy and cost competitive process.2 Among the products, 1,3- propanediol (1,3-PD) is the most desirable one due to its wide application as monomer in polyester industry (polytrimethylene terephthalate (PTT)). Nevertheless, this reaction is rather challenging, for the formation of 1,2-propanediol (1,2-PD) is more thermodynamically favourable than 1,3-PD. In aqueous phase glycerol hydrogenolysis, to date, Pt-W and Ir-Re catalysts appear to be the only effective catalysts with high selectivity to 1,3-PD instead of to 1,2-PD. 1

Highly isolated Pt/WOx catalyst was prepared by employing mesoporous WOx as the support. Its large surface area and abundant oxygen vacancies help improve the Pt dispersion and stabilize the Pt isolation. This novel catalyst exhibited outstanding hydrogenolysis activity under 1MPa H2 pressure with the highest time-space-yield towards 1,3-propanediol (3.78 g g-1Pt h-1) in Pt-W-containing catalysts to date. The highly isolated structure was supposed to contribute to the superior H2 dissociation capacity over Pt/WOx. The high selectivity towards 1,3-propanediol was assigned to the bonding between glycerol and WOx, which favoured/stabilized the formation of secondary carbocation in intermediate, as well as triggered the redox cycle of W species (W6+ ↔W5+). Meanwhile, the hydroxyl groups on tungsten atoms associated with Pt can provide specific Brønsted acid sites, which also take part in the hydrogenolysis of glycerol.

REFERENCES

[1] Nakagawa, Y.; Tamura, M.; Tomishige, K., J Mater Chem A 2014, 2, 6688. [2] Ruppert, A. M.; Weinberg, K.; Palkovits, R., Angew Chem Int Ed 2012, 51, 2564.

P1-2

Single-atom Pd1-graphene achieved by atomic layer deposition:

remarkable performance in selective hydrogenation of 1,3-butadiene

Huan Yan, Hao Cheng, Hong Yi, Yue Lin, Tao Yao, Chunlei Wang, Junjie Li, Shiqiang

Wei,* and Junling Lu*

Department of Chemical Physics, National Synchrotron Radiation Laboratory, Collaborative Innovation Center of Chemistry for Energy Materials (iChem), Hefei

National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Materials for Energy Conversion, University of Science and Technology of China, Hefei,

Anhui 230026 (P. R. China) junling@ustc.edu.cn

ABSTRACT

Atomically dispersed noble metal catalyst has attracted rapidly increasing attention

due to its unique catalytic properties and maximized atom efficiency for low-cost.[1-2] Here, the obtained graphene oxide powder was carefully reduced via thermal

deoxygenation to precisely tune the type and amount of surface oxygen functional

groups (anchor sites selection). Then we fabricated a single-atom Pd catalyst on

graphene using the ALD technique. HAADF-STEM and EXAFS data confirm the

dominant presence of isolated Pd atoms on graphene. We also find that Pd single atom

catalysts show remarkable performance in selective hydrogenation of 1,3-butadiene

(butadiene hydrogenation in an excess of alkenes is an important industrial process to

purify the alkenes streams from petroleum cracking.[3]). Single atom catalyst achieves

high butene selectivity, especially 1-butene. The 1-butene selectivity is 71%, when the

conversion is up to 95%. Pd1/graphene shows excellent durability against deactivation

during a total 100 h of reaction time on stream without any visible activity decline or

selectivity change.[4]

Figure 1. a) Representive HAADF-STEM images of Pd1/graphene at low and high magnifications. b) the

K2-weighted Fourier transform spectra of different Pd catalyst. c) 1-butene selectivity as a function of 1,3-butadiene conversion on different Pd catalysts.

References

[1] Qiao,B.; Wang,A.; Yang,X.; Zhang,T. Nat. Chem. 2011, 3. 634.

[2] Lin,J.; Wang,A.; Qiao,B.; Zhang,T.; J. Am. Chem. Soc. 2013, 135. 15314.

[3] Derrien, M. L. Stud. Surf. Sci. Catal., 1986, 27. 613

[4] Yan,H.; Chen,H.; Yi,H.; Lin,Y.; Yao,T.; Wang,C.L. Li,J.J. Wei, S.Q.;Lu,J.L.;

accepted by JACS.

P1-3

Precisely Controlled Porous Alumina Overcoating on Pd Catalyst by

Atomic Layer Deposition: Enhanced Selectivity and Durability in

Hydrogenation of 1,3-Butadiene

Hong Yia, Hongyi Dua, Yingli Hub, Huan Yana, Hai-Long Jiangb, Junling Lua

aDepartment of Chemical Physics, Hefei National Laboratory for Physical Sciences at

the Microscale, iChEM, CAS Key Laboratory of Materials for Energy Conversion, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China

bDepartment of Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China

aE-mail: junling@ustc.edu.cn

ABSTRACT

Partial hydrogenation of dienes to mono-olefins is of great industrial importance.

Butadiene is an impurity from steam cracking. It will adsorb on the catalysts surface in

butene polymerization, deactivating the catalysts. Pd catalysts are often used to remove

butadiene from olefin stream due to its high activity, however, the selectivity to butenes

is poor, especially to 1-butene. Thus it is necessary to develop a catalyst to address this

problem. Recently, we have successfully improved the stability and selectivity of Pd

catalysts in oxidative dehydrogenation of ethane reaction by selectively blocking the

low coordination sites of Pd with porous alumina coating using atomic layer

deposition(ALD).[1-3]

Here we report that precisely controlled porous alumina overcoating on a Pd

catalyst using atomic layer deposition (ALD) not only remarkably enhances the

selectivity to butenes, especially to 1-butene, but also achieves the best ever durability

against deactivation in selective hydrogenation of 1,3-butadiene in the absence (or

presence) of propene. Therein no visible activity declines or selectivity changes were

observed during a total 124 h of reaction time on stream.[4]

REFERENCES

[1] Lu, J. et al. Science 2012, 335, 1205.

[2] Feng, H.; Lu, J.; Stair, P. C.; Elam, J. W. Catal. Lett. 2011, 141, 512.

[3] B.J. O'Neill et al. Angew. Chem. Int. Ed. 2013, 125, 14053.

[4] Yi,H. et al. ACS Catal. 2015, 5, 2735.

P1-4

Hydrogenation of CO2 into CH4 over Ru/TiO2 catalyst: A mechanism

consideration

Yanqiang Huang, Tao Zhang

Dalian Institute of Chemical Physics, CAS , Dalian, China, 116023 yqhuang@dicp.ac.cn

ABSTRACT

It is generally accepted that the interaction between metal and support plays a

critical role toward the catalytic performance of CO2 methanation [1]. The simplest

method for forming a strong interaction between metal and support is to treat a Ru/TiO2

catalyst at elevated temperatures in H2. However, the high-temperature treatment also

leads to particle growth, which is considered to be another important factor on the

catalytic performance of CO2 methanation [2]. This makes it difficult to independently

assess the real role of particle size and the interaction between metal and support. In the

present work, we surprisingly observed that rutile TiO2 was able to stabilize Ru nano

particles even with the rise of reduction temperature to 800 oC, which may be attributed

to the SMSI effect [3]. Therefore, the finely tuned interaction between Ru and TiO2 has

been demonstrated to be the sole reason of the enhanced CO2 methanation reaction

activity, but without the particle size effect. The calculated rate of TOF increased

significantly (from 0.26 s-1 as the catalyst reduced at 300 oC to 1.59 s-1 at 600 oC). In

addition, the CO2 methanation reaction mechanism has also been studied. We assume

that CO2 methanation proceeds with the formation of Ru-bonded carbonyl intermediates

at the interface of Ru and TiOx via a formate based dissociation mechanism through the

reverse water gas shift reaction.

REFERENCES

[1] Li, D. et al. Appl. Catal. A 1999.180. 227.

[2] Kwak, J. h.;et al. ACS Catal. 2013. 3. 2449.

[3] Lin, Q. Q.; et al.a Catal. Sci. Technol.2014. 4. 2058.

P1-5

1st International Symposium on Energy Chemistry & Materials, Oct. 29‒31 2015, Fudan University, Shanghai, China

Adsorbate-adsorbate Interaction Model for the Microkinetic Trend Studies of C1 Catalysis

Bo Yanga,b, Thomas Bligaardb, Jens K. Nørskovb

a�School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road,

Shanghai, 201210 b SUNCAT Center for Interface Science and Catalysis, Department of Chemical

Engineering, Stanford University, Stanford, 94305, USA; SLAC National Accelerator Laboratory, Menlo Park, 94025, USA

yangbo1@shanghaitech.edu.cn

ABSTRACT Presence of steps and edges has been proven to be important for catalytic reactions and in many cases these sites are the active sites transforming the reactants to products. The strong adsorption at the under coordinated step and edge sites leads to rather high coverages of the adsorbates. Hence the inclusion of adsorbate-adsorbate interactions can become important for catalytic activity descriptions. Here we propose a model to describe the interaction between the adsorbates adsorbed at two different sites of a same surface, since the metal nanoparticles in general consist of many different surface sites, such as terrace, steps, edges, kink and corners. For this study we have chosen the stepped (211) surface as our model surface. This surface consists of three different sites: steps, four fold and terrace. The adsorbate-adsorbate interaction model is parameterized for the (211) surface to find the correct parameters to describe the interaction between different adsorbates on a single surface consisting multiple sites. Three model reactions are selected, namely steam reforming and dry reforming of methane and CO metanation, in order to verify the 'multi-site model'. The volcanoes shown in Figure 1 are obtained for CO methanation. The difference in the formulation between the previous one-site interaction model and this newly proposed multi-site interaction model, along with the difference in predicted catalytic activities are discussed in detail.

Figure 1. CH4 formation rate in CO methanation as a function of the carbon (EC) and oxygen (EO)

binding energies.

P1-6

Selective Hydrogenation of Phenol to Cyclohexanone over Pd-HAP

Catalyst in Aqueous Media

Guangyue Xu a, Jianhua Guo a, Ying Zhang a*, Yao Fu a, Jinzhu Chen b, Longlong Ma b

and Qingxiang Guo a

a Collaborative Innovation Centre of Chemistry for Energy Materials, Anhui Province

Key Laboratory for Biomass Clean Energy and Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China.

b CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, P. R. China.

zhzhying@ustc.edu.cn

ABSTRACT

It is a great challenge to produce pure cyclohexanone under mild conditions over

catalysts with high reactivity, selectivity, compatibility, stability and low cost. Here we

report a hydroxyapatite-bound palladium catalyst (Pd-HAP) to show its excellent

performance on phenol hydrogenation to cyclohexanone. Based on characterization, the

Pd nano-clusters (~0.9 nm) are highly dispersed and bounded by phosphate in HAP.

Only basic active sites on HAP surface are detected. At 25 ºC and ambient H2 pressure

in water, phenol can be 100% converted into cyclohexanone with 100% selectivity. This

system shows a universal applicability to temperature, pH, solvent, low H2 purity and

pressure. The catalyst reveals high stability to be recycled without deactivation or

morphology change; and Pd nano-clusters barely aggregate even at 400 ºC. During

reaction, HAP adsorbs phenol, and Pd nano-clusters activate and spillover H2. The

mechanism is also investigated, proposed and verified. [1]

REFERENCES

[1] Xu,G.Y.; Guo,J.H.; Zhang,Y.; Fu, Y.; Chen, J.Z.;Ma ,L.L.; Guo, Q.X. ChemCatChem 2015, 7, 2485.

P1-7

Thermo-catalytic conversion and ammonization of biomass-derived

platform molecules

Qian Yaoa, Lujiang Xua, Ying Zhanga* and Yao Fua*

a Collaborative Innovation Center of Chemistry for Energy Materials, Anhui Province Key Laboratory for Biomass Clean Energy and Department of chemistry, University of

Science and Technology of China, Hefei, Anhui, China. zhzhying@ustc.edu.cn fuyao@ustc.edu.cn.

ABSTRACT

Chemical conversion of biomass to value-added products provides a sustainable

alternative to the current chemical industry that is predominantly dependent on fossil

fuels. N-heterocycles, including pyrroles, pyridines and indoles etc., are most abundant

and important classes of heterocycles in nature and widely applied as pharmaceuticals,

agrochemicals, dyes, and other functional materials. Here we developed a new

sustainable technique to thermo-catalytically convert biomass-derived platform

molecules (including furan, furfural and glycerol) with ammonia to a range of

N-heterocycles over commercial zeolite catalysts. We outlined the chemistry for the

conversion of biomass-derived platform molecules into N-heterocycle molecules by

addition of ammonia into pyrolysis reactors demonstrating how industrial chemicals

could be produced from renewable biomass resources.

REFERENCES

[1] Yao,Q.; Xu, L.; Han, Z.; Zhang, Y. Chem. Eng. J., 2015, 280, 74.

[2] Xu, L.; Jiang,Y.; Yao,Q.; Han,Z.; Zhang, Y.; Fu, Y.; Huber, G. W. Green Chem., 2015,

17, 1281.

[3] Xu, L.; Han, Z.; Yao, Q.; Deng, J.; Zhang, Y.; Fu, Y.; Guo, Q. Green Chem., 2015,

17, 2426.

P1-8

Studies of macroporous effects on Fischer-Tropsch synthesis using

cobalt catalyst over hierarchical Meso/macro sillica support

Hansheng Lia,b，Jungang Wang a,Bo Hou a ,Debao Li a

a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese

Academy of Sciences, Taiyuan 030001, Shanxi, PR China b University of Chinese Academy of Sciences,Beijing 100049, PR China

lihansheng7@sina.com wangjg@sxicc.ac.cn

ABSTRACT

In this paper，meso/macro sillica with mesoporous walls was prepared by sol-gel

process1 and was used to prepare Co/SiO2 catalyst via excessive impregnation method to support active metal cobalt on sillica.The prepared meso/macro sillica was separately grinded into 10-20 mesh and below 100 mesh. Co/SiO2-IM was prepared via excessive impregnation using meso/macro sillica（10-20 mesh）as support.Co/SiO2-IM-10-20 was kept 10-20 mesh and Co/SiO2-IM-60-80 was prepared by grinding Co/SiO2-IM-10-20 into 60-80 mesh. Co/SiO2-PIM was prepared via excessive impregnation using meso/macro sillica (below100 mesh) as support.The Co/SiO2-PIM was previously tableted to obtain a 60–80 mesh and 10-20 mesh labeled as Co/SiO2-PIM-60-80 and Co/SiO2-PIM-10-20. N2 adsorption/desorption, XRD, SEM, TEM, TPR, and Hg Intrusion techniques were used to characterize the support and (or) catalyst. The presence of macroporosity in Co/SiO2-IM-10-20 and Co/SiO2-IM-60-80 was confirmed by Hg intrusion analysis .However,there was no macroporosity in Co/SiO2-PIM-60-80 and Co/SiO2-PIM-10-20.The selectivity of methane was very close for Co/SiO2-PIM-60-80 and Co/SiO2-PIM-10-20.However，the selectivity of methane for Co/SiO2-IM-10-20 was much higher than Co/SiO2-IM-60-80，indicating the influence of mass transfer of reactants and products in macropores.2

REFERENCES

[1]Yang,H.Q.; Liu,Q.; Liu,Z.C.; Gao,H.X.; Xie,Z.K.Micropor Mesopor Mate. 2010, 127, 213. [2]Becker, H.; Güttel, R.; Turek, T. Chem Ing Tech. 2014, 86, 544.

P1-9

Activation of Aryl Chlorides in Water under Ligand-free Suzuki

Coupling by Heterogeneous Palladium Supported on Hybrid

Mesoporous Carbon

Ying Wan*, Linlin Duan, Rao Fu

Department of Chemistry, Shanghai Normal University, Shanghai, 200234, China ywan@shnu.edu.cn

ABSTRACT

Ligand-free heterogeneous Pd-based catalysts have attracted much attention in

Palladium-catalyzed Heck and Suzuki coupling reactions because they possess great

advantages in terms of recyclability.[1] Aryl chlorides, which are more economical and

accessible than aryl iodides and triflates, have rarely been used as electrophiles in

Pd-catalyzed Suzuki coupling due to the high activation barriers associated with the

difficult oxidative insertion of Pd(0) species into the Ar-Cl bond.

Here, heterogeneous palladium catalysts supported on ordered mesoporous

carbonaceous nanocomposites including carbon-silica, [2] CoO-C [3,4] and quaternary

ammonium phase transfer agent modified mesoporous carbonaceous resins, were

applied to the water-mediated Heck or Suzuki coupling reaction using chlorobenzene as

the substrate and exhibited a high yields of target products under mild reaction

conditions free of phase transfer agents and ligands. For example, the heterogeneous Pd

catalysts which were loaded onto quaternary ammonium phase transfer agent modified

mesoporous polymers were highly active in the Heck coupling of aryl bromides and

styrene to produce trans-stilbene at high yields (84 %) without the need to exclude air or

to use water as a solvent. The electron-rich environment stabilized by functional

quaternary ammonium groups was responsible to the high activity in converting aryl

bromides. Furthermore, the mesoporous Pd/CoO-C catalyst showed a high yield of

biphenyl (49 %) in the water-mediated Suzuki coupling reaction of chlorobenzene and

phenylboronic acid. Product yields in the reaction of aryl chlorides containing

electron-withdrawing groups attached to their benzene ring can reach approximately

90%. Very small Pd clusters consisting of approximately 3 atoms and Pd-O bonds

formed on the interface between CoO and Pd nanoparticles. The unsaturated

coordinative Pd may be responsible for the activation of chlorobenzene in the absence

of any additives or ligands.

Thiol-functionalized mesoporous silica, which can trap soluble Pd species, was

used to confirm the negligible leaching in solution and therefore heterogeneous reaction.

These heterogeneous catalyst are stable, showing unobvious activity loss after ten

catalytic runs. Additionally, uniform mesopores and the hydrophobic nature of the

carbon support may also facilitate the mass transfer of the reactant molecules and

enrichment inside pores.

REFERENCES

[1] Xiang, L.; Liebscher, J. Chem. Rev. 2007, 107, 133.

[2] Wan, Y.; Wang, H. Y.; Zhao, Q. F.; D. Y. Zhao, J. Am.Chem. Soc. 2009, 131, 4541.

[3] Kong, L. N.; Wei, W.; Zhao, Q. F.; Wang, J. Q.; Wan, Y. ACS Catal. 2012, 2, 2577.

[4] Duan, L. L.; Fu, R.; Wang, J. Q.; Chen, S. J.; Wan, Y.; ACS Catal. 2015, 5, 575.

P1-10

Catalysis of zeolite SRZ-21 for the selective synthesis of linear alkyl

benzene

Ming Xu＊, Huanxin Gao, Hui Yao, Yilun Wei, Ruifang Gu

Shanghai Resrearch Institude of Petrochemical Technology, SINOPEC, China

dongxueyinzi@163.com

ABSTRACT

Linear alkyl benzenes (LAB), the primary intermediates in detergent industry, are commercially manufactured by the alkylation of benzene with n-alkenes under the catalyst of HF or AlCl3.[1] Among LAB isomers, 2-phenyl isomers (2-LAB) are the most favorable materials for the production of ecofriendly domestic and industrial detergents because of their high solubility and biodegradability.[2] Therefore, environmental benign solid catalysts with high selectivity for 2-LAB production are badly needed. Here, zeolite SRZ-21 was prepared from the mixture of the inorganic silica and organic silane with the silica to Al2O3 ratio in the range of 10-90. The introduction of the organic silane induces the crystal growth in two-dimensional direction with layered structure. TEM image (Figure 1a) shows the thickness of the layers is around 2.6 nm while SEM image shows disorder stacks which could provide amount of macropores (Figure 1b). These large pores can be efficient diffusion channel for reaction molecular. Then, zeolite SRZ-21 was applied for the alkylation of benzene with dodecene. The results show extremely high dodecene conversion of 99 % at 353 K and 2-LAB isomer selectivity of 55 % (Figure 1c). Moreover, the conversion maintains at 99% during 700 hr time on stream, showing adequate catalytic stability for commercial viability. Because of this ideal balance between high activity and stability, it is anticipated that zeolite SRZ-21 may see applications in LAB production and industrial acid catalyzed reactions.

Figure 1. TEM image (a) and SEM image (b) of zeolite SRZ-21; c) Conversion of dodecene and 2-LAB selectivity versus time curve. REFERENCES

[1] Kocal, J. A.; Vora, B. V.; Imai, T. Appl. Catal. A 2001, 221, 295. [2] Kang, J. J.; Rao, Y. X.; Trudeau, M.; Antonelli, D. Angew. Chem. Int. Ed. 2008, 47, 4896–4899.

P1-11

Hydrodeoxygenation of lignin-derived phenols into alkanes over

carbon nanotube supported Ru catalysts in biphasic systems

Menyuan Chena, Yaobing Huanga, Huan Panga, Xinxin Liua, Yao Fu*a

a University of Science and Technology of China, No. 96 Jinzhai Road, Hefei City

fuyao@ustc.edu.cn

ABSTRACT

Phenolic compounds derived from lignin are important feedstocks for the

sustainable production of alkane fuels with C6–C9 carbons.[1] Hydrodeoxygenation (HDO) is the main chemical process to remove oxygen-containing functionalities.[2] Here, we have reported the HDO of phenols in a biphasic H2O/n-dodecane system.[3] A series of supported Ru catalysts were prepared, characterized and explored for the reaction among which Ru/CNT showed the highest catalytic activity towards the production of alkanes. The model reaction with eugenol achieved a high conversion (>99%) and a high alkane selectivity (98%), which was much higher than the results from the monophasic system (56.5% yield of alkanes in H2O). The reaction conditions including reaction temperature, hydrogen pressure and the ratio of H2O/n-C12H26were optimized. The kinetic experiments revealed that eugenol was first hydrogenated to 4-propyl-guaiacol, and then deoxygenated into 4-propyl-cyclohexanol which was the main detected intermediate of the reaction. After that, 4-propyl-cyclohexanol was dehydrated and hydrogenated into propylcyclohexane. Moreover, various phenols and dimeric lignin model compounds were also successfully converted into alkanes in the biphasic systems. The construction of the biphasic solvent-Ru/CNT catalyst system highlights an efficient route for the conversion of lignin-derived phenolic compounds to biofuels.

REFERENCES

[1] Zhao, C.; Kou, Y.; Lemonidou, A. A.; Li, X.; Lercher, J. A. Angew. Chem., Int. Ed. 2009, 48, 3987. [2] Xia, Q. N.; Cuan, Q.; Liu, X. H.; Gong, X. Q.; Lu, G. Z.; Wang, Y. Q. Angew. Chem., Int. Ed. 2014, 53, 9755. [3] Chen, M. Y.; Huang, Y. B.; Pang H.; Liu, X. X.; Fu, Y. Green Chemistry 2015, 17, 1710.

P1-12

Selective Hydrogenolysis of Phenols and Phenyl Ethers to Arenes

Through Direct C–O Cleavage Over Ruthenium–Tungsten

Bifunctional Catalysts

Yao-Bing Huanga,b, Long Yana, Meng-Yuan Chena, Qing-Xiang Guoa, and Yao Fu*a

a Collaborative Innovation Center of Chemistry for Energy Materials, CAS Key

Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of

Biomass Clean Energy, Department of Chemistry, University of Science and

Technology of China, Hefei 230026, China. b College of Chemical Engineering, Nanjing Forestry University, Nanjing

210037,China

E-mail: fuyao@ustc.edu.cn

ABSTRACT:

Direct hydrogenolysis of the aromatic Csp2–O bonds in both phenols and phenyl ethers to form arenes selectively is a core enabling technology that can expand greatly the scope of chemical manufacture from biomass. However, conventional hydrogenolysis of phenols typically led to aromatic ring saturation instead of the cleavage of the Csp2–O bonds. Herein, we report a recyclable Ru–WOx bifunctional catalyst that showed high catalytic activities for the hydrogenolysis of a wide range of phenols and phenyl ethers, including dimeric lignin model compounds and the primitive phenols separated from pyrolysis lignin, to form arenes selectively in water. Preliminary mechanistic studies supported that the reactions occurred via a direct cleavage of the Csp2–O bonds and the concerted effects of the hydrogenating Ru sites and the Lewis acidic W sites are the key to such an unusual reactivity. REFERENCES Yao-Bing, H.; Long, Y.; Meng-Yuan, C.; Qing-Xiang, G.; Yao, F. Green. Chem. 2015, 17, 3010.

P1-13

Borax-assisted hydrothermal carbonization to fabricate monodisperse

carbon spheres

M. Zhao1, J. X. Cai1, B. Li1*, K. Zhang1,2*,

1 Zhengzhou Tobacco Research Institute of CNTC, Zhengzhou 450001, China

2 School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450052, China

*Corresponding authors: ztrilibin@163.com, hfzhangke@126.com

ABSTRACT

A slightly modified hydrothermal carbonization process was used to fabricate monodispersed carbon spheres[1]. Borax, as a structure directing agent, could change the carbonaceous particles morphology as well as the average diameter and chemical structures. The synthesis principle is based on the catalysis impact on transformation starch into hydroxymethylfurfural and the retardation the process of the hydrothermal carbonization owing to the borax buffer function[2]. Herein, uniform solid carbon spheres with diameters ranging from 1.6 to 3μm can be tuned by the borax concentration (Fig. 1) and the reaction conditions in a simple one step hydrothermal process. For the thermal behaviors, the main mass loss of HTC without borax from 260 to 350oC was caused by the decomposition of oxygen-containing functional groups, sp3-hybridized carbon motif and partial furan rings and the second mass loss occurring from 350-580 oC can be ascribed to the oxidation of conjugated carbon atoms. While, boron-containing carbons increased the thermostability (Fig. 2) from 580 to 680 oC at higher concentration.

0，12h 0.005M，12h 0.01M，12h

0.015M，12h 0.01M，18h 0.01M，24h 100 200 300 400 500 600 700 800

0

20

40

60

80

100

TG

/%

Temp./°C

HTC-S

HTC-S-0.005

HTC-S-0.01

HTC-S-0.015

100 200 300 400 500 600 700 800-7

-6

-5

-4

-3

-2

-1

0

1

DT

G/(

%/m

in)

Temp./°C

HTC-S

HTC-S-0.005

HTC-S-0.01

HTC-S-0.015

585.8℃ 645.8℃ 668.3℃

a b

Fig.1 SEM images of the HTC spheres Fig. 2 (a) TG and (b) DTG curves of the HTC

of starch with and without borax of starch with and without borax REFERENCES

[1] Gong Y; Xie L; Li H; Wang Y. Chemical Communications. 2014, 84, 12633. [2] Baccile N.; Laurent G; Babonneau F; Fayon F; Titirici M.M. J Phys Chem C. 2009, 113, 9644. [3] Falco C. ; Caballero F. P; Babonneau F, Gervais C. ; Laurent G.; Titirici M.M.; Baccile N. Langmuir. 2011, 27, 14460.

P1-14

1st International Symposium on Energy Chemistry & Materials, Oct. 29�31 2015, Fudan University, Shanghai, China

Electrocatalytic reduction of CO2 over Pd nanoparticles

Guoxiong Wanga, Jianguo Wangb, Dunfeng Gaoa, Zhou Hub, Xinhe Baoa

a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese

Academy of Sciences, Dalian 116023, China b College of Chemical Engineering, Zhejiang University of Technology, Hanzhou

310032, China Email: wanggx@dicp.ac.cn; xhbao@dicp.ac.cn

ABSTRACT

The accelerated depletion of fossil fuel resources leads to increasing accumulation

of greenhouse gas, CO2, in the atmosphere, which raises serious environmental

concerns. Electrocatalytic reduction of CO2 to fuel and chemical feedstock, powered by

intermittent renewable electricity, is an attractive route for simultaneous conversion of

CO2 and renewable energy sources. However, there are several fundamental challenges

in the electrocatalytic reduction of CO2, such as high overpotential, low Faradic

efficiency due to the competitive hydrogen evolution reaction (HER), etc. Key points in

addressing these issues are the successive CO2 adsorption, intermediates formation and

product removal on active sites during the electrocatalytic reaction.

In this work, unique size-dependent electrocatalytic reduction of CO2 over Pd

nanoparticles (NPs) is reported.[1] Faradaic efficiency for CO production increases with

decreasing Pd NP size in a size range of 2.4-10.3 nm, which varies from 5.8% at -0.89 V

(vs. reversible hydrogen electrode, RHE) over 10.3 nm NPs to 91.2% over 3.7 nm NPs,

along with an 18.4 fold increase in current density for CO production. Density

functional theory (DFT) calculations indicate that corner and edge sites (small Pd NPs)

facilitate the adsorption of CO2 and formation of key reaction intermediates COOH*

during CO2 reduction compared with terrace one (large Pd NPs), while the formation of

H* for competitive HER is similar on all three sites. Furthermore, a volcano-like curve

of the turnover frequency (TOF) for CO production within the size range suggests that

CO2 adsorption, COOH* formation and CO* removal during CO2 reduction can be

tuned on differently sized Pd NPs due to the changing ratio of corner, edge and terrace

sites. It provides a good example on tuning nanoparticle dimension to enhance both

Faradaic efficiency and current density for CO production from electrocatalytic

reduction of CO2. REFERENCES [1] Gao, D. F.; Zhou, H.; Wang J.; Miao S.; Yang F.; Wang, G. X.; Wang, J. G., Bao, X. H. J. Am. Chem. Soc. 2015, 137,4288.

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1st International Symposium on Energy Chemistry & Materials, Oct. 29‒31 2015, Fudan University, Shanghai, China

Carbon-based nanofluidics and bio-inspired energy conversion

Wei Guoa, Lei Jianga

a Laboratory of Bio-inspired Smart Interface Science, Technical Institute of Physics and

Chemistry, Chinese Academy of Sciences, Beijing 100190.

wguo@iccas.ac.cn

ABSTRACT

Hierarchically integrated nanoscale ionic conductors, including ion channels and

ion pumps, are the structural and functional basis of many bioelectric organs, such as

the electric eel. Recently, we have built artificial nanofluidic devices with graphene (2D)

and mesoporous carbon (3D) based nanomaterials to control the mass and charge

transportation as effectively as natural cells. Graphene and other 2D atomic crystals can

be reassembled into laminar structures without sacrificing the surface-governed

properties on the nanoscale. Firstly, we demonstrate the surface-charge-governed ion

transport in graphene nanochannels and further develop the mechanism into

macroscopic 2D nanofluidic generators. On another aspect, mesoporous materials, with

highly uniform pore size, high specific surface area, and simple fabrication methods,

become the ideal material for nanofluidic use. We report a membrane-scale nanofluidic

device with asymmetric structure, chemical composition, and surface charge polarity,

termed ionic diode membrane (IDM), for harvesting electric power from salinity

gradient.

REFERENCES

[1] Guo, W.; Cheng, C.; Wu, Y.; Jiang, Y.; Gao, J.; Li, D.*; and Jiang, L.*; Adv. Mater.

2013, 25, 6064.

[2] Gao, J.; Guo, W.*; Feng, D.; Wang, H.; Zhao, D.*; and Jiang, L.*; J. Am. Soc. Soc.

2014, 136, 12265.

[3] Guo, W.; Tian, Y.; and Jiang, L.*; Acc. Chem. Res. 2013, 46, 2834.

[4] Guo, W.; Cao, L.; Xia, J.; Nie, F-Q.; Ma, W.; Xue, J.; Song, Y.; Zhu, D.; Wang, Y.*;

and Jiang, L.*; Adv. Funct. Mater. 2010, 20, 1339.

[5] Cao, L.; Guo, W.*; Ma, W.; Wang, L.; Xia F.; Wang S.; Wang Y.*; Jiang, L.; and Zhu,

D.; Energy Environ. Sci. 2011, 4, 2259.

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