Citation: ZHANG Xiao-feng, XUE Ji-long, MENG Yue, QIAN Meng-dan, XIA Sheng-jie, NI Zhe-ming. Reaction mechanism of water gas shift reaction Au_n clusters:A density functional theory study[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(12): 1473-1480. shu

Reaction mechanism of water gas shift reaction Au_n clusters:A density functional theory study

1.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
2.
School of Life Sciences, Huzhou University, Huzhou 313000, China

Corresponding author: NI Zhe-ming, jchx@zjut.edu.cn
Received Date: 12 June 2017
Revised Date: 28 September 2017

Fund Project: The project was supported by the National Natural Science Foundation of China (21503188) and the Zhejiang Provincial Natural Science Foundation of China (LQ15B030002)the Zhejiang Provincial Natural Science Foundation of China LQ15B030002the National Natural Science Foundation of China 21503188

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The stability and catalytic activity of Au₁₀, Au₁₃ and Au₂₀ clusters in water gas shift reaction (WGSR) were investigated by density functional theory (DFT); the adsorption behavior of reaction species and the reaction mechanism of WGSR on various Au_n clusters were explored. The results indicated that the stability of three Au_n clusters follows the order Au₁₀ < Au₁₃ < Au₂₀, whereas their electron delocalization and adsorption capacity decreases in the sequence of Au₁₃ > Au₁₀ > Au₂₀. Three Au_n clusters exhibit the same rate-determining step for WGSR, i.e. H₂O dissociation; however, they are quite different in the actual reaction routes. Over Au₁₀ cluster, the WGSR reaction follows the carboxyl mechanism, characterized by the direct dissociation of COOH^*; over Au₁₃ cluster, the redox mechanism applies, suggested by the disproportionation of two OH^*; over Au₂₀ cluster, the WGSR reaction proceeds via the carboxyl mechanism, represented by the disproportionation of COOH^* and OH^*. A comparison for the optimal reaction paths over three Au_n clusters suggests that the Au₁₃ cluster has the highest catalytic activity in the WGSR reaction at low temperature.
- Au cluster,
- water gas shift reaction,
- density functional theory,
- reaction mechanism
1. [1]
  ZHU Qiao-qiao, CHENG Ji-hua. Research progress of hydrogen energy preparation technology[J]. Energy Conserv Emiss, 2015,12:51-54.
2. [2]
  CHEN L, NI G, HAN B, ZHOU C G, WU J P. Mechanism of water gas shift reaction on Fe₃O₄ (111) surface[J]. Acta Chim Sin, 2011,69(4):393-398.
3. [3]
  MAO Jiang-hong, NI Zhe-ming, PAN Guo-xiang, XU Qian. Mechanism of the copper catalyzed water gas shift reaction[J]. Acta Phys Chim Sin, 2008,24(11):2059-2064. doi: 10.3866/PKU.WHXB20081121
4. [4]
  NGUYEN-PHAN T D, BABER A E, RODRIGUEZ J A, SENANAYAKE S D. Au and Pt nanoparticle supported catalysts tailored for H₂ production: from models to powder catalysts[J]. Appl Catal A: Gen, 2015,518:18-47.
5. [5]
  PEREZ P, SORIA M A, CARABINEIRO S A C, MALDONADO-HODAR F J, MENDES A. Application of Au/TiO₂ catalysts in the low temperature water gas shift reaction[J]. Int J Hydrogen Ene, 2016,41(8):4670-4681. doi: 10.1016/j.ijhydene.2016.01.037
6. [6]
  ÖZYONUM G N, YILDIRIM R. Water gas shift activity of Au-Re catalyst over microstructured cordierite monolith wash-coated by ceria[J]. Int J Hydrogen Enegy, 2016,41(12):5513-5521. doi: 10.1016/j.ijhydene.2016.02.025
7. [7]
  GAMBOA-ROSALES N K, AYASTUY J L, GUTIERREZ-ORTIZ M A. Effect of Au in Au-Co₃O₄/CeO₂ catalyst during oxygen-enhanced water gas shift[J]. Int J Hydrogen Enegy, 2016,41(42):19408-19417. doi: 10.1016/j.ijhydene.2016.05.237
8. [8]
  RODRIGUEZ J A, LIU P, HRBEK J, PEREZ M, EVANS J. Water gas shift activity of Au and Cu nanoparticles supported on molybdenum oxides[J]. J Mol Catal A Chem, 2008,281(1/2):59-65.
9. [9]
  YU Qing-qiang, DONG Yuan-yuan, LIAO Wei-ping, JIN Ming-shan, HE Tao, SUO Zhang-huai. Preparation of ceria-alumina and catalytic activity of gold catalyst supported on ceria-alumina for water gas shift reaction[J]. J Fuel Chem Technol, 2010,38(2):223-229.
10. [10]
  CASTANO , REINA T R, IVANOVA S, CENTENO M A, ODRIOZOLA J A. Pt vs. Au in water gas shift reaction[J]. J Catal, 2014,314:1-9. doi: 10.1016/j.jcat.2014.03.014
11. [11]
  HUANG Jun. Gold nanoparticles catalyzed low-temperature CO oxidation and novel system for green reduction[D]. Shanghai: Fudan University, 2013.
12. [12]
  CHEN Y, WANG H, BURCH R, HARDACRE C, HU P. New insight into mechanisms in water gas shift reaction on Au/CeO₂(111): a density functional theory and kinetic study[J]. Faraday Discuss, 2011,152(1)121.
13. [13]
  CHEN Y, CHENG J, HU P, WANG H. Examining the redox and formate mechanisms for water gas shift reaction on Au/CeO₂ using density functional theory[J]. Surf Sci, 2008,602(17):2828-2834. doi: 10.1016/j.susc.2008.06.033
14. [14]
  FEDOROV A V, KHMEL'T A. DFT and in situ EXAFS investigation of gold/ceria-zirconia low temperature water gas shift catalysts: identification of the nature of the active form of gold[J]. J Phys Chem B, 2005,109(47):2253-9.
15. [15]
  SAQLAIN M A, HUSSAIN A, SIDDIQ D M, LEENAERTS O, LEITAO A A. DFT study of synergistic catalysis of the water gas shift reaction on Cu-Au bimetallic surfaces[J]. ChemCatChem, 2016,8(6):1208-1217. doi: 10.1002/cctc.201501312
16. [16]
  JIANG Jun-hui, CAO Yong-yong, NI Zhe-ming, ZHANG Lian-yang. Comparison of reaction mechanism of thiophene hydrodesulfurization on Au₁₃ and Pt₁₃ clusters[J]. J Fuel Chem Technol, 2016,44(8):961-969.
17. [17]
  ANDERSSON T, ZHANG C, BJORNEHOLM O, MIKKELA M H, JANKALA K. Electronic structure transformation in small bare Au clusters as seen by X-ray photoelectron spectroscopy[J]. J Phys B: At Mol Ophys, 2017,50(1)015102. doi: 10.1088/1361-6455/50/1/015102
18. [18]
  CHENG X, LI F, WANG C. Density functional theory study of CO oxidation by O₂, on Au_n, (n=11, 13 and 14) clusters as catalysis: from a comparative review[J]. Comput Theor Chem, 2016,1097:1-7. doi: 10.1016/j.comptc.2016.10.007
19. [19]
  DENG Xiao-hui. A theoretical study on geometries and electronic structure of gold clusters[D]. Chengdu: Sichuan University, 2007.
20. [20]
  WANG S, WANG W N, LU J, CHEN G H, FAN K N. A theoretical study on Au_n (n=2-20) with combined density functional and genetic algorithm methods[J]. Acta Chim Sin, 2007,65(19):2085-2091.
21. [21]
  LIU Xiao-ming, NI Zhe-ming, YAO Ping, XU Qian, MAO Jiang-hong, WANG Qiao-qiao. Comparison of three reaction mechanisms for the water gas shift reaction on Au(111) surface[J]. Acta Phys-Chim Sin, 2010,26(6):1599-1606.
22. [22]
  REN N N, GUO L, DONG X N, WEN C X. Theoretical study on menchanism of water gas shift reaction catalyzed by binary copper cluster[J]. Acta Chim Sinica, 2015,73(4):343-348. doi: 10.6023/A14110790
23. [23]
  MOHSENZADEH A, RICHARDS T, BOLTON K. DFT study of the water gas shift reaction on Ni(111), Ni(100) and Ni(110) surfaces[J]. Surf Sci, 2016,644:53-63. doi: 10.1016/j.susc.2015.09.014
24. [24]
  ZHOU M X, LIU B. DFT investigation on the competition of the water gas shift reaction versus methanation on clean and potassium-modified Nickel(111) surfaces[J]. ChemCatChem, 2015,7:3928-3935. doi: 10.1002/cctc.201500547
25. [25]
  ZHAO Guo-li, LIU Dan, LIU Shi, ZHANG Xiao-tong, GUI Jian-zhou, SUN Zhao-lin. DFT studies of activity of water gas shift reaction by several metals catalyzed[J]. J Petrochem Univ, 2005,8(2):19-23.
26. [26]
  WILLIAMS W D, GREELEY J P, DELGASS W N, RIBEIRO F H. Water activation and carbon monoxide coverage effects on maximum rates for low temperature water-gas shift catalysis[J]. J Catal, 2017,347:197-204. doi: 10.1016/j.jcat.2017.01.016
27. [27]
  LIN R J, CHEN H L, JU S P. Quantum-chemical calculations on the mechanism of the water-gas shift reaction on nanosized gold cluster[J]. J Phys Chem C, 2012,116(1):336-342. doi: 10.1021/jp209172w
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沈阳化工大学材料科学与工程学院沈阳 110142

Reaction mechanism of water gas shift reaction Aun clusters:A density functional theory study

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通讯作者: 陈斌, bchen63@163.com

Reaction mechanism of water gas shift reaction Au_n clusters:A density functional theory study