Citation: Wu Kuangheng, Zhou Yawei, Ma Xianyin, Ding Chen, Cai Wenbin. Controlled Synthesis of Gold-Platinum Catalysts for Ethanol Electro-oxidation Reaction[J]. Acta Chimica Sinica, ;2018, 76(4): 292-297. doi: 10.6023/A17110478 shu

Controlled Synthesis of Gold-Platinum Catalysts for Ethanol Electro-oxidation Reaction

a.
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200433
b.
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090

Corresponding author: Cai Wenbin, wbcai@fudan.edu.cn
Received Date: 2 November 2017
Available Online: 9 April 2018
Fund Project: 973 program 2015CB932303the National Natural Science Foundation of China 21733004Science and Technology Commission of Shanghai Mu-nicipality 17520711200Project supported by the National Natural Science Foundation of China (Nos. 21473039, 21733004), Science and Technology Commission of Shanghai Mu-nicipality (No. 17520711200) and 973 program (No. 2015CB932303)the National Natural Science Foundation of China 21473039

Figures(8)

Ethanol oxidation reaction (EOR) is a common anode process for direct ethanol fuel cell (DEFC) and ethanol reforming electrolyzer. Au@Pt and AuPt alloy are widely used bimetallic catalysts, yet no comparative study has been reported of electrocatalysis of EOR on these two differently structured catalysts. The present work aims to synthesize and characterize carbon supported Au@Pt and AuPt with controlled composition and size, and compare their electrocatalytic activities and stabilities toward EOR in alkaline media. For the synthesis of Au@Pt/C, a 5-nm Au colloid was first obtained by adding excessive amount of sodium borohydride to a chloroauric acid precursor containing sodium citrate with a mixed ice-water bath. CO gas was bubbled into the Au colloidal solution at 60℃ under strong stirring to reduce a desired amount of potassium tetrachloroplatinate(Ⅱ) to terminate Pt quasi-monolayer shell on Au nanoparticle core. A sonicated carbon black (Vulcan XC-72) aqueous slurry was then dropwise added to the above Au@Pt colloid, and the mixture was kept stirring for 48 h to ensure the exhaustive loading of Au@Pt nanoparticles onto the carbon support. For the synthesis of AuPt/C with the same Au:Pt molar ratio and metal loading as that for Au@Pt/C, coreduction of the Au(Ⅲ) and Pt(Ⅱ) species was attained by using sodium borohydride as the reducing agent with the rest procedures being same as the above mentioned. X-ray diffractometry (XRD) revealed that the diffraction peaks for Au@Pt/C were virtually same as those for Au/C, consistent with a Pt quasi-monolayer, while the diffraction peaks for AuPt/C located in between those for Au/C and Pt/C. X-ray photoelectron spectroscopy (XPS) results were consitent with the different structures of the two catalysts, and the Pt core level shift suggested an upshift of Pt d-band center for both bimetallic catalysts. Cyclic voltammetry and chronoamperometry revealed markedly increased EOR current on Au@Pt/C and AuPt/C, as compared to that of Pt/C and Au/C. CO-stripping voltammetry on Au@Pt/C and AuPt/C indicated that surface reconstruction occurred by potential cycling, resulting in a decrease of exposed Pt sites but not the electrocatalytic activities. ¹H NMR analysis confirmed the C2 pathway is predominant. Nevertheless, Au@Pt/C outperformed AuPt/C and Pt/C with a lower onset oxidation potential and a higher peak current for EOR, as well as a slightly higher selectivity toward C1 pathway. Although the synergetic effect of Au-Pt bimetallic interface for EOR is not well understood, the enhanced adsorption of ethanol, OH, acetyl and CO on Pt sites may be accountable for the observed results.
- ethanol oxidation reaction,
- electrocatalysis,
- AuPt bimetallic catalysts,
- core-shell structure,
- alloy structure
1. [1]
  Li, H. H.; Zhao, S.; Gong, M.; Cui, C. H.; He, D.; Liang, H. W.; Liang, W.; Yu, S. H. Angew. Chem., Int. Ed. 2013, 52, 7472. doi: 10.1002/anie.201302090
2. [2]
  Coutanceau, C.; Baranton, S. WIREs Energy Environ. 2016, 5, 388. doi: 10.1002/wene.193
3. [3]
  de Lucas-Consuegra, A.; Ana, R.; Calcerrada, A. B.; Linares, J. J.; Horwat, D. J. Power Sources 2016, 321, 248. doi: 10.1016/j.jpowsour.2016.05.004
4. [4]
  Chen, H. M.; Xing, Z. L.; Zhu, S. Q.; Zhang, L. L.; Chang, Q. W.; Huang, J. L.; Cai, W. B.; Kang, N.; Zhong, C. J.; Shao, M. H. J. Power Sources 2016, 321, 264. doi: 10.1016/j.jpowsour.2016.04.072
5. [5]
  Lamy, C.; Lima, A.; LeRhun, V.; Delime, F.; Coutanceau, C.; Léger, J. M. J. Power Sources 2002, 105, 283 doi: 10.1016/S0378-7753(01)00954-5
6. [6]
  Rao, L.; Jiang, Y. X.; Zhang, B. W.; You, L. X. H.; Li, Z. H.; Sun, S. G. Prog. Chem. 2014, 26, 727(in Chinese).
7. [7]
  Zheng, H. T.; Li, Y.; Chen, S.; Shen, P. K. J. Power Sources 2006, 163, 371. doi: 10.1016/j.jpowsour.2006.09.062
8. [8]
  Wang, Y.; Zou, S.; Cai, W. B. Catalysts 2015, 5, 1507. doi: 10.3390/catal5031507
9. [9]
  Xu, C. W.; Cheng, L. Q.; Shen, P. K.; Liu, Y. L. Electrochem. Commun. 2007, 9, 997. doi: 10.1016/j.elecom.2006.12.003
10. [10]
  Wang, Y.; Jiang, K.; Cai, W. B. Electrochim. Acta 2015, 162, 100. doi: 10.1016/j.electacta.2014.11.182
11. [11]
  Adzic, R. R.; Zhang, J.; Sasaki, K.; Vukmirovic, M. B.; Shao, M.; Wang, J. X.; Nilekar, A. U.; Mavrikakis, M.; Valerio, J. A.; Uribe, F. Top. Catal. 2007, 46, 249. doi: 10.1007/s11244-007-9003-x
12. [12]
  Mulvaney, S. P.; Keating, C. D. Anal. Chem. 2000, 72, 145. doi: 10.1021/a10000155
13. [13]
  Enache, D. I.; Edwards, J. K.; Landon, P.; Solsona-Espriu, B.; Carley, A. F.; Herzing, A. A.; Watanabe, M.; Kiely, C. J.; Knight, D. W.; Hutchings, G. J. Science 2006, 311, 362. doi: 10.1126/science.1120560
14. [14]
  Song, H. M.; Anjum, D. H.; Sougrat, R.; Hedhili, M. N.; Khashab, N. M. J. Mater. Chem. 2012, 22, 25003. doi: 10.1039/c2jm35281h
15. [15]
  Chen, Y. G.; Zhuang, L.; Lu, J. T. Chin. J. Catal. 2007, 28, 870(in Chinese). doi: 10.3321/j.issn:0253-9837.2007.10.007
16. [16]
  Li, J. F.; Yang, Z. L.; Ren, B.; Liu, G. K.; Fang, P. P.; Jiang, Y. X.; Wu, D. Y.; Tian, Z. Q. Langmuir 2006, 22, 10372. doi: 10.1021/la061366d
17. [17]
  Dai, Y.; Chen, S. L. ACS Appl. Mater. 2014, 7, 823.
18. [18]
  Brankovic, S. R.; Wang, J. X.; Adžić, R. R. Surf. Sci. 2001, 474, 173. doi: 10.1016/S0039-6028(00)01103-1
19. [19]
  Liu, Y.; Gokcen, D.; Bertocci, U.; Moffat, T. P. Science 2012, 338, 1327. doi: 10.1126/science.1228925
20. [20]
  Engelbrekt, C.; Šešelj, N.; Poreddy, R.; Riisager, A.; Ulstrup, J.; Zhang, J. D. J. Mater. Chem. A 2016, 4, 3278. doi: 10.1039/C5TA08922K
21. [21]
  Zhou, Y. W.; Du, C. Y.; Han, G.; Gao, Y. Z.; Yin, G. P. Electrochim. Acta 2016, 217, 203. doi: 10.1016/j.electacta.2016.09.070
22. [22]
  Xu, C. X.; Wang, R. Y.; Chen, M. W.; Zhang, Y.; Ding, Y. Phys. Chem. Chem. Phys. 2010, 12, 239. doi: 10.1039/B917788D
23. [23]
  Zeng, J.; Yang, J.; Lee, J. Y.; Zhou, W. J. Phys. Chem. B 2006, 110, 24606. doi: 10.1021/jp0640979
24. [24]
  Xu, Y. Y.; Dong, Y. N.; Shi, J.; Xu, M. L.; Zhang, Z. F.; Yang, X. K. Catal. Commun. 2011, 13, 54. doi: 10.1016/j.catcom.2011.06.018
25. [25]
  Ye, W.; Kou, H.; Liu, Q.; Yan, J.; Zhou, F.; Wang, C. Int. J. Hydrogen Energ. 2012, 37, 4088. doi: 10.1016/j.ijhydene.2011.11.132
26. [26]
  Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.; Chen, J. G. Phys. Rev. Lett. 2004, 93, 156801. doi: 10.1103/PhysRevLett.93.156801
27. [27]
  Demirci, U. B. J. Power Sources 2007, 173, 11. doi: 10.1016/j.jpowsour.2007.04.069
28. [28]
  Wakisaka, M.; Mitsui, S.; Hirose, Y.; Kawashima, K.; Uchida, H.; Watanabe, M. J. Phys. Chem. B 2006, 110, 23489. doi: 10.1021/jp0653510
29. [29]
  Zhu, C.; Hai, Y.; Zhao, Z. G.; Yang, Y. Y. Acta Chim. Sinica 2017, 76, 30. in Chinese
30. [30]
  Zhou, W.; Lee, J. Y. Electrochem. Commun. 2007, 9, 1725. doi: 10.1016/j.elecom.2007.03.016
31. [31]
  Maillard, F.; Savinova, E. R.; Stimming, U. J. Electroanal. Chem. 2007, 599, 221. doi: 10.1016/j.jelechem.2006.02.024
32. [32]
  Qin, Y. H.; Yang, H. H.; Zhang, X. S.; Li, P.; Zhou, X. G.; Niu, L.; Yuan, W. K. Carbon 2010, 48, 3323. doi: 10.1016/j.carbon.2010.05.010
33. [33]
  Liang, Z. X.; Zhao, T. S.; Xu, J. B.; Zhu, L. D. Electrochim. Acta 2009, 54, 2203 doi: 10.1016/j.electacta.2008.10.034
34. [34]
  Lebedeva, N. P.; Koper, M. T. M.; Feliu, J. M.; Van Santen, R. A. J. Electroanal. Chem. 2002, 524, 242.
35. [35]
  McCallum, C.; Pletcher, D. J. Electroanal. Chem. 1976, 70, 277. doi: 10.1016/S0022-0728(76)80196-9
36. [36]
  Gilman, S. J. Phys. Chem. 1964, 68, 70. doi: 10.1021/j100783a013
37. [37]
  Suntivich, J.; Xu, Z.; Carlton, C. E.; Kim, J.; Han, B.; Lee, S. W.; Bonnet, N.; Marzari, N.; Allard, L. F.; Gasteiger, H. A.; Hamad-Schifferli, K.; Shao-Horn, Y. J. Am. Chem. Soc. 2013, 135, 7985. doi: 10.1021/ja402072r
38. [38]
  Chen, G. L.; Chen, S. P.; Zhen, C. H.; Zhou, Z. Y.; Sun, S. G. Acta Chim. Sinica 2001, 59, 1253(in Chinese). doi: 10.3321/j.issn:0567-7351.2001.08.016
39. [39]
  Bayer, D.; Berenger, S.; Joos, M.; Cremers, C.; Tübke, J. Int. J. Hydrogen Energ. 2010, 35, 12660. doi: 10.1016/j.ijhydene.2010.07.102
40. [40]
  Teng, X. In Materials and Processes for Energy: Communicating Current Research and Technological Developments, Atrazhev, V. V. ; Burlatsky, S. F., Formatex Research Center, Durham, 2013, pp. 473~484.
41. [41]
  Wang, S. Y.; Kristian, N.; Jiang, S. P.; Wang, X. Nanotechnology 2008, 20, 025605.
42. [42]
  Wang, H.; Jiang, K.; Chen, Q.; Xie, Z.; Cai, W. B. Chem. Commun. 2016, 52, 374. doi: 10.1039/C5CC06551H
1. [1]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
2. [2]
  Tongtong Zhao , Yan Wang , Shiyue Qin , Liang Xu , Zhenhua Li . New Experiment Development: Upgrading and Regeneration of Discarded PET Plastic through Electrocatalysis. University Chemistry, 2024, 39(3): 308-315. doi: 10.3866/PKU.DXHX202309003
3. [3]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
4. [4]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
5. [5]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-. doi: 10.3866/PKU.WHXB202404012
6. [6]
  Xi Xu , Chaokai Zhu , Leiqing Cao , Zhuozhao Wu , Cao Guan . Experiential Education and 3D-Printed Alloys: Innovative Exploration and Student Development. University Chemistry, 2024, 39(2): 347-357. doi: 10.3866/PKU.DXHX202308039
7. [7]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
8. [8]
  Ran HUO , Zhaohui ZHANG , Xi SU , Long CHEN . Research progress on multivariate two dimensional conjugated metal organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2063-2074. doi: 10.11862/CJIC.20240195
9. [9]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
10. [10]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
11. [11]
  Asif Hassan Raza , Shumail Farhan , Zhixian Yu , Yan Wu . 用于高效制氢的双S型ZnS/ZnO/CdS异质结构光催化剂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406020-. doi: 10.3866/PKU.WHXB202406020
12. [12]
  Yaping Li , Sai An , Aiqing Cao , Shilong Li , Ming Lei . The Application of Molecular Simulation Software in Structural Chemistry Education: First-Principles Calculation of NiFe Layered Double Hydroxide. University Chemistry, 2025, 40(3): 160-170. doi: 10.12461/PKU.DXHX202405185
13. [13]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
14. [14]
  Yang WANG , Xiaoqin ZHENG , Yang LIU , Kai ZHANG , Jiahui KOU , Linbing SUN . Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165
15. [15]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
16. [16]
  .
  CCS Chemistry 综述推荐│绿色氧化新思路：光/电催化助力有机物高效升级
  . CCS Chemistry, 2025, 7(10.31635/ccschem.024.202405369): -.
17. [17]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081
18. [18]
  Zelong LIANG , Shijia QIN , Pengfei GUO , Hang XU , Bin ZHAO . Synthesis and electrocatalytic CO₂ reduction performance of metal-organic framework catalysts loaded with silver particles. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 165-173. doi: 10.11862/CJIC.20240409
19. [19]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
20. [20]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029

Get Citation

PDF

XML

Metrics

PDF Downloads(42)
Abstract views(2736)
HTML views(630)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142