采用改进的B?nnemann法成功制备了Pt/C、Pt-Ni1/3/C、Pt-SnO2/C、Pt-Nix-SnO2/C（x=1/4，1/3，2/3，1）阳极电催化剂。利用X射线衍射（XRD）、高分辨透射电子显微镜（HR-TEM）以及X射线光电子能谱（XPS）对催化剂晶型结构、表面形貌和表面电子结构进行了表征。运用线性扫描伏安（LSV）和电流密度-时间（j-t）曲线进行电化学测试，研究了乙醇电催化氧化（EOR）活性。并用原位红外光谱（in situ FT-IR）研究了EOR过程中产物的分布。结果表明，Pt-Ni1/3-SnO2/C是由Pt-Ni合金和SnO2两相组成。XPS结果表明，在Pt-SnO2中添加微量的Ni，Pt表面电子结构发生了改变。电化学结果表明，三元催化剂的EOR活性均优于二元和纯Pt，其中Pt-Ni1/3-SnO2/C的EOR活性最佳。Ni和SnO2的加入并没有显著提高乙醇C-C键的断裂能力，但是二者的协同作用在低电位（0.1 V）下加强了乙醛的进一步氧化，生成了乙酸。 A series of Pt/C, Pt-Ni1/3/C, Pt-SnO2/C and Pt-Nix-SnO2/C (x=1/4, 1/3, 2/3, 1) anode electro-catalysts have been synthesized by an improved B?nnemann method. The crystal structure, surface morphology and surface electronic structure were characterizated by X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The electro-catalytic activities were characterizated by linear sweep voltammetry (LSV) and amperometric current density-time (j-t) curve techniques for ethanol oxidation reaction (EOR). In situ spectroelectrochemical studies have been used to identity adsorbed reaction intermediates and products (in situ Fourier transform infrared spectroscopy, FT-IR). XRD and HR-TEM analysis revealed two phases in the ternary Pt-Ni-SnO2/C catalyst:Pt-Ni alloys and SnO2. XPS results show that the electronic structure of the Pt in Pt-Ni1/3-SnO2/C might be changed due to the addition of Ni. The activity of Pt-Ni-SnO2/C for EOR was found to be higher than that of Pt/C, Pt-Ni/C and Pt-SnO2/C catalysts. The incorporation of Ni and SnO2 did not significantly improve C-C bond breaking for complete oxidation of ethanol, but the synergy under the low potential (0.1 V) to strengthen the further oxidation of acetaldehyde, generate the acetic acid
References
[1]
3 Roelofs K. S. ; Hirth T. ; Schiestel T. Mater. Science Eng. B 2011, 176, 727. doi: 10.1016/j.mseb.2011.02.029
[2]
4 Li H. Q. ; Sun G. Q. ; Cao L. ; Jiang L. H. ; Xin Q. Electrochim. Acta 2007, 52, 6622. doi: 10.1016/j.electacta.2007.04.056
[3]
5 Lamy C. ; Belgsir E. M. ; Léger J. M. J. Appl. Electrochem. 2001, 31 (7), 799. doi: 10.1023/A:1017587310150
14 Kowal A. ; Li M. ; Shao M. ; Sasald K. ; Vulcmirovic M. B. ; Zhang J. ; Marinkovic N. S. ; Liu P. ; Frenkel A. I. ; Adzic R. R. Nat. Mater. 2009, 8, 325. doi: 10.1038/nmat2359
[8]
17 Jin B. Y. ; Sun H. Y. ; Zhao L. H. Electrochim. Acta 2014, 142, 223. doi: 10.1016/j.electacta.2014.07.099
[9]
18 Spinacé E. V. ; Linardi M. ; Neto A. O. Electrochem. Commun. 2005, 7, 365. doi: 10.1016/j.elecom.2005.02.006
[10]
26 Sun H. Y. ; Zhao L. H. ; Yu F. C. Acta Phys. -Chim. Sin. 2013, 29, 959. doi: 10.3866/PKU.WHXB201303042
33 Lambert D. K. Electrochim. Acta 1996, 41, 623. doi: 10.1016/0013-4686(95)00349-5
[13]
1 Vigier F. ; Rousseau S. ; Coutanceau C. ; Leger J. M. ; Lamy C. Top Catal. 2006, 40, 111. doi: 10.1007/s11244-006-0113-7
[14]
2 Antolini E. J. Power Sources 2007, 170, 1. doi: 10.1016/j.jpowsour.2007.04.009
[15]
7 Chu D. B. ; Yin X. J. ; Feng D. X. ; Lin H. S. ; Tian Z. W. ActaPhys. -Chim. Sin. 2006, 22, 1238. doi: 10.3866/PKU.WHXB20061013
[16]
9 Rousseau S. ; Coutanceau C. ; Lamy C. ; Léger J. M. J. PowerSources 2006, 158, 18. doi: 10.1016/j.jpowsour.2005.08.027
[17]
10 Zhou W. ; Zhou Z. ; Song S. ; Li W. ; Sun G. Q. ; Xin Q. Appl.Cata1. B 2003, 46, 273. doi: 10.1016/S0926-3373(03)00218-2
[18]
11 Hayden B. E. ; Rendall M. E. J. Am. Chem. Soc. 2003, 125, 7738. doi: 10.1021/ja0214781
[19]
12 Vigier F. ; Coutanceau C. ; Hahn F. ; Belgsir E. M. ; Lamy C.J. Electroanal. Chem. 2004, 563, 81. doi: 10.1016/j.jelechem.2003.08.019
[20]
13 Takeguchi T. ; Wang G. X. ; Muhamad E. N. ; Ueda W. ECSTransactions 2008, 16, 713. doi: 10.1149/1.2981907
[21]
15 Zhao L. H. ; Mitsushima S. ; Ishihara A. ; Matsuzawa K. ; Ota K. Chin. J. Catal. 2011, 32, 1856. doi: 10.1016/S1872-2067(10)60297-5
[22]
16 Lee E. ; Park I. S. ; Manthiram A. J. Phys. Chem. C 2010, 114, 10634. doi: 10.1021/jp101843h
[23]
23 Parreira L. S. ; da Silva J. C. M. ; D′Villa-Silva M. ; Simoes F.C. ; Garcia S. ; Gaubeur I. ; Cordeirob M. A. L. ; Leite E. R. ; dos Santos M. C. Electrochim. Acta 2013, 96, 243. doi: 10.1016/j.electacta.2013.02.054
[24]
24 B?nnemann H. ; Brijoux W. ; Brinkmann R. ; Dinjus E. ; Joussen T. ; Korall B. Angew. Chem. Int. Ed. Engl. 1991, 30, l312. doi: 10.1002/anie.199113121
[25]
27 Sandoval-Gonzáleza A. ; Borja-Arcoa E. Int. J. Hydrog. Energy 2012, 37, 1752. doi: 10.1016/j.ijhydene.2011.10.049
[26]
28 Sakamoto R. ; Kaoru O. J. Power Sources 2014, 269, 117. doi: 10.1016/j.jpowsour.2014.07.011
[27]
29 Jiang L. H. ; Sun G. Q. ; Sun S. G. ; Liu J. G. ; Tang S. H. ; Li H. Q. ; Zhou B. ; Xin Q. Electrochim. Acta 2005, 50, 5384. doi: 10.1016/j.electacta.2013.02.054
[28]
6 Tang Y. W. ; Ma G. X. ; Zhou Y. M. ; Bao J. C. ; Lu L. D. ; Lu T. H. Acta Phys. -Chim. Sin. 2008, 24, 1615. doi: 10.3866/PKU.WHXB20080915
19 Zhang Z. ; Xin L. ; Sun K. ; Li W. Int. J. Hydrog. Energy 2011, 36, 12686. doi: 10.1016/j.ijhydene.2011.06.141
[31]
20 Bagchi J. ; Bhattacharya S. K. J. Power Sources 2007, 163, 661. doi: 10.1016/j.jpowsour.2006.09.063
[32]
21 dos Santos Correa P. ; da Silva E. L. ; da Silva R. F. ; Radtke C. ; Moreno B. ; Chinarro E. ; de Fraga Malfatti C. ; Kamarudin M. Z. F. ; Kamarudin S. K. ; Masdar M. S. ; Daud W. R. W. Int.J. Hydrog.Energy 2013, 38, 9438. doi: 10.1016/j.ijhydene.2012.07.059
[33]
22 Almeida T. S. ; Kokoh K. B. ; De Andrade A. R. Int. J. Hydrog.Energy 2011, 36, 3803. doi: 10.1016/j.ijhydene.2010.12.066
[34]
25 Radmilovic V. ; Gasteiger H. A. ; Ross P. N. J. Catal. 1995, 154, 98. doi: 10.1006/jcat.1995.1151
[35]
30 Gonzalo G. ; Nikolaos T. ; Elena P. ; Miguel A. P. ; Jose L. G. ; Fierro M. V. ; Martínez H. Int. J. Hydrog. Energy 2012, 37, 7131. doi: 10.1016/j.ijhydene.2011.11.031
[36]
31 Wang Q. ; Sun G. Q. ; Jiang L. H. ; Xin Q. ; Sun S. G. ; Jiang Y.X. ; Chen S. P. ; Jusys Z. ; Behm R. J. Phys. Chem. Chem. Phys. 2007, 9, 2686. doi: 10.1039/B700676B
[37]
32 De Souza R. F. B. ; Parreira L. S. ; Rascio D. C. ; Silva J. C.M. ; Teixeira-Neto E. ; Calegaro M. L. ; Spinace E. V. ; Neto A.O. ; Santos M. C. J. Power Sources 2010, 195, 1589. doi: 10.1016/j.jpowsour.2009.09.065
