Abstract
The nano-cubic Pt modified by tin (Sn) was synthesized and used to investigate the role of this adatom played in the ethanol oxidation. The onset potential of ethanol oxidation was significantly shifted negatively which can be forward about 300 mV when the coverage of Sn (θSn)was 0.9. The electrtochemical in situ FTIR result demonstrated that the amount of CO2 increased first, and then decreased with θSn increased, and reached the maximun when θSn was 0.38. Furthermore, the formation of acetic acid could be observed at very low potential (-0.05 V) after modifying Sn adatom, and the amount of acetic acid increased with θSn increased. That is, Sn deposited on Pt surfaces has a double effect on the ethanol oxidation. First, it facilitates the oxidation of CO coming from the cleavage of the C—C bond in ethanol by a bifunctiontal mechanism. Second, the Pt–Sn ensemble catalyzes the oxidation of ethanol to acetic acid. This means that the main product in the oxidation of ethanol for the Pt–Sn system should be acetic acid unless the Pt surface structure has some special sites able to break the C—C bond.
Graphical Abstract
Keywords
tin modified, nano-cubic Pt, ethanol, electrocatalysis, in situ FTIR
Publication Date
2014-10-28
Online Available Date
2014-04-27
Revised Date
2014-04-22
Received Date
2014-02-19
Recommended Citation
Lu RAO, Bin-wei ZHANG, Yan-yan LI, Yan-xia JIANG, Shi-gang SUN.
Electrochemical and Spectroscopic Studies of Ethanol Oxidation on Nano-Cubic Pt Modified by Tin Adatoms[J]. Journal of Electrochemistry,
2014
,
20(5): 395-400.
DOI: 10.13208/j.electrochem.131177
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol20/iss5/1
References
[1] Annett Rabis P R, Thomas J, Schmidt A. Electrocatalysis for polymer electrolyte fuel cells: Recent achievements and future challenges[J]. ACS Catalysis, 2012, 2(5): 864-890.
[2] Hu C G, Cheng H H, Zhao Y, et al. Newly-designed complex ternary Pt/PdCu nanoboxes anchored on three-dimensional graphene framework for highly efficient ethanol oxidation[J]. Advanced Materials, 2012, 24(40): 5493-5498.
[3] Brouzgou A, Tsiakaras P. PEMFCs and AEMFCs directly fed with ethanol: A current status comparative review[J]. Journal of Applied Electrochemistry, 2013, 43(2): 119-136.
[4] Santasalo Aarnio A, Tuomi S, Jalkanen K, et al. The correlation of electrochemical and fuel cell results for alcohol oxidation in acidic and alkaline media[J]. Electrochimica Acta, 2013, 87(20): 730-738.
[5] Song S Q, Tsiakaras P. Recent progress in direct ethanol proton exchange membrane fuel cells[J]. Applied Catalysis B: Environmental, 2006, 63(3/4): 187-193.
[6] Cui G F, Song S Q, Shen P K, et al. First-principles considerations on catalytic activity of Pd toward ethanol oxidation[J]. Journal of Physical Chemistry C, 2009, 113(35): 15639-1564.
[7] Wu H X, Li H J, Zhai Y J, et al. Facile synthesis of free-standing Pd-based nanomembranes with enhanced catalytic performance for methanol/ethanol oxidation[J]. Advanced Materials, 2012, 24(12): 1594-1597.
[8] Du W X, Deskins N A, Su D, et al. Iridium-ruthenium alloyed nanoparticles for the ethanol oxidation fuel cell reactions[J]. ACS Catalysis, 2012, 2(6): 1226-1231.
[9] Wang F W, Liu Z P. Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: New transition-state searching method for resolving the complex reaction network[J]. Journal of the American Chemical Society, 2008, 130(33): 10996-11004.
[10] He Q G, Shyam B, Macounova K, et al. Dramatically enhanced cleavage of the C—C bond using an electrocatalytically coupled reaction[J]. Journal of the American Chemical Society, 2012, 134(20): 8655-8661.
[11] Dutta A, Datta J. Outstanding catalyst performance of PdAuNi nanoparticles for the anodic reaction in an alkaline direct ethanol (with Anion-Exchange Membrane) fuel cell[J]. Journal of Physical Chemistry C, 2012, 116(49): 25677-25688.
[12] Li M, Cullen D A, Sasaki K, et al. Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: Making Ir capable of splitting C—C bond[J]. Journal of the American Chemical Society, 2013, 135(1): 132-141.
[13] Wang X D, Stover J, Zielasek V, et al. Colloidal synthesis and structural control of PtSn bimetallic nanoparticles[J]. Langmuir 2011, 27(17): 11052-11061.
[14] Zhou W J, Song S Q, Li W Z, et al. Direct ethanol fuel cells based on PtSn anodes: The effect of Sn content on the fuel cell performance[J]. Journal of Power Sources, 2005, 140(1): 50-58.
[15] Colle V D, Berna A, Tremiliosi-Filho G, et al. Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: Electrochemical and spectroscopic studies[J]. Physical Chemistry Chemical Physics, 2008, 10(5): 3766-3773.
[16] Camara G A, de Lima R B, Iwasita T. Catalysis of ethanol electrooxidation by PtRu: The influence of catalyst composition[J]. Electrochemistry Communications 2004, 6(8): 812-815.
[17] Vigier F, Coutanceau C, Hahn F, et al. On the mechanism of ethanol electro-oxidation on Pt and PtSn catalysts: Electrochemical and in situ IR reflectance spectroscopy studies[J]. Journal of Electroanalytical Chemistry, 2004, 563(1): 81-89.
[18] Del Colle V, Souza-Garcia J, Tremiliosi-Filho G, et al. Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms[J]. Physical Chemistry Chemical Physics, 2011, 13(50): 12163-12173.
[19] Li Y Y(李艳艳), Rao L(饶路), Jiang Y X(姜艳霞), et al. Electrooxidation of ethanol on platinum nanocubes supported on multi-walled carbon nanotubes[J]. Chemical Journal of Chinese Universities, 2013, 34(2): 408-413.
[20] Giz M J, Camara G A, Maia G. The ethanol electrooxidation reaction at rough PtRu electrodeposits: A FTIRS study[J]. Electrochemistry Communications, 2009, 11(8): 1586-1589.
[21] García-Rodríguez S, Rojas S, Pe?a M A, et al. An FTIR study of Rh-PtSn/C catalysts for ethanol electrooxidation: Effect of surface composition[J]. Applied Catalysis B: Environmental, 2011, 106(3/4): 520-528.
[22] Lu G Q, Sun S G, Chen S P, et al. Novel properties of dispersed Pt and Pd thin layer supported on GC for CO adsorption studied using in situ MS-FTIR spectroscopy[J]. Journal of Electroanalytical Chemistry, 1997, 421(1/2): 19-23.
[23] Yan Y G, Yang Y Y, Peng B, et al. Study of CO oxidation on polycrystalline Pt electrodes in acidic solution by ATR-SEIRAS[J]. Journal of Physical Chemistry C, 2011, 115(33): 16378-16388.
Included in
Analytical Chemistry Commons, Catalysis and Reaction Engineering Commons, Engineering Science and Materials Commons, Materials Chemistry Commons, Materials Science and Engineering Commons, Nanoscience and Nanotechnology Commons, Physical Chemistry Commons, Power and Energy Commons