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A Revisit to the Role of Bridge-adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid at Pt Electrodes (cited: 2)
Jie Xu,Dong Mei,Dao-fu Yuan,Zun-biao Zhang,Shao-xiong Liu,Yan-xia Chen*
Author NameAffiliationE-mail
Jie Xu Hefei National Laboratory for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Dong Mei Hefei National Laboratory for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Dao-fu Yuan Hefei National Laboratory for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Zun-biao Zhang Hefei National Laboratory for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Shao-xiong Liu Hefei National Laboratory for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Yan-xia Chen* Hefei National Laboratory for Physical Science at Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China yachen@ustc.edu.cn 
Abstract:
The mechanism and kinetics of electrocatalytic oxidation of formic acid at Pt electrodes is discussed in detail based on previous electrochemical in-situ ATR-FTIRS data [Langmuir 22, 10399 (2006) and Angewa. Chem. Int. Ed. 50, 1159 (2011)]. A kinetic model with formic acid adsorption (and probably the simultaneous C-H bond activation) as the rate determining step, which contributes to the majority of reaction current for formic acid oxi-dation, was proposed for the direct pathway. The model simulates well the IR spectroscopic results obtained under conditions where the poisoning effect of carbon monoxide (CO) is negligible and formic acid concentration is below 0.1 mol/L. The kinetic simulation predicts that in the direct pathway formic acid oxidation probably only needs one Pt atom as active site, formate is the site blocking species instead of being the active intermediate. We review in detail the conclusion that formate pathway (with either 1st or 2nd order reaction kinetics) is the direct pathway, possible origins for the discrepancies are pointed out.
Key words:  Formic acid oxidation, Mechanism, Electrocatalysis, Formate pathway, Direct pathway
FundProject:
重新审视桥式吸附甲酸根在铂电极上电催化氧化甲酸过程中的作用 (cited: 2)
徐杰,梅东,袁道福,张尊彪,刘少雄,陈艳霞*
摘要:
基于以前报道的电化学原位ATR-FTIRS数据(Langmuir 22,10399 (2006)和Angewa. Chem. Int. Ed., 50,1159 (2011)),详细讨论了甲酸在铂电极上电催化氧化机理及动力学过程.提出了直接反应路径的动力学模型,即甲酸吸附(同时C-H键活化)作为此反应的决速步骤,此反应路径贡献甲酸氧化反应的大部分电流.该动力学模型可以很好地拟合在无CO毒化影响和浓度在0.1 mol/L以下的红外光谱结果.这种机理预测了甲酸氧化直接途径可能只需要一个Pt原子作为反应位点,甲酸根阻碍活性位点,并非为反应中间物.另外还详细检验了之前其他小组曾提出的甲酸根途径(一级或二级反应)为甲酸氧化直接途径,并指出了引起分歧的原因.
关键词:  甲酸氧化,机理,电催化,甲酸根途径,直接途径
DOI:10.1063/1674-0068/26/03/321-328
分类号: