A Revisit to the Role of Bridge-adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid at Pt Electrodes (cited: 2)

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 withformic 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.     

Pt电极上甲酸电催化氧化机理研究进展

本文综述了甲酸在铂电极上电催化氧化机理的实验和理论研究进展. 铂电极甲酸的电化学氧化主要有两种途径：1）间接途径,甲酸经由CO中间物氧化为最终产物CO₂,室温下该途径对总电流贡献不超过1%;2）直接途径,甲酸直接氧化生成CO₂. 作者课题组对文献中桥式吸附甲酸根是否是甲酸氧化反应直接途径的反应中间物的争论进行了详细的分析和探讨,认为桥式吸附的甲酸根不是间接途径中生成CO的前驱体,也不是甲酸直接氧化途径的中间物. 作者课题组还指出了支持甲酸根是甲酸直接氧化途径的反应中间物的推论的问题所在.     

Hydride Pinning Pathway in the Hydrogenation of CO2 to Formic Acid on Dimeric Tin Dioxide

Capture of CO₂ and its conversion into organic feedstocks are increasingly needed as society moves towards a renewable energy economy. Here, a hydride-assisted selective reduction pathway is proposed for the conversion of CO₂ to formic acid (FA) over SnO₂ monomers and dimers. Our density functional theory calculations infer a strong chemisorption of CO₂ on SnO₂ clusters forming a carbonate structure, whereas heterolytic cleavage of H₂ provides a new pathway for the selective reduction of CO₂ to formic acid at low overpotential. Among the two investigated pathways for reduction of CO₂ to HCOOH, the hydride pinning pathway is found promising with a unique selectivity for HCOOH. The negatively-charged hydride forms on the cluster during the dissociation of H₂ and facilitates the formation of a formate intermediate, which determines the selectivity for FA over the alternative CO and H₂ evolution reaction. It is confirmed that SnO₂ clusters exhibit a different catalytic behaviour from their surface equivalents, thus offering promise for future work investigating the reduction of CO₂ to FA via a hydride pinning pathway at low overpotential and CO₂ capturing.     

碱性介质中CO对甲醇在PtAu(111)和Pt(111)表面氧化生成甲酸的影响的第一性原理研究

采用密度泛函理论计算研究了碱性介质中甲醇在清洁的PtAu(111)和Pt(111)表面、及有CO存在的PtAu(111)和Pt(111)表面的氧化。计算结果表明,在碱性介质中,预吸附的CO促进了甲醇在PtAu(111)和Pt(111)表面氧化的每一步反应,这与其在Au(111)表面的作用相似。究其原因,是由于CO的吸附增强了OH的稳定性和碱性,从而增强了OH夺取氢原子的能力。