The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum
The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum
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DOI：
10.1002/anie.201004782
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发表时间：
2011-01-01
影响因子：
16.6
通讯作者：
Gutierrez, Claudio
中科院分区：
文献类型：
--
作者：
Osawa, Masatoshi;Komatsu, Kei-ichi;Gutierrez, Claudio
甲酸（HCOOH）在铂电极上的氧化作为一个模型电催化反应已被广泛研究。[1-4]一般认为，HCOOH通过双途径机制氧化为CO2：一种途径（主要途径）涉及通过反应性中间体的快速反应，第二种途径包括形成有毒物质的步骤。这种在高电位下被氧化成CO2的物质已被鉴定为吸附CO，其通过HCOOH脱水形成。吸附的羟基羰基（COOHads）长期以来被认为是主要途径中的反应中间体，[1-4]但迄今为止还没有报道这种物质的光谱检测。通过使用衰减全反射模式（ATRSEIRAS）的表面增强红外吸收光谱，[5]三木等人。[6]观察到甲酸在HCOOH氧化过程中以桥键结构吸附在Pt电极上。在系统的时间分辨ATR-SEIRAS分析的氧化动力学的基础上，Samjeskovich et al. [7-9]提出吸附甲酸盐（HCOOads）是主要途径中的反应中间体，其分解为CO2是速率决定步骤（rds）。吸附的甲酸盐与本体溶液中的HCOOH处于平衡状态，反应途径（甲酸盐途径）可由方程式（1）表示[8-10]
The oxidation of formic acid (HCOOH) on platinum electrodes has been extensively investigated as a model electrocatalytic reaction.[1–4] It is generally accepted that HCOOH is oxidized to CO2 through a dual-pathway mechanism: one pathway (the main pathway) involves a fast reaction via a reactive intermediate and the second pathway includes a step in which a poisoning species is formed. This species, which is oxidized to CO2 at high potentials, has been identified as adsorbed CO, which is formed by dehydration of HCOOH. Adsorbed hydroxycarbonyl (COOHads) has long been assumed to be the reactive intermediate in the main pathway,[1–4] but the spectroscopic detection of this species has not been reported to date.By using surface-enhanced infrared absorption spectroscopy in the attenuated total reflection mode (ATRSEIRAS),[5] Miki et al.[6] observed that formate is adsorbed in a bridge-bonded configuration on Pt electrodes during HCOOH oxidation. On the basis of systematic time-resolved ATR-SEIRAS analysis of the oxidation dynamics, SamjeskØ et al.[7–9] suggested that adsorbed formate (HCOOads) is a reactive intermediate in the main pathway and its decomposition to CO2 is the rate-determining step (rds). The adsorbed formate is in equilibrium with HCOOH in the bulk solution and the reaction pathway (formate pathway) can be represented by Equation (1)[8–10]