化学
催化作用
析氧
拉曼光谱
反应中间体
反应机理
原位
价(化学)
氧气
合理设计
光化学
金属
化学工程
无机化学
电化学
纳米技术
电极
物理化学
有机化学
材料科学
光学
物理
工程类
作者
Yunfeng Hu,Cejun Hu,Aoxuan Du,Tianshu Xiao,Linfeng Yu,Chengkai Yang,Wei Xie
标识
DOI:10.1021/acs.analchem.2c04931
摘要
Disclosing the roles of reactive sites at catalytic interfaces is of paramount importance for understanding the reaction mechanism. However, due to the difficulties in the detection of reaction intermediates in the complex heterophase reaction system, disentangling the highly convolved roles of different surface atoms remains challenging. Herein, we used CoOx as a model catalyst to study the synergy of CoTd2+ and CoOh3+ active sites in the electrocatalytic oxygen evolution reaction (OER). The formation and evolution of reaction intermediates on the catalyst surface during the OER process were investigated by in situ surface-enhanced Raman spectroscopy (SERS). According to the SERS results in ion-substitution experiments, CoOh3+ is the catalytic site for the conversion of OH- to O-O- intermediate species (1140-1180 cm-1). CoOOH (503 cm-1) and CoO2 (560 cm-1) active centers generated during the OER, at the original CoTd2+ sites of CoOx, eventually serve as the O2 release sites (conversion of O-O- intermediate to O2). The mechanism was further confirmed on Co2+-Co3+ layered double hydroxides (LDHs), where an optimal ratio of 1:1.2 (Co2+/Co3+) is required to balance O-O- generation and O2 release. This work highlights the synergistic role of metal atoms at different valence statuses in water oxidation and sheds light on surface component engineering for the rational design of high-performance heterogeneous catalysts.
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