On the origin of the elusive first intermediate of CO2 electroreduction
On the origin of the elusive first intermediate of CO2 electroreduction
复制标题
DOI：
10.1073/pnas.1802256115
复制
发表时间：
2018-10-02
影响因子：
11.1
通讯作者：
Ponnurangam, Sathish
中科院分区：
文献类型：
--
作者：
Chernyshova, Irina, V;Somasundaran, Ponisseril;Ponnurangam, Sathish
我们解决了长期存在的争议的第一步的CO2电解质水溶液中的燃料，通过提供红色光谱的证据表明，第一个中间体的CO2转化为甲酸铜是羧酸根阴离子 *CO2-协调的表面通过其C-O键之一。我们确定这种中间体，并深入了解其形成，其化学和电子性质，以及其依赖于电极电位的优势，利用尖端的方法，包括operandi表面增强拉曼散射（Sers）授权的同位素交换和电化学斯塔克效应，反应动力学（塔菲尔）分析，和密度泛函理论（DFT）模拟。Sers光谱是在工作的Cu表面上测量的。这些结果推进了对CO2电还原及其对一氧化碳和甲酸盐选择性的机理理解。
We resolve the long-standing controversy about the first step of the CO2 electroreduction to fuels in aqueous electrolytes by providing red spectroscopic evidence that the first intermediate of the CO2 conversion to formate on copper is a carboxylate anion *CO2- coordinated to the surface through one of its C-O bonds. We identify this intermediate and gain insight into its formation, its chemical and electronic properties, as well as its dependence on the electrode potential by taking advantage of a cutting-edge methodology that includes operandi surface-enhanced Raman scattering (SERS) empowered by isotope exchange and electrochemical Stark effects, reaction kinetics (Tafel) analysis, and density functional theory (DFT) simulations. The SERS spectra are measured on an operating Cu surface. These results advance the mechanistic understanding of CO2 electroreduction and its selectivity to carbon monoxide and formate.