CO 电还原难以捉摸的第一个中间产物的起源。
On the origin of the elusive first intermediate of CO electroreduction.
机构信息
Department of Earth and Environmental Engineering, Columbia University, New York, NY 10027;
Department of Earth and Environmental Engineering, Columbia University, New York, NY 10027.
出版信息
Proc Natl Acad Sci U S A. 2018 Oct 2;115(40):E9261-E9270. doi: 10.1073/pnas.1802256115. Epub 2018 Sep 17.
Abstract
We resolve the long-standing controversy about the first step of the CO electroreduction to fuels in aqueous electrolytes by providing direct spectroscopic evidence that the first intermediate of the CO conversion to formate on copper is a carboxylate anion *CO 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 operando 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 CO electroreduction and its selectivity to carbon monoxide and formate.
摘要
我们通过提供直接的光谱证据解决了在水溶液电解质中 CO 电还原为燃料的第一步的长期争议，该证据表明在铜上将 CO 转化为甲酸盐的第一步中间产物是通过其 C-O 键之一与表面配位的羧酸根阴离子*CO。我们通过利用包括借助同位素交换和电化学斯塔克效应增强的原位表面增强拉曼散射（SERS）、反应动力学（塔菲尔）分析和密度泛函理论（DFT）模拟等前沿方法来识别这种中间产物，并深入了解其形成、化学和电子性质以及其对电极电势的依赖性。SERS 光谱是在工作的 Cu 表面上测量的。这些结果推进了对 CO 电还原及其对一氧化碳和甲酸盐选择性的机理理解。
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