Bohra Divya, Ledezma-Yanez Isis, Li Guanna, de Jong Wiebren, Pidko Evgeny A, Smith Wilson A
Materials for Energy Conversion and Storage (MECS), Department of Chemical Engineering, Delft University of Technology, 2629, HZ, Delft, The Netherlands.
Large-Scale Energy Storage (LSE), Department of Process and Energy, Delft University of Technology, 2629, HZ, Delft, The Netherlands.
Angew Chem Int Ed Engl. 2019 Jan 28;58(5):1345-1349. doi: 10.1002/anie.201811667. Epub 2018 Dec 18.
Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO ER). Herein, we study the role of the formate (HCOO ) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton-electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface-enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O-bound bidentate species on polycrystalline Ag during CO ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO and H production and a higher selectivity towards CO.
银是通过二氧化碳电化学还原（CO₂ER）生产一氧化碳（CO）的一种很有前景的催化剂。在此，我们研究甲酸盐（HCOO⁻）中间体OCHO的作用，旨在解决银在理论理解和实验性能之间的差异。我们表明，CO生成途径中的第一步耦合质子-电子转移（CPET）步骤与形成H的Volmer步骤竞争，而这个Volmer步骤是形成*OCHO的先决条件。我们表明，由于溶剂化作用和有利的结合强度，OCHO应该很容易在银表面形成。原位表面增强拉曼光谱（SERS）实验给出了在CO₂ER过程中多晶银表面存在O键合双齿物种的初步证据，我们将其归因于OCHO。OCHO存在时的横向吸附质相互作用对H的表面覆盖有显著影响，导致HCOO⁻和H生成受到抑制，并对CO具有更高的选择性。
Zotero 插件
