Activity and Selectivity Control in CO2 Electroreduction to Multicarbon Products over CuOx Catalysts via Electrolyte Design
Activity and Selectivity Control in CO2 Electroreduction to Multicarbon Products over CuOx Catalysts via Electrolyte Design
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DOI：
10.1021/acscatal.8b02587
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发表时间：
2018-11-01
期刊：
影响因子：
12.9
通讯作者：
Roldan Cuenya, Beatriz
中科院分区：
文献类型：
--
作者：
Gao, Dunfeng;McCrum, Ian T.;Roldan Cuenya, Beatriz
CO2电还原反应（CO2 RR）对化学品和燃料具有基础和实际意义，因为它将导致更有效地储存可再生能源，同时关闭碳循环。在这里，我们报道了通过电解质设计，在O-2-等离子体活化的Cu催化剂上，CO2 RR对多碳烃和醇的活性和选择性增强（类似于69%的法拉第效率和-45.5 mA cm（-2）的C2+在-1.0 V vs RHE下的部分电流密度）。增加电解质中碱金属阳离子的尺寸，结合有利于其吸附的表面下氧物质的存在，显著改善了CuOx电极上的C-C耦合。Cs+和I-的共存诱导的CuOx表面的剧烈重组，形成含有稳定的CuI物种的形状的颗粒，以及更有利的反应中间体的稳定化和伴随的高C2+选择性。本工作结合实验和密度泛函理论，提供了深入了解氧化物衍生的铜催化剂的CO2 RR的活性中心和反应机理。
The CO, electroreduction reaction (CO2RR) to chemicals and fuels is of both fundamental and practical significance, since it would lead to a more efficient storage of renewable energy while closing the carbon cycle. Here we report enhanced activity and selectivity for the CO2RR to multicarbon hydrocarbons and alcohols (similar to 69% Faradaic efficiency and -45.5 mA cm(-2) partial current density for C2+ at -1.0 V vs RHE) over O-2-plasma-activated Cu catalysts via electrolyte design. Increasing the size of the alkali-metal cations in the electrolyte, in combination with the presence of subsurface oxygen species which favor their adsorption, significantly improved C-C coupling on CuOx electrodes. The coexistence of Cs+ and I- induced drastic restructuring of the CuOx surface, the formation of shaped particles containing stable CuI species, and a more favorable stabilization of the reaction intermediates and concomitant high C2+ selectivity. This work, combining both experiment and density functional theory, provides insights into the active sites and reaction mechanism of oxide-derived Cu catalysts for the CO2RR.