Recent advances in copper-based catalysts for electrocatalytic CO2 reduction toward multi-carbon products

Qiang Wang, Hehe Wei, Ping Liu, Zixiang Su, Xue-Qing Gong
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Abstract

Electrocatalytic carbon dioxide reduction reaction (CO2RR) holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals. Electrocatalytic CO2 reduction toward carbon-containing products, including C1 products (carbon monoxide, formic acid, etc), C2 products (ethylene, ethanol, etc.) and multi-carbon products (e.g., npropanol), provides beneficial fuel and chemicals for industrial production. The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO2 reduction toward multi-carbon(C2+) products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products. In this paper, we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years, introduce the basic principles of electrocatalytic CO2RR, and detailly elucidate two widely accepted mechanisms of C-C coupling reactions. Among abundant nanomaterials, copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO2RR attributing to effective C-C coupling reactions. Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts, we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products, where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming CC bond to form the key intermediates and increase the production of multi-carbon products. Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO2 reduction reaction are also proposed.

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铜基催化剂在电催化二氧化碳还原为多碳产品方面的最新进展
电催化二氧化碳还原反应(CO2RR)有望同时克服温室效应和合成大量化学品。电催化二氧化碳还原反应生成含碳产物,包括 C1 产物(一氧化碳、甲酸等)、C2 产物(乙烯、乙醇等)和多碳产物(如正丙醇),为工业生产提供了有益的燃料和化学品。与 C1 产物的催化剂相比,电化学 CO2 还原多碳(C2+)产物过程中多质子转移过程的复杂性和 C-C 偶联的困难性引起了人们对催化剂设计的越来越多的关注。本文回顾了近年来电催化二氧化碳还原合成多碳产物的主要进展,介绍了电催化二氧化碳还原反应的基本原理,并详细阐明了两种广为接受的 C-C 偶联反应机理。在丰富的纳米材料中,铜基催化剂是电化学二氧化碳还原反应制备多碳化学品的优秀催化剂,这归功于其有效的 C-C 偶联反应。针对广泛应用的铜基催化剂在制备多碳化学品方面的不同选择性,我们通过分离不同的多碳产物对各种铜基催化剂进行了分类和总结,其中空间结构和电子结构的修饰有利于增加 CO 的覆盖率或降低形成 CC 键的活化能垒,从而形成关键的中间产物,提高多碳产物的产量。此外,还提出了铜基催化剂在电化学二氧化碳还原反应中的基础研究和开发所面临的挑战和前景。
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