电催化还原二氧化碳制一氧化碳催化剂研究进展

电催化还原CO₂作为缓解能源危机和全球变暖的有效途径已成为催化领域的研究热点。然而，不同反应途径的氧化还原电位较为接近，使产物的选择性成为电催化还原CO₂所需解决的主要问题。迄今为止，在水性电解质中可实现CO₂选择性地转化为一氧化碳（CO）和甲酸（HCOOH）。本文简述了电催化还原CO₂制CO的机理，包括CO₂吸附过程、二电子转移过程和CO脱附过程。从贵金属的晶面设计、形貌调控和表面功能化对反应活性和产物选择性的影响，铁卟啉、钴酞菁和镍三嗪在还原CO₂为CO反应中的电子转移途径，非金属碳基材料中杂原子和碳基质间的耦合效应等方面，重点介绍了近年来贵金属催化剂、过渡金属络合物催化剂和非金属碳基材料催化剂的研究进展，总结了各类催化剂的优缺点。指出在三类电催化还原CO₂制CO的催化剂中，非金属碳材料具有较高的CO法拉第效率，尤其是非金属碳材料成本较低、制备简单、结构易调控，在电催化还原中具有潜在的应用优势，是有望实现商业化应用的新型催化剂的候选材料之一。

Research progress on catalysts for electrocatalytic reduction of carbon dioxide to carbon monoxide

Electrocatalytic reduction of CO₂ to alleviate the energy crisis and global warming has become a research hotspot in catalysis. However, due to the close oxidation-reduction potentials of different reaction pathways, the product selectivity of electrocatalytic reduction of CO₂ is not high and should be improved. So far, carbon monoxide (CO) and formic acid (HCOOH) can be obtained with high-selectivity in aqueous electrolytes. The mechanism of electrocatalytic reduction of CO₂ to CO is described in a three-step process of CO₂ adsorption, two-electron transfer and CO desorption. The recent research progress of noble metal catalysts, transition metal complex catalysts and non-metallic carbon-based materials is introduced, including:①the influence of crystal face design, morphology control and surface functionalization of noble metals on the reaction activity and product selectivity; ②the electron transfer paths of iron porphyrin, cobalt phthalocyanine and nickel triazine in the reduction of CO₂ to CO; ③the coupling effect between heteroatoms and carbon matrix in non-metallic carbon-based materials. The advantages and disadvantages of various catalysts are briefly summarized. Among the three kinds of catalysts for electrocatalytic reduction of CO₂ to CO, the non-metallic carbon materials have high CO Faraday efficiency, and they have potential application advantages in the electrocatalytic reduction because of their low cost, simple preparation and controllable structure. Carbon materials will be one of the candidate materials of novel catalysts which could realize commercial application.