p区金属基电催化还原二氧化碳制甲酸催化剂研究进展

The progress on Electrochemical CO_(2)-to-Formate Conversion by p-Block Metal Based Catalysts

以清洁可再生电能为驱动力,常温常压下将二氧化碳(CO_(2))选择性还原转化生成高附加值化学品或燃料,是解决目前能源和环境问题、实现CO_(2)资源化利用、促进碳循环回归平衡的有效手段之一。由于生成不同产物的还原电位和反应历程不同,单位产物的生产成本各有差异。最近研究表明,HCOOH是所有电化学CO_(2)还原产物中最具有经济效益和实用价值的产物之一。本文从电催化还原CO_(2)制HCOOH生成机理出发,综述了p区金属(如Sn、Bi、In)基催化剂在电催化还原CO_(2)制HCOOH领域取得的重要研究进展,其中以典型催化剂为例分析了CO_(2)还原生成HCOOH活性提高策略如氧化物还原转化、形貌调控、掺杂和合金化等,重点探讨了活性位点种类、数量以及催化剂电子结构在关键中间体*CO_(2)^(·-)、*OCHO的形成和吸附中的作用,最后总结了目前该领域面临的挑战以及未来发展方向。

Electrochemical CO_(2)reduction to value added chemical feedstocks and fuels driven by renewable electricity gives a promising and appealing approach to address the global challenges in energy and sustainability and eventually close the anthropogenic carbon cycle.The most crucial step for this conversion is to develop robust electrocatalysts promoting adsorption of CO_(2)molecule and subsequent activation with low energy barriers.Due to the different overpotentials and electron transfer amount needed for various reduction products,there is huge gap of producing price among a variety of products.Based on recent research,formic acid(or formate)is one of the most economically viable and useful reduction product in a couple of chemical processes.In this paper,starting with fundamental understanding of reaction mechanism,we review the main progress of p-block post-transition metal(e.g.,Sn,Bi,and In)based electrocatalysts for electrochemical CO_(2)reduction to produce formic acid.In addition,strategies to facilitate the catalytic performance of CO_(2)to formic acid)conversion including reduction conversion of metal oxides,morphology control,doping and alloying to modulate the electronic structure are also be briefly reviewed.Finally,we summarize the existing challenges and present perspectives for the future development of this exciting field.