干旱区生态环境知识资源中心(Arid): Mechanistic Insights into Water-Mediated CO2 Electrochemical Reduction Reactions on Cu@C2N Catalysts: A Theoretical Study

Arid

DOI	10.3866/PKU.WHXB202303040
	Mechanistic Insights into Water-Mediated CO2 Electrochemical Reduction Reactions on Cu@C2N Catalysts: A Theoretical Study
	Xu, Hanyu; Song, Xuedan; Zhang, Qing; Yu, Chang; Qiu, Jieshan
通讯作者	Song, XD ; Qiu, JS
来源期刊	ACTA PHYSICO-CHIMICA SINICA
ISSN	1000-6818
出版年	2024
卷号	40 期号:1
英文摘要	CO2 molecules can be converted into various fuels and industrial chemicals through electrochemical reduction, effectively addressing the problems of global warming, desertification, ocean acidification, and other adverse environmental changes and energy supply issues such as excessive utilization of nonrenewable fossil fuels. Generally, the pathway of the CO2 reduction reaction (CO2RR) involves multiple proton-electron pairs transferred to the reactants, resulting in the production of multiple reduction products. Here, protons are derived from water molecules under aqueous solvent conditions. Therefore, exploring the effect of water molecules on the proton-electron pair transfer process in CO2RRs is essential. In this study, we developed a water-mediated hydrogen shuttle model (H-shuttling) as a hydrogenation model to investigate the effect of water molecules on the proton-electron pair transfer process in CO2RRs and compared it with the widely used water-free direct hydrogenation model (H-transfer), wherein the hydrogen atom is used as a proton. Because copper is a metal electrode material capable of producing hydrocarbons from CO2 electroreduction with a high faraday efficiency, and nitrogen-doped graphene (C2N) exhibits excellent catalytic CO2 activation, we selected a single copper atom-embedded C2N (Cu@C2N) as the catalyst. Furthermore, to study the effect of graphene on the CO2RR activity of Cu@C2N/G, we selected a graphene-loaded Cu@C2N composite (Cu@C2N/G) as the catalyst because graphene was utilized as a substrate to boost the conductivity of the catalyst. In the two hydrogenation models, we investigated the mechanisms of CO2RRs on Cu@C2N and Cu@C2N/G catalysts through density functional theory calculations. Notably, in the H-shuttling model, the H atom combines with the water molecule to form H3O, which transfers one of its own H atoms to a reactant on the catalyst surface, yielding a reaction intermediate. The H-shuttling model enhances the interaction between the catalyst and intermediate. Graphene, as a substrate, transfers electrons to the Cu@C2N surface of the Cu@C2N/G catalyst, which is demonstrated by calculations of the Bader charge transferred between the reaction intermediate and catalyst, as well as the Gibbs free energy of the CO2 reduction elementary reaction. This effectively lowers the Gibbs free energy of the potential-determining step and enhances the CO2RR catalytic activity of Cu@C2N/G. Moreover the limiting potentials of the CO2RR and hydrogen evolution reaction are determined to obtain the activity and selectivity of the Cu@C2N and Cu@C2N/G catalysts. The results indicate that CO2 molecules on the Cu@C2N and Cu@C2N/G catalysts generate HCOOH at low applied potentials, and are able to produce CO, CH3OH, CH4, and H2 as the applied potentials increases.
英文关键词	CO2 reduction reaction Electrocatalysis Nitrogen-doped graphene Water-mediated hydrogen shuttle Reaction mechanism Density functional theory
类型	Article
语种	英语
开放获取类型	Bronze
收录类别	SCI-E
WOS记录号	WOS:001069889400006
WOS关键词	CARBON-DIOXIDE
WOS类目	Chemistry, Physical
WOS研究方向	Chemistry
资源类型	期刊论文
条目标识符	http://119.78.100.177/qdio/handle/2XILL650/402603
推荐引用方式 GB/T 7714	Xu, Hanyu,Song, Xuedan,Zhang, Qing,et al. Mechanistic Insights into Water-Mediated CO2 Electrochemical Reduction Reactions on Cu@C2N Catalysts: A Theoretical Study[J],2024,40(1).
APA	Xu, Hanyu,Song, Xuedan,Zhang, Qing,Yu, Chang,&Qiu, Jieshan.(2024).Mechanistic Insights into Water-Mediated CO2 Electrochemical Reduction Reactions on Cu@C2N Catalysts: A Theoretical Study.ACTA PHYSICO-CHIMICA SINICA,40(1).
MLA	Xu, Hanyu,et al."Mechanistic Insights into Water-Mediated CO2 Electrochemical Reduction Reactions on Cu@C2N Catalysts: A Theoretical Study".ACTA PHYSICO-CHIMICA SINICA 40.1(2024).