Molecular engineering binuclear copper catalysts for selective CO_(2) reduction to C_(2) products  

作　　者：Qi Zhao Kai Lei Bao Yu Xia Rachel Crespo-Otero Devis Di Tommaso 

机构地区：[1]Department of Chemistry,School of Physical and Chemical Sciences,Queen Mary University of London,London,E14NS,UK [2]Key Laboratory of Material Chemistry for Energy Conversion and Storage(Ministry of Education),Hubei Key Laboratory of Material Chemistry and Service Failure,State Key Laboratory of Materials Processing and Die&Mould Technology,School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology(HUST),Wuhan 430074,Hubei,China [3]Department of Chemistry,University College London,London,WC1H 0AJ,UK [4]Digital Environment Research Institute,Queen Mary University of London,Empire House,London E11HH,UK

出　　处：《Journal of Energy Chemistry》2024年第6期166-173,I0005,共9页能源化学（英文版）

基　　金：the HUST-QMUL Strategic Partnership Research Funding(No.2022-HUST-QMUL-SPRF-03),which funded the project“Design of Binuclear Copper Electrocatalysts for CO_(2) Conversion from First Principles”;the China Scholarship Council for financial support。

摘　　要：Molecular copper catalysts serve as exemplary models for correlating the structure-reaction-mechanism relationship in the electrochemical CO_(2) reduction(eCO_(2)R),owing to their adaptable environments surrounding the copper metal centres.This investigation,employing density functional theory calculations,focuses on a novel family of binuclear Cu molecular catalysts.The modulation of their coordination configuration through the introduction of organic groups aims to assess their efficacy in converting CO_(2) to C_(2)products.Our findings highlight the crucial role of chemical valence state in shaping the characteristics of binuclear Cu catalysts,consequently influencing the eCO_(2)R behaviour,Notably,the Cu(Ⅱ)Cu(Ⅱ)macrocycle catalyst exhibits enhanced suppression of the hydrogen evolution reaction(HER),facilitating proton trans fer and the eCO_(2)R process.Fu rthermore,we explo re the impact of diverse electro n-withdrawing and electron-donating groups coordinated to the macrocycle(R=-F,-H,and-OCH_3)on the electron distribution in the molecular catalysts.Strategic placement of-OCH_3 groups in the macrocycles leads to a favourable oxidation state of the Cu centres and subsequent C-C coupling to form C_(2) products.This research provides fundamental insights into the design and optimization of binuclear Cu molecular catalysts for the electrochemical conversion of CO_(2) to value-added C_(2) products.

关 键 词：Molecular catalyst design Selective CO_(2)reduction C_(2)products Density functional theory calculations 

分 类 号：TQ426[化学工程]