Enhancing ^(*)CO coverage on Sm-Cu_(2)O via 4f-3d orbital hybridization for highly efficient electrochemical CO_(2) reduction to C_(2)H_(4)  

作　　者：Xiaojun Wang Lanlan Shi Weikun Ren Jingxian Li Yuanming Liu Weijie Fu Shiyu Wang Shuyun Yao Yingjie Ji Kang Ji Liwen Zhang Zhiyu Yang Jiangzhou Xie Yi-Ming Yan 

机构地区：[1]State Key Laboratory of Organic-Inorganic Composites,Beijing Advanced Innovation Center for Soft Matter Science and Engineering,Beijing University of Chemical Technology,Beijing100029,China [2]School of Mechanical and Manufacturing Engineering,University of New South Wales,Sydney 2052,New South Wales,Australia [3]Zolix Instruments Company Limited,Beijing 101102,China

出　　处：《Journal of Energy Chemistry》2024年第12期409-416,共8页能源化学（英文版）

基　　金：Financial support from the National Natural Science Foundation of China(grant nos.22379006,21575016,U20A20154,22279005);from the National Program for Support of Top-notch Young Professionals is gratefully acknowledged。

摘　　要：The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing CO_(2) to C_(2+)products,the instability of Cu^(+)species,which tend to reduce to Cu~0 at cathodic potentials during CO_(2) reduction,poses a significant challenge.Here,we report the development of SmCu_(2)O and investigate the influence of f-d orbital hybridization on the CO_(2) reduction reaction (CO_(2)RR).Supported by density functional theory (DFT) calculations,our experimental results demonstrate that hybridization between Sm^(3+)4f and Cu^(+)3d orbitals not only improves the adsorption of *CO intermediates and increases CO coverage to stabilize Cu^(+) but also facilitates CO_(2) activation and lowers the energy barriers for CAC coupling.Notably,Sm-Cu_(2)O achieves a Faradaic efficiency for C_(2)H_(4) that is 38%higher than that of undoped Cu_(2)O.Additionally,it sustains its catalytic activity over an extended operational period exceeding 7 h,compared to merely 2 h for the undoped sample.This research highlights the potential of fd orbital hybridization in enhancing the efficacy of copper-based catalysts for CO_(2)RR,pointing towards a promising direction for the development of durable,high-performance electrocatalysts for sustainable chemical synthesis.

关 键 词：Electrochemical CO_(2)reduction F-d orbital hybridization Adsorption of^(*)CO CO coverage C_(2+)products 

分 类 号：TQ426[化学工程] TQ221.211