Cu_(2)O-Cu界面上的Cu^(+)和Cu^(0)协同促进电催化CO_(2)还原高效和高选择性地生成C_(2+)产物  

Synergistic Cu^(+)/Cu^(0)on Cu_(2)O-Cu interfaces for efficient and selective C2+production in electrocatalytic CO_(2)conversion

作　　者：王胜楠 王丹 田本强 高响响 韩璐 钟洋 宋舒畅 王智立 李亚平 归家宁 Marshet G.Sendeku 张颖 邝允 孙晓明 Shengnan Wang;Dan Wang;Benqiang Tian;Xiangxiang Gao;Lu Han;Yang Zhong;Shuchang Song;Zhili Wang;Yaping Li;Jianing Gui;Marshet G.Sendeku;Ying Zhang;Yun Kuang;Xiaoming Sun(Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China;State Key Laboratory of Chemical Resource Engineering,Beijing Advanced Innovation Center for Soft Matter Science and Engineering,College of Chemistry,Beijing University of Chemical Technology,Beijing 100029,China;Weichai Power Co.,Ltd.,Weifang 261061,China;Ocean Hydrogen Energy R&D Center,Research Institute of Tsinghua University in Shenzhen,Shenzhen 518000,China)

机构地区：[1]Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China [2]State Key Laboratory of Chemical Resource Engineering,Beijing Advanced Innovation Center for Soft Matter Science and Engineering,College of Chemistry,Beijing University of Chemical Technology,Beijing 100029,China [3]Weichai Power Co.,Ltd.,Weifang 261061,China [4]Ocean Hydrogen Energy R&D Center,Research Institute of Tsinghua University in Shenzhen,Shenzhen 518000,China

出　　处：《Science China Materials》2023年第5期1801-1809,共9页中国科学（材料科学（英文版）

基　　金：supported by the National Key Research and Development Project(2018YFB1502401 and 2018YFA0702002);the Program for Changjiang Scholars and Innovation Research Team in the University(IRT1205);the Fundamental Research Funds for the Central Universities;the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of China。

摘　　要：电催化CO_(2)还原技术有望同时缓解化石燃料濒临枯竭及大气中CO_(2)浓度不断攀升等问题.然而,对于高附加值的电催化CO_(2)还原多碳产物的选择性提升,仍然面临巨大挑战.密度泛函理论(DFT)计算表明,Cu_(2)O-Cu界面上Cu^(+)和Cu^(0)的协同耦合效应使其表面上^(*)COCO中间体的生成能降低,同时H_(2)O的解离自由能也降低,从而有利于电催化CO_(2)还原高选择性生成多碳产物特别是C_(2)H_(4).受DFT计算结果的启发,本文设计了一种氧化物衍生铜电极的活化策略,构建Cu_(2)O-Cu界面,以Cu^(+)和Cu^(0)协同促进电催化CO_(2)还原高效高选择性生成C_(2+)产物.其中,Cu_(2)O立方体被用作初始催化剂,经方波电位处理后,在Cu_(2)O-Cu界面上形成了具有Cu^(+)和Cu^(0)协同作用的S W-Cu_(2)O/Cu立方体.在H型电解池中,SW-Cu_(2)0/Cu电催化CO_(2)还原生成C_(2)H_(4)和C_(2+)产物的法拉第效率分别为60%和75%,约为前驱体Cu_(2)O立方体的1.5倍,证明Cu^(0)和Cu^(+)在Cu_(2)O-Cu界面上的协同作用的确可提高电催化CO_(2)还原过程中特定高附加值多碳产物的选择性.The electrocatalytic CO_(2)reduction technology is expected to simultaneously alleviate increasing CO_(2)emissions and the depletion of fossil resources.However,it is still a big challenge to improve the selectivity toward valuable multicarbon products in electrocatalytic CO_(2)reduction reaction.In this study,the synergistic role of Cu^(+)and Cu^(0)species in Cu_(2)OCu interfaces is unravelled through density functional theory(DFT)calculations,in which the electrode surface exhibits low free energy of ^(*)COCO intermediate formation and H2O dissociation,which are beneficial to the high selectivity towards multi-carbon products,especially C2H4.Guided by these DFT results,an oxide-derived copper electrode activation strategy that builds the synergistic Cu^(+)and Cu^(0)on Cu_(2)O-Cu interfaces is designed to boost the selectivity toward multi-carbon products.Interestingly,Cu_(2)O cubes chosen as the pristine catalyst are activated via a square-wave(SW)potential treatment to form SW-Cu_(2)O cubes that bear Cu^(+)and Cu^(0)species.The asprepared SW-Cu_(2)O cubes exhibit superior Faradaic efficiencies for C2H4(60%)and C2+products(75%)in an H-type cell,which are about 1.5 times that of the Cu_(2)O cubes.This study demonstrates the synergistic Cu^(0)and Cu^(+)on Cu_(2)O-Cu interfaces for improving the selectivity of a specific valuable multi-carbon product in electrocatalytic CO_(2)conversion.

关 键 词：Cu^(+)and Cu^(0) C-C coupling CO_(2)RR Cu_(2)O-Cu interfaces SQUARE-WAVE 

分 类 号：TQ426[化学工程] X701[环境科学与工程—环境工程]