Selective CO_(2)-to-formic acid electrochemical conversion by modulating electronic environment of copper phthalocyanine with defective graphene  

作　　者：Hanqing Zhang Xiaoxia Wang Chen Chen Xianfeng Yang Chungli Dong Yucheng Huang Xiaoliang Zhao Dongjiang Yang 

机构地区：[1]School of Environmental Science and Engineering,State Key Laboratory of Bio-fibers and Eco-textiles,Shandong Collaborative Innovation Center of Marine Bio-based Fibers and Ecological Textiles,Qingdao University,Qingdao,266071,China [2]Analytical and Testing Centre,South China University of Technology,Guangzhou,510640,China [3]Research Center for X-ray Science,Department of Physics,Tamkang University,Tamsui,25137,Taiwan,China

出　　处：《Chinese Journal of Structural Chemistry》2023年第10期4-12,共9页结构化学（英文）

基　　金：support by the National Natural Science Foundation of China(No.52102362);Taishan Scholar Foundation(No.ts201712030);Outstanding Youth of Natural Science in Shandong Province(No.JQ201713);Natural Science Foundation of Shandong Province(Nos.ZR2021QB022,ZR2021QB083,ZR2021ME012);State Key Laboratory of Bio-Fibers and Eco-Textiles(Qingdao University,Nos.ZKT10,ZKT25,ZKT30,and ZDKT202105).

摘　　要：In the carbon dioxide reduction reaction(CO_(2)RR),the activity of transition metal center depends largely on its electronic structure,since the electronic rich region enhances the adsorption of intermediates at active sites,thus improving the selectivity to reduction products.In this work,we prepared CuPc/DG composite(CuPc:copper phthalocyanine;DG:defective graphene)to achieve selective CO_(2)-to-formic acid(HCOOH)electrochemical conversion through modulating the electronic structure of Cu active centers with DG via π-π stacking.Evaluated as the electrocatalyst,the CuPc/DG composite displays a high faradaic efficiency(FE)of 44.6%−0.78 V vs.RHE for CO_(2)RR to HCOOH.Partial current density is 5.28 mA cm^(−2) for HCOOH together with an exceptional stability throughout at least 20 h of reaction.On the basis of density functional theory(DFT)calculation results,defects in DG can effectively promote the charge redistribution of dispersed CuPc,where electrons transfer to CuPc from defects,forming rich electronic environment around Cu sites.The abundance of electrons makes the d-band center of Cu approach to the Fermi level and decrease the energy barrier of CuPc/DG composite for the intermediate of ∗OCHO,thus accelerating the reduction of CO_(2) to HCOOH.

关 键 词：CO_(2)RR CuPc/DG composite Electron-rich region on Cu atoms HCOOH selectivity DFT calculations 

分 类 号：O641.4[理学—物理化学]