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 activ...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.展开更多
基金support by the National Natural Science Foundation of China(No.52102362)Taishan Scholar Foundation(No.ts201712030)+2 种基金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).
文摘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.
