Electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)represents one of the most promising technologies for sustainable conversion of CO_(2) to value-added products.Although metal-organic frameworks(MOFs)can be...Electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)represents one of the most promising technologies for sustainable conversion of CO_(2) to value-added products.Although metal-organic frameworks(MOFs)can be vastly functionalized to create active sites for CO_(2)RR,low intrinsic electrical conductivity always makes MOFs unfavorable candidates for eCO_(2)RR.Besides,studies on how to regulate eCO_(2)RR activity of MOFs from linkers'functionalities viewpoint lag far behind when compared with the assembly of multinuclear metal-centered clusters.In this work,non-toxic bismuth(Ⅲ)oxide(Bi2O3)was incorporated into a series of two-dimensional(2D)MOFs(ZrLX)established from Zr-oxo clusters and triazine-centered 3-c linkers with different functionalities(LX=1-5)to give composites ZrLX/Bi2O3.To investigate how functionalities on linkers distantly tune the eCO_(2)RR performance of MOFs,electron-donating/withdrawing groups were installed at triazine core or benzoate terminals.It is found that ZrL2/Bi2O3(-F functionalized on triazine core)exhibits the best eCO_(2)RR performance with the highest Faradaic efficiency(FE)of 96.73%at-1.07 V vs.RHE,the largest electroactive surface(Cdi=4.23 mF cm-2)and the highest electrical conductivity(5.54 x 10-7 S cm-1),highlighting tuning linker functionalities and hence electronic structure as an alternative way to regulate eCO_(2)RR.展开更多
基金supported by the National Natural Science Foundation of China(22371054,22301045)the Foundation of Basic and Applied Basic Research of Guangdong Province(2020B1515120024,2024A1515012801)+1 种基金Science and Technology Planning Project of Guangdong Province(2021A0505030066,2023A0505050164)Science and Technology Program of Guangzhou(202201010244).
文摘Electrocatalytic carbon dioxide reduction reaction(eCO_(2)RR)represents one of the most promising technologies for sustainable conversion of CO_(2) to value-added products.Although metal-organic frameworks(MOFs)can be vastly functionalized to create active sites for CO_(2)RR,low intrinsic electrical conductivity always makes MOFs unfavorable candidates for eCO_(2)RR.Besides,studies on how to regulate eCO_(2)RR activity of MOFs from linkers'functionalities viewpoint lag far behind when compared with the assembly of multinuclear metal-centered clusters.In this work,non-toxic bismuth(Ⅲ)oxide(Bi2O3)was incorporated into a series of two-dimensional(2D)MOFs(ZrLX)established from Zr-oxo clusters and triazine-centered 3-c linkers with different functionalities(LX=1-5)to give composites ZrLX/Bi2O3.To investigate how functionalities on linkers distantly tune the eCO_(2)RR performance of MOFs,electron-donating/withdrawing groups were installed at triazine core or benzoate terminals.It is found that ZrL2/Bi2O3(-F functionalized on triazine core)exhibits the best eCO_(2)RR performance with the highest Faradaic efficiency(FE)of 96.73%at-1.07 V vs.RHE,the largest electroactive surface(Cdi=4.23 mF cm-2)and the highest electrical conductivity(5.54 x 10-7 S cm-1),highlighting tuning linker functionalities and hence electronic structure as an alternative way to regulate eCO_(2)RR.
