摘要
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.
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)
Science and Technology Planning Project of Guangdong Province(2021A0505030066,2023A0505050164)
Science and Technology Program of Guangzhou(202201010244).
