Boosting CO_(2)Electroreduction by Preactivation Strategy over Carbene-Based Metal-Organic Framework  

作　　者：Zi-Yan Jing Duan-Hui Si Hui Guo Li-Li Han Rong Cao Yuan-Biao Huang 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,350002 Fujian [2]College of Chemistry,Fuzhou University,Fujian 350108 [3]University of Chinese Academy of Science,Beijing 100049 [4]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou,350108 Fujian

出　　处：《CCS Chemistry》2024年第12期3053-3064,共12页中国化学会会刊(英文)

基　　金：supported by the National Key Research and Development Program of China(grant nos.2023YFA1507904 and 2021YFA1501500);National Natural Science Foundation of China(grant nos.U22A20436,22071245,22220102005,and 22033008);Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(grant no.2021ZZ103);Talent Plan of Shanghai Branch,Chinese Academy of Sciences(grant no.CASSHB-QNPD-2023-020);supported by the Open Science Promotion Plan 2023 of China Science and technology Cloud.The authors thank the Taiwan beamline BL-12B2 at SPring-8(Japan)and the beamline TPS 44A of the National Synchrotron Radiation Research Center for EXAFS measurements.

摘　　要：Developing nonmetallic active sites-based catalysts for efficient electrocatalytic CO_(2)reduction reaction(CO_(2)RR)remains challenging.Active N-heterocyclic carbenes(NHCs)as typical nonmetal catalysts have shown high efficiency in organic catalysis but rarely used in electrochemistry.Herein,we report for the first time using the CO_(2)-masked NHCs functionalized metal-organic framework(UiO-66-NHC-CO_(2))as efficient electrocatalyst for the CO_(2)RR towards production of CO.The active NHCs sites protected by the COO-group in the UiO-66-NHC-CO_(2)can activate CO_(2)and the Faradaic efficiency of CO reaches 80.1%at-2.5 V versus Ag/Ag+,outcompeting current metal-free catalysts with well-defined active sites.Experimental results and DFT indicate that the NHCs species shielded by CO_(2)have a lower adsorption activation energy for CO_(2)compared to imidazolium salts,making it easier to bind and activate CO_(2),thus leading to easy reduction to CO.Therefore,the NHCs portion of UiO-66-NHC-CO_(2)can be capable of activating CO_(2)and facilitating its reduction to CO.This discovery provides valuable insights for the preactivation of CO_(2)and efficient electrocatalytic reduction of CO_(2).

关 键 词：metal-organic frameworks N-heterocyclic carbenes CO_(2)electrocatalysis UiO-66 CO 

分 类 号：O64[理学—物理化学]