Artificial Chlorophyll-like Structure for Photocatalytic CO_(2)Chemical Fixation  

作　　者：Lei Li Wenxiu Liu Hanghao Ying Xin He Shu Shang Peng Zhang Xiaodong Zhang Shuhu Liu Hui Wang Yi Xie 

机构地区：[1]Hefei National Research Center for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei,Anhui 230026 [2]Institute of Energy,Hefei Comprehensive National Science Center,Hefei,Anhui 230031 [3]Institute of High Energy Physics,Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2024年第12期3077-3088,共12页中国化学会会刊(英文)

基　　金：supported by the National Key R&D Program of China(grant nos.2022YFA1502903 and 2021YFA1501502);the Strategic Priority Research Program of the Chinese Academy of Sciences(CAS;grant nos.XDB0450000 and XDB36000000);the National Natural Science Foundation of China(grant nos.92163105,T2122004,U2032212,and 22275179);Anhui Provincial Key Research and Development Program(grant no.2022a05020054);the China Postdoctoral Science Foundation(CPSF;grant nos.2023TQ0341 and 2023M743369);the Youth Innovation Promotion Association of CAS(grant no.Y2021123);the Fundamental Research Funds for the Central Universities(grant nos.WK2060000039 and WK2060000068);the Postdoctoral Fellowship Program of CPSF(grant no.GZB20230706).

摘　　要：In nature,green leaves accomplish photosynthesis via chloroplasts,where the Mg-N4-centered chlorophyll and enzymes undertake light absorption and catalytic reaction,involving CO_(2)fixation,with the resultant six-carbon compound,respectively.This intriguing phenomenon inspired us to design an artificial photosynthetic system that synergizes these dual attributes,a field that has remained largely unexplored.Herein,we developed a highly stable artificial chlorophyll-like nitrogen-decorated amorphous carbon material(Mg-NC)featuring abundant Mg-N4 moieties(with high Mg content reaching≈9.2 wt%),which simultaneously integrated the light-absorption center and catalytic reaction center to mimic natural photosynthesis of CO_(2)valorization.As demonstrated,taking the photocatalytic CO_(2)cycloaddition reaction as an example,the Mg-N4 active center in Mg-NC played the role of an electronic donor,which could readily inject hot electrons into the adsorbed substrates,resulting in the swift formation of cyclic carbonate products.Remarkably,the as-designed Mg-NC exhibited outstanding photocatalytic CO_(2)cycloaddition performance,achieving an impressive reaction rate up to 9.67 mmol·g^(-1)·h^(-1)under mild conditions,which could be sustained even under gram scale conditions.Our current study offers an artificial biomimetic enzyme heterogeneous photocatalysis for CO_(2)valorization.

关 键 词：CO_(2)chemical fixation cyclic carbonates artificial chlorophyll-like structure PHOTOCATALYSIS density functional calculations 

分 类 号：O64[理学—物理化学]