A novel metal-free porous covalent organic polymer for efficient room-temperature photocatalytic CO_(2) reduction via dry-reforming of methane  

作　　者：Sheng-Yan Yin Ziyi Li Yingcai Hu Xiao Luo Jishan Li 

机构地区：[1]College of Chemistry and Chemical Engineering,Hunan University,Changsha,410082,China [2]Institute of Basic Medicine and Cancer(IBMC),Chinese Academy of Sciences,Hangzhou,Zhejiang,310022,China

出　　处：《Green Energy & Environment》2024年第9期1407-1418,共12页绿色能源与环境（英文版）

基　　金：supported by National Natural Science Foundation of China (Nos. 22274039 and 22178089);Hunan Provincial Innovation Foundation for Postgraduate (No.CX20220392)。

摘　　要：At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.

关 键 词：METAL-FREE Photocatalytic CO_(2)reduction Covalent organic polymer Dry-reforming of methane Electron donor and acceptor 

分 类 号：TQ426[化学工程] X701[环境科学与工程—环境工程]