Hybridization of covalent organic frameworks and photosensitive metal-organic rings:A new strategy for constructing supramolecular Z-scheme heterostructures for ultrahigh photocatalytic hydrogen evolution  

作　　者：Xin-Ao Li Zi-Zhan Liang Ye-Cheng Zhou Jian-Feng Huang Xiao-Lin Wang Li-Min Xiao Jun-Min Liu 

机构地区：[1]The Key Laboratory of Low-Carbon Chemistry&Energy Conservation of Guangdong Province,School of Materials Science and Engineering,Sun Yat-sen University,Guangzhou,China [2]School of Computer Science and Engineering,Beihang University,Beijing,China

出　　处：《Aggregate》2024年第2期239-249,共11页聚集体（英文）

基　　金：National Natural Science Foundation Project of China,Grant/Award Numbers:21975291,22171211;NSF of Guangdong Province,Grant/Award Numbers:2022A1515011949,2020A1515110474。

摘　　要：The rational design of Z-scheme heterojunction photosystems based on covalent organic frameworks(COFs)is a promising strategy for harnessing solar energy for hydrogen conversion.Herein,a direct Z-scheme single-atom photocatalyst based on COF and metal-organic ring has been constructed through the supramolecular interactions of coral-like COF(S-COF)and photosensitized Pd2L2 type metal-organic ring(MAC-FA1).The MAC-FA1/S-COF heterojunction exhibits good light absorption,efficient charge separation and transfer,slow electron-hole recombination,and highly dispersed Pd active sites,enabling an efficient and stable H_(2) evolution reaction.The optimized 4%MAC-FA1/S-COF achieves an H_(2) evolution rate of 100 mmol g^(−1)h^(−1)within 5 h and obtains a total accumulated turn-over number relative to Pd(TON_(Pd))of 437,685 within 20 h,far superior to S-COF,MAC-FA1,M-5/S-COF,Pd/S-COF,and M-5/Pd/S-COF,which is one of the highest records among COF-based photocatalysts for solar-driven H_(2)evolution.This is the first work to incorporate photosensitized metal-organic rings/cages into porous crystalline COFs to form a supramolecular Z-scheme heterojunction,which has significant potential as a high-performance photocatalyst for solar-driven H_(2)production.

关 键 词：covalent organic framework metal-organic ring single-atom catalyst visible-light-driven H2 production Z-scheme heterojunction 

分 类 号：O62[理学—有机化学]