Efficient Photogeneration of Hydrogen Boosted by Long-Lived Dye-Modified Ir(III)Photosensitizers and Polyoxometalate Catalyst  

作　　者：Lin Qin Chongyang Zhao Liao-Yuan Yao Hongbin Dou Mo Zhang Jing Xie Tsu-Chien Weng Hongjin Lv Guo-Yu Yang 

机构地区：[1]MOE Key Laboratory of Cluster Science,School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 102488 [2]Department of Chemistry,The University of Hong Kong,Hong Kong 999077 [3]School of Physical Science and Technology,ShanghaiTec University,Shanghai 201210

出　　处：《CCS Chemistry》2022年第1期259-271,共13页中国化学会会刊（英文）

基　　金：The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China(nos.21871025 and 21831001);the Recruitment Program of Global Experts(Young Talents),and the BIT Teli Young Fellow Program.

摘　　要：Developing efficient catalysts and photosensitizers is crucial for the construction of effective photocatalytic H2-evolving systems.Here,we report the facile preparation of Coumarin-modified Ir(III)complexes(PS-2 and PS-3)and their utilization as chromophores to drive favorable photocatalytic H2 evolution using Ni-substituted polyoxometalate(Ni_(3)PW_(10))catalyst and triethanolamine(TEOA)as an electron donor.Compared with the commercially available unmodified Ir(III)complex(PS-1),both PS-2 and PS-3 displayed intensive absorption in the range of 400–550 nm with ε_(max) of 110,620 and 91,430 M^(−1) cm6(−1),respectively.Varying the substitutes on the bipyridine ligand affected their physicochemical properties and the corresponding photocatalytic activity dramatically.Under photocatalytic conditions,the quantity of H2 molecules generated by PS-2-and PS-3-containing systems were 13.1 and 2.1 times,respectively,that of the PS-1-containing system.When PS-2 was used as a photosensitizer,the highest turnover number(TON)of 19,739 was obtained versus Ni_(3)PW_(10) catalyst.Various spectroscopic and computational studies have revealed that factors such as strong and broad visible-light-absorbing ability,long-lived triplet state,suitable redox potential,opposed by using polyoxometalate(POM)catalyst,and large highest occupied molecular orbital(HOMO)–lowest unoccupied molecular orbital(LUMO)gap of PS-2 attributed to drastically enhanced photocatalytic activity.

关 键 词：dye-modified Ir(III)complexes Ni-substituted polyoxometalate visible-light-driven H_(2)evolution efficient intersystem crossing DFT calculations 

分 类 号：O64[理学—物理化学]