Li Lei, Wang Jia-Jun, Zhao Yan, Ding Bo, Wang Xiu-Guang, Zhao Xiao-Jun, Yang En-Cui
College of Chemistry, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387, People's Republic of China.
Henan Province Key Laboratory of New Opto-Electronic Functional Materials, School of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, Henan Province 455002, People's Republic of China.
Nanotechnology. 2021 Jan 22;32(4):045710. doi: 10.1088/1361-6528/abc038.
Three isostructural pillared-layer frameworks with M-BDC-X layers supported by ditopic HL connectors, [M(HL)(BDC)X] (HL = 4'-(4-hydroxyphenyl)-4,2':6',4″-terpyridine, BDC = terephthalate, M = Cd, X = Cl for (1), M = Cd, X = formate for (2), and M = Co, X = formate for (3)), were solvothermally synthesized, and used as photocatalysts for Pt-assisted visible-light-initiated hydrogen evolution from water splitting. These water-durable frameworks exhibit varied hydrogen production rates of 361.2, 271.3, and 327.5 μmol · g · h in 12 h due to their slightly different donor environments of the octahedral Cd and Co ions. Further experimental and theoretical investigations reveal that the metal ions and the local coordination surroundings have essentially dominated the conduction band minimum and electric resistance of the charge transport, which play highly important roles for the improved catalytic hydrogen evolution ability. These findings demonstrate the electronic effect of the slightly ligand field modifications on the boosting hydrogen generation activity in the noble metal-assisted MOF photocatalytic systems.
