Photocatalytic hydrogen evolution activity over Pt-assisted metal-organic frameworks dominated by transition metal...

Three isostructural pillared-layer frameworks with M-BDC-X layers supported by ditopic HL connectors, [M(HL)(BDC)_0.5X] _n (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^-1 · h^-1 in 12 h due to their slightly different donor environments of the octahedral Cd^II and Co^II 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.