title: Fabrication of Low Adsorption Energy Ni-Mo Cluster Cocatalyst in Metal-Organic Frameworks for Visible Photocatalytic Hydrogen Evolution.
abstract: An effective cocatalyst is crucial for enhancing the visible photocatalytic performance of the hydrogen generation reaction. By using density-functional theory (DFT) and frontier molecular orbital (FMO) theory calculation analysis, the hydrogen adsorption free energy (ΔGH) of Ni-Mo alloy (458 kJ·mol(-1)) is found to be lower than that of Ni itself (537 kJ·mol(-1)). Inspired by these results, the novel, highly efficient cocatalyst NiMo@MIL-101 for photocatalysis of the hydrogen evolution reaction (HER) was fabricated using the double solvents method (DSM). In contrast with Ni@MIL-101 and Mo@MIL-101, NiMo@MIL-101 exhibited an excellent photocatalytic performance (740.2 μmol·h(-1) for HER), stability, and high apparent quantum efficiency (75.7%) under 520 nm illumination at pH 7. The NiMo@MIL-101 catalyst also showed a higher transient photocurrent, lower overpotential (-0.51 V), and longer fluorescence lifetime (1.57 ns). The results uncover the dependence of the photocatalytic activity of HER on the ΔGH of Ni-Mo (MoNi4) alloy nanoclusters, i.e., lower ΔGH corresponding to higher HER activity for the first time. The NiMo@MIL-101 catalyst could be a promising candidate to replace precious-metal catalysts of the HER.
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, P. R. China.|College of Chemistry and Chemical Engineering, Lanzhou University , Lanzhou 730000, P. R. China.
authors.forename: Wenlong
authors.initials: W
authors.lastname: Zhen
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, P. R. China.|College of Chemistry and Chemical Engineering, Lanzhou University , Lanzhou 730000, P. R. China.
authors.forename: Haibo
authors.initials: H
authors.lastname: Gao
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
authors.forename: Bin
authors.initials: B
authors.lastname: Tian
authors.affiliation: College of Chemistry and Chemical Engineering, Lanzhou University , Lanzhou 730000, P. R. China.
authors.forename: Jiantai
authors.initials: J
authors.lastname: Ma
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, P. R. China.|College of Chemistry and Chemical Engineering, Lanzhou University , Lanzhou 730000, P. R. China.
authors.forename: Gongxuan
authors.initials: G
authors.lastname: Lu
keywords: NiMo@MIL-101; apparent quantum efficiency; density functional theory; low adsorption energy; visible photocatalytic hydrogen generation