Application of a Ni mercaptopyrimidine MOF as highly efficient catalyst for sunlight-driven hydrogen generation

Microscale crystals of a 2D layered MOF [Ni-2(PymS)(4)](n) (PymSH = Pyrimidine-2-thio) with a thiolate-bridged binuclear Ni(II) node similar to the active site of the [NiFe]-hydrogenase were prepared. This material shows high catalytic activity for visible-light-driven hydrogen production under the illumination of white LED or direct sunlight. The turnover frequency (TOF) of the catalyst can reach up to 10.6 h(-1). In this study, the heterogeneous nature and recyclability of the catalyst, as well as the factors that affect the catalytic activity have been investigated and described. Moreover, the photocatalytic mechanism for the hydrogen generation of [Ni-2(PymS)(4)](n) has been also proposed, based on fluorescence spectra and cyclic voltammetry.