Synthesis, structure, characterization and catalytic behavior of a bis(thiosemicarbazonato)-nickel complex

Abstract

4-Phenyl-3-thiosemicarbazide reacts with 2,3-butanedione to provide a new compound, diacetyl-bis(N4-phenyl-3-thiosemicarbazonato) (H2ATSP). In the presence of triethylamine (Et3N), the reaction of H2ATSP with NiCl2 affords a new nickel complex, diacetyl-bis(N4-phenyl-3-thiosemicarbazonato)nickle(II) (NiII-ATSP), a diamagnetic material, which has been characterized by physicochemical and spectroscopic methods. Studies exhibit that Ni-ATSP has good catalytic activities for both electrochemical and photochemical driven hydrogen evolution. Under an overpotential (OP) of 837.6 mV, 188.7 moles of hydrogen per mole of catalyst per hour (mol H2/mol catalyst/h) are afforded from an electrolysis of neutral water with Ni-ATSP. With blue light (λ = 469 nm) irradiation, together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H2A) as a sacrificial electron donor, Ni-ATSP can catalyze hydrogen generation with a turnover number (TON) of 9554 moles H2 per mol of catalyst (mol of cat−1) during 50 h irradiation in a heterogeneous environment.