Synthesis and Characterization of Cobalt and Nickel Thiolate Complexes for Hydrogen evolution

  • 黃 柏華

Student thesis: Master's Thesis

Abstract

A challenge to produce dihydrogen for renewable energy is to develop high efficient catalysts for proton reduction The first-row transition metal complexes are ideal catalysts due to their low cost and high abundance in the earth Based on this motivation we have been aiming on develop nickel and cobalt catalysts that carry the reduction of proton to dihydrogen In this study bis(benzenethiolato)phosphine ligand derivative [PS2”]H2 (PS2”H2 = [P(C6H5)(C6H3-3-Me3Si-2-SH)2]) was used to explore nickel and cobalt chemistry A nickel(II) thiolate complex [NiII(PSSH”)2] (1) was obtained by the reaction of nickel(II) species with [PS2”]H2 Complex 1 was characterized by X-ray crystallography UV-vis-NIR spectrum ESI-MS spectrum and NMR spectrum Furthermore complex 1 was found to react with oxygen and produce a nickel(IV) species [NiIV(PS2”)2] (2) Complex 2 was characterized by X-ray crystallography UV-vis-NIR spectrum NMR spectrum and cyclic voltammetry Importantly the irradiation of complex 1 produced dihydrogen that was identified by gas chromatography On the same time complex 1 was changed to complex 2 that was characterized by ESI-MS spectrum A dinickel(II) thiolate complex [NiII(PS2”)2]2 (3) was obtained by the reaction of nickel(II) species with [PS2”]H2 The complex 3 was characterized by X-ray crystallography UV-vis-NIR spectrum and NMR spectrum A cobalt(III) thiolate complex [PPh4][Co(PS2”)2] (4) was obtained by the reaction of cobalt(II) species with [PS2”]H2 The complex 4 was characterized by X-ray crystallography element analysis UV-vis-NIR spectrum ESI-MS spectrum NMR spectrum and cyclic voltammetry
Date of Award2015 Aug 4
Original languageEnglish
SupervisorKonopka Richard L. (Supervisor)

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