[Mo2S12]2− Complex as a Precursor for In‐situ Generation of Molybdenum Sulfide Catalyst During the H2 Evolution

Abstract

AbstractFor decades, the sulfido molybdenum complexes like [MoS4]2−, [Mo2S12]2−, [Mo3S13]2− have gained great attention because of their chemical versatility as well as their structural similarity to the edge‐plan of the molybdenum disulfide (MoS2) which shows promising catalytic ability for the H2 generation. In this work, we report on the investigation of the dinuclear complex [Mo2S12]2− in both organic and aqueous solution. We demonstrate that [Mo2S12]2− is not intact during the H2 evolution catalysis when it is assayed as a homogeneous catalyst in an electrolyte solution (e. g. in DMF or water solvent) nor when it is immobilized on an electrode surface (e. g. mesoporous carbon black). It transforms into the polymeric amorphous molybdenum sulfide [MoS] which subsequently acts as an actual catalyst. We discuss on the possible [Mo2S12]2− to [MoS] transformation mechanism by employing an arsenal of electrochemical analysis, spectroscopic analyses and microscopic analyses. Effects of the electrochemical operating conditions to the [Mo2S12]2− to [MoS] transformation as well as to the chemical nature and the catalytic performance of the [MoS] product are also emphasized.