Structural Properties of Gas Phase Molybdenum Sulfide Clusters [Mo₃S₁₃]^2-, [HMo₃S₁₃]^-, and [H₃Mo₃S₁₃]⁺ as Model Systems of a Promising Hydrogen Evolution Catalyst.

ABSTRACT: Amorphous molybdenum sulfide (MoS _x ) is a potent catalyst for the hydrogen evolution reaction (HER). Since mechanistic investigations on amorphous solids are particularly difficult, we use a bottom-up approach and study the [Mo₃S₁₃]^2- nanocluster and its protonated forms. The mass selected pure [Mo₃S₁₃]^2- as well as singly and triply protonated [HMo₃S₁₃]^- and [H₃Mo₃S₁₃]⁺ ions, respectively, were investigated by a combination of collision induced dissociation (CID) experiments and quantum chemical calculations. A rich variety of H _x S _y elimination channels was observed, giving insight into the structural flexibility of the clusters. In particular, it was calculated that the observed clusters tend to keep the Mo₃ ring structure found in the bulk and that protons adsorb primarily on terminal disulfide units of the cluster. Mo-H bonds are formed only for quasi-linear species with Mo centers featuring empty coordination sites. Protonation leads to increased cluster stability against CID. The rich variety of CID dissociation products for the triply protonated [H₃Mo₃S₁₃]⁺ ion, however, suggests that it has a large degree of structural flexibility, with roaming H/SH moieties, which could be a key feature of MoS _x to facilitate HER catalysis via a Volmer-Heyrovsky mechanism.

SUBMITTER: Baloglou A 

PROVIDER: S-EPMC6453024 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature