Abstract
Although molybdenum sulfide materials show promise as electrocatalysts for proton reduction, the hydrido species proposed as intermediates remain poorly characterized. We report herein the synthesis, reactions and spectroscopic properties of a molybdenum-hydride complex featuring an asymmetric Mo2S2 core. This molecule displays rich redox chemistry with electrochemical couples at E½ = −0.45, −0.78 and −1.99 V vs. Fc/Fc+. The corresponding hydrido-complexes for all three redox levels were isolated and characterized crystallographically. Through an analysis of solid-state bond metrics and DFT calculations, we show that the electron-transfer processes for the two more positive couples are centered predominantly on the pyridinediimine supporting ligand, whereas for the most negative couple electron-transfer is mostly Mo-localized.
Highlights
Efficient electro or photocatalytic reduction of protons to produce H2 gas remains an important challenge [1,2,3,4,5]
A tremendous amount of research has revolved around discovery and optimization of new materials for the hydrogen evolution reaction (HER) [1,2,3,4,5]
Preparation of hydrido complexes featuring an Mo2 S2 core and an examination of their redox properties, reactions and electronic structure
Summary
Efficient electro or photocatalytic reduction of protons to produce H2 gas remains an important challenge [1,2,3,4,5]. Is H2 a potential clean fuel, but is by far the most used chemical reductant [6]. H2 is typically produced industrially by the steam reforming of methane [7]. This process utilizes a nonrenewable hydrocarbon feedstock and generates large volumes of greenhouse gases, the low efficiency of current water splitting technologies makes steam reforming by far the most economical process [5]. Some of the most promising heterogeneous catalysts for this reaction are molybdenum sulfides (MoSx ),which exhibit comparable overpotentials and current densities to Pd/Pt electrodes but are significantly cheaper [8,9,10]
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