Homogeneous visible light-driven hydrogen evolution by the molecular molybdenum sulfide model [Mo₂S₁₂]²⁻

Abstract

The first example of light driven, homogeneous hydrogen evolution reactivity by the smallest thiomolybdate cluster [Mo2S12]2− is reported together with initial insights into the catalytic and deactivation mechanism.

Polymeric carbon nitride coupled with a molecular thiomolybdate catalyst: exciton and charge dynamics in light-driven hydrogen evolution

“…The [Mo3S13] 2 molecular clusters have been established as one of such promising co-catalysts for dark electrocatalytic 16,[19][20][21][22] and photocatalytic HER under heterogeneous [23][24][25] and homogeneous conditions. 26,27 Anchoring of the cluster onto various solid catalyst supports or light absorbers is straightforward and has been demonstrated for TiO2, 28 carbon materials, 20,21 and recently also for polymeric carbon nitride-based material. 25 More specifically, X. Wang et al have coupled [Mo3S13] 2 [={Mo3}] to protonated mesoporous carbon nitride with rod-like morphology (diameter ca.…”

New Methods for the Functionalization of Polymer Matrices with Thiomolybdate Clusters Applied for Hydrogen Evolution Reaction Catalysis

“…[8,9] In particular, molybdenum sulfides and their molecular analogues, thiomolybdate clusters, [10] have been used as high-performance HER catalysts under electrochemical and photochemical conditions. [11][12][13][14][15][16][17][18][19][20][21] These clusters are also known for their sulfur resistance (e.g., against sulfur poisoning with sulfide). [22] However, thiomolybdate clusters are not long-term stable under typical HER conditions, as ligand exchange reactions lead to the deactivation of the catalyst.…”

Assembly and Redox-Rich Hydride Chemistry of an Asymmetric Mo2S2 Platform

“…Although the mechanism of proton reduction by MoS x materials is not fully understood, calculations implicate molybdenum-hydrido intermediates that are protonated to give H 2 [ 11 , 12 , 13 , 14 ]. A number of molecular analogues for the surface interface of MoS x materials have been shown to be active HER catalysts, although Mo–H intermediates, if they are formed, have not been well-characterized [ 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ]. Indeed, molecular Mo–H complexes featuring sulfur-donor ligands, particularly sulfides, are uncommon [ 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 ].…”