Understanding homogeneous hydrogen evolution reactivity and deactivation pathways of molecular molybdenum sulfide catalysts

Abstract

The first example of light driven, homogeneous hydrogen evolution reactivity of a molecular molybdenum sulfide is presented together with experimental and theoretical insights into the reasons for the unusually high activity.

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

“…The presence of 10% MeOH in the reaction medium, apart from playing a role of sacrificial reducing agent, also inhibits ligand-exchange reaction of the {Mo3} cluster, where surface S2 2 might be gradually exchanged with hydroxide or water ligands. 27 The pristine carbon nitride sample (CNx) does not show any significant H2 evolution activity under given conditions (Fig. 4a), while the CNx-{Mo3} is clearly active in this reaction.…”

“…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 Transition Metal Oxo‐Thiostannate: Synthesis, Characterization, and Investigation of its Photocatalytic Properties

“…A comparison of the photocatalytic activity with data reported in literature is difficult because the activity depends on a large number of parameters like, e.g., the solvents, the amount of the catalyst, the co‐catalyst, the photosensitizer, the intensity and wavelength of the light source, the sacrificial compound, pH value etc. In addition, the amount of hydrogen produced is reported as different quantities like e · g · mmol · g –1 , mmol, mL, TON (turnover number, Table ) or TOF (turnover frequency) . Nevertheless, the TON of 83.1 for the title compound is in the range of data reported for Ni 2+ and Co 2+ centered complexes (Table ).…”

Insights into the Electrochemical Polymerization of [Mo3S13]2− Generating Amorphous Molybdenum Sulfide

“…The MoS x ‐CE film can also be built from the [Mo 3 S 13 ] 2− building block through an electrochemical reduction process. Actually, under the reductive conditions induced by a photoexcited [Ru(bpy) 3 ] 2+ light sensitizer, the removal of the terminal S 2 2− ligands from the [Mo 3 S 13 ] 2− cluster resulting in the formation of the [Mo 3 S 7 (H 2 O) 6 ] 4+ species has been demonstrated . The electrochemical reductive elimination of the terminal S 2 2− ligand within a sputtered MoS x catalyst when it is conditioned under the H 2 ‐evolving conditions was recently reported with the identification of H 2 S as a product .…”

“…Actually,u nder the reductive conditions induced by ap hotoexcited [Ru(bpy) 3 ] 2 + light sensitizer,t he removal of the terminal S 2 2À ligandsf rom the [Mo 3 S 13 ] 2À cluster resulting in the formation of the [Mo 3 S 7 (H 2 O) 6 ] 4 + species has been demonstrated. [14] The electrochemical reductive elimination of the terminal S 2 2À ligand within as puttered MoS x catalyst when it is conditioned under the H 2 -evolving conditions was recently reported with the identificationofH 2 Sasaproduct. [7] Thus,atwo-electronr eductionp rocess causingt he elimination of terminal S 2 2À ligands and creation of Mo-& vacant sites as described in Equation (3) is very likely when as ufficient cathodic potential such as À0.8 Visa pplied.…”