Electrocatalytic Hydrogen Production Using Molybdenum Sulfides

Electrocatalytic hydrogen production via the hydrogen evolution reaction (HER) is at the forefront of sustainable energy research. Molybdenum sulfides, notably MoS₂ and related amorphous or cluster-like analogues, have emerged as promising non-precious metal catalysts. Their activity stems primarily from unsaturated molybdenum edge sites or terminal sulphide ligands, whose electronic structure favours proton adsorption and hydrogen desorption at modest overpotentials. Tailoring the phase (2H semiconducting versus 1T metallic versus amorphous), defect density and nanoscale morphology enables optimisation of active-site density, electronic conductivity and catalyst durability. Composite strategies—such as integration with conductive carbon supports, heterogenisation of molecular clusters on semiconductor photocathodes or doping with transition metals—further enhance kinetics and facilitate charge transfer. Stability under operating conditions is a critical consideration: dissolution of Mo or S species, phase transformation and active-site restructuring must be controlled. Collectively, these advances point towards moieties capable of replacing platinum in proton-exchange membrane water electrolyser systems, underscoring the global significance of molybdenum sulfide electrocatalysts for large-scale clean hydrogen generation.

Research from Nature Portfolio

Recent studies have revealed the allotrope-dependent stability and activity of molybdenum sulfide catalysts. A detailed investigation using flow-cell analytics demonstrated that layered MoS₂ undergoes significant dissolution under open-circuit conditions, while amorphous MoS₃₋ₓ loses sulphur during HER, generating under-coordinated molybdenum centres. Stability-number metrics were introduced to guide the operation of non-noble-metal water electrolyser devices, and a mechanistic framework was proposed linking Mo and S dissolution pathways to active-site generation. Earlier foundational work explored the tuning of immobilised metal-chalcogenide molecular catalysts by controlling metal–chalcogen stoichiometry. It showed that fine structural control yields hydrogen evolution at low overpotential with no degradation over extended cycling. Density functional calculations provided mechanistic insight into unimolecular catalytic cycles and the role of redox-active frameworks in sustaining high activity.

Electrocatalytic Hydrogen Production Using Molybdenum Sulfides publication trend

The graph below shows the total number of articles in electrocatalytic hydrogen production using molybdenum sulfides across all publications each year (not limited to Nature Index journals).

Technical terms

Electrocatalytic hydrogen evolution reaction (HER): Electrochemical process in which protons are reduced to molecular hydrogen at a cathode.

Overpotential: Extra voltage beyond the thermodynamic requirement needed to drive an electrochemical reaction at a given rate.

Tafel slope: Parameter expressing the relationship between overpotential and log(current density), indicative of reaction kinetics.

Active site: Specific atomic ensemble on a catalyst surface where substrate adsorption and reaction occur.

Phase (2H, 1T, amorphous): Crystal or disordered structures of MoS₂ that influence electronic conductivity and catalytic activity.

Heterogenization: Immobilisation of molecular catalysts or clusters onto solid supports to combine homogeneous activity with solid-state robustness.

Faradaic efficiency: Fraction of electrical charge that is effectively used for the desired chemical transformation (here, H₂ production).

References

1. Molybdenum disulfide as hydrogen evolution catalyst: From atomistic to materials structure and electrocatalytic performance. Journal of Energy Chemistry (2023).
2. Allotrope-dependent activity-stability relationships of molybdenum sulfide hydrogen evolution electrocatalysts. Nature Communications (2024).
3. Tuning and mechanistic insights of metal chalcogenide molecular catalysts for the hydrogen-evolution reaction. Nature Communications (2019).
4. A review on ultra‐small undoped MoS2 as advanced catalysts for renewable fuel production. Carbon Energy (2024).
5. Direct Anchoring of Molybdenum Sulfide Molecular Catalysts on Antimony Selenide Photocathodes for Solar Hydrogen Production. ACS Energy Letters (2024).