Electrocatalysis of Hydrogen Evolution Reactions

Electrocatalysis of the hydrogen evolution reaction (HER) is central to sustainable hydrogen production via water electrolysis. This multi-step process typically involves proton or water reduction at the electrode surface through sequential Volmer, Heyrovsky and Tafel steps, with overall rates governed by hydrogen adsorption and desorption energetics. Platinum remains the benchmark catalyst, but its scarcity and cost have motivated the exploration of robust alternatives, including transition-metal alloys, single-atom catalysts and novel topological materials. Nanostructuring and surface‐valence engineering can induce unique reaction intermediates and lower activation barriers, enabling high performance under alkaline, neutral and acidic conditions. Recent advances highlight the critical role of interfacial water structure, local electric fields, cation–electrolyte interactions and surface valence states in modulating catalytic activity. Computational modelling and in situ spectroscopies have converged to reveal mechanistic insights that guide the rational design of cost-effective, durable electrocatalysts. By bridging fundamental surface chemistry and practical electrolyser technologies, this field underpins global efforts to establish a carbon-neutral hydrogen economy.

Research from Nature Portfolio

Recent studies have elucidated the interplay between catalyst surface chemistry and reaction environment through advanced operando techniques. One investigation demonstrated that high-valence ruthenium surfaces modulate interfacial water dissociation and intermediate adsorption energies, selectively generating distinct hydrogen species that accelerate alkaline HER. Combining in situ Raman spectroscopy with theoretical calculations, researchers revealed how hydrated cations stabilise transition states and moderate adsorption energies across different valence states, offering a strategy to tune catalyst activity by valence-state regulation. Another report tackled neutral-pH HER by engineering the interfacial water network at ruthenium single-atom and cluster sites. Operando absorption spectroscopy and ab initio molecular dynamics showed that disrupting rigid interfacial water layers enhances water transport and intermediate availability, yielding mass-specific activities several times higher than conventional benchmarks at low overpotentials. These findings converge on the central importance of interfacial water management for high-performance HER across diverse electrolyte conditions.

Electrocatalysis of Hydrogen Evolution Reactions publication trend

The graph below shows the total number of articles in electrocatalysis of hydrogen evolution reactions across all publications each year (not limited to Nature Index journals).

Technical terms

Electrocatalysis: Acceleration of electrochemical reactions by a catalyst at electrode surfaces.

Hydrogen evolution reaction (HER): Electrochemical process in which protons or water molecules are reduced to molecular hydrogen.

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

Volmer step: Initial electrochemical proton discharge or water dissociation step forming adsorbed hydrogen on the catalyst surface.

Heyrovsky step: Electrochemical desorption where adsorbed hydrogen reacts with a proton and electron to release H₂.

Tafel step: Chemical recombination of two adsorbed hydrogen atoms to form molecular hydrogen.

Interfacial water: Structured water molecules at the electrode–electrolyte interface that influence reaction kinetics and intermediate formation.

References

1. Volcano plots in hydrogen electrocatalysis – uses and abuses. Beilstein Journal of Nanotechnology (2014).
2. Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction. Nature Communications (2023).
3. Interfacial water engineering boosts neutral water reduction. Nature Communications (2022).
4. The Interrelated Effect of Cations and Electrolyte pH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media. Angewandte Chemie International Edition (2021).
5. Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction. Angewandte Chemie International Edition (2023).