Electrocatalytic Water Splitting with Perovskite Oxides

Electrocatalytic water splitting converts electrical energy into hydrogen and oxygen through two half-reactions: the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode. Perovskite oxides, typically with the formula ABO₃, have attracted intense interest as earth-abundant catalysts for both HER and OER. Their compositional flexibility allows systematic tuning of A-site and B-site cations, introduction of oxygen vacancies and control of electronic structure, all of which govern catalytic activity and stability. Recent advances have focused on enhancing surface area via nanostructuring, promoting active lattice oxygen participation, engineering super-exchange interactions and constructing heterostructures to enable synergistic effects. Achieving low overpotentials and favourable Tafel slopes remains essential to reduce energy losses and accelerate reaction kinetics. Beyond fundamental insights into bond covalency, defect chemistry and adsorption energetics, perovskite catalysts are being integrated into alkaline electrolyser designs for sustainable hydrogen production. This field sits at the interface of materials chemistry, solid-state physics and renewable energy technologies and promises to underpin the hydrogen economy.

Research from Nature Portfolio

Studies of Sr-substituted cobaltite perovskites have elucidated how A-site doping controls oxygen vacancy concentration and Co–O bond covalency, revealing that optimal compositions such as SrCoO₂.₇ deliver exceptional OER activity at room temperature. Detailed computational modelling has confirmed the active role of lattice oxygen in the evolution mechanism. In parallel, heterostructures combining La₀.₅Sr₀.₅CoO₃–δ with MoSe₂ have showcased a local phase transition in MoSe₂ and charge-transfer-induced oxidation of cobalt, producing a robust bifunctional catalyst that operates continuously at high current densities for more than 1,000 hours. Finally, single-phase SrTi₀.₇Ru₀.₃O₃–δ perovskites exploit an intrinsic super-exchange effect to create atomic-scale active centres: Ti sites mediate nearly barrier-free water dissociation, Ru sites facilitate hydroxide desorption and oxygen vacancies optimise hydrogen adsorption, collectively achieving ultrafast HER in alkaline media.

Electrocatalytic Water Splitting with Perovskite Oxides publication trend

The graph below shows the total number of articles in electrocatalytic water splitting with perovskite oxides across all publications each year (not limited to Nature Index journals).

Technical terms

Perovskite oxide: A crystalline material with the general formula ABO₃, where A and B are metal cations occupying distinct lattice sites.

Oxygen evolution reaction (OER): The anodic half-reaction in water splitting that produces O₂ from OH⁻, typically requiring high overpotential.

Hydrogen evolution reaction (HER): The cathodic half-reaction in water splitting that reduces protons or water molecules to H₂ gas.

Overpotential: The extra voltage beyond the thermodynamic potential needed to drive an electrochemical reaction at a given rate.

Tafel slope: A parameter indicating how the reaction rate (current density) changes with overpotential; lower values denote faster kinetics.

Exsolution: The process by which metal nanoparticles emerge from a host oxide lattice under reductive conditions, creating surface active sites.

Heterostructure: A composite material formed by interfacing two distinct phases to exploit synergistic electronic or structural interactions.

References

1. Perovskite Oxides Toward Oxygen Evolution Reaction: Intellectual Design Strategies, Properties and Perspectives. Electrochemical Energy Reviews (2024).
2. Microwave shock motivating the Sr substitution of 2D porous GdFeO3 perovskite for highly active oxygen evolution. Journal of Energy Chemistry (2024).
3. Combined Exsolution and Electrodeposition Strategy for Enhancing Electrocatalytic Activity of Ti‐Based Perovskite Oxides in Oxygen and Hydrogen Evolution Reactions. Advanced Science (2024).
4. In-situ local phase-transitioned MoSe2 in La0.5Sr0.5CoO3-δ heterostructure and stable overall water electrolysis over 1000 hours. Nature Communications (2019).
5. Single-phase perovskite oxide with super-exchange induced atomic-scale synergistic active centers enables ultrafast hydrogen evolution. Nature Communications (2020).