Photocatalytic Production of Hydrogen Peroxide

Photocatalytic production of hydrogen peroxide harnesses solar energy to convert water and dioxygen into H₂O₂ via sequential light-driven redox reactions. Central to this process are two half-reactions: the two-electron water oxidation reaction (WOR) to generate O₂ and protons, and the two-electron oxygen reduction reaction (ORR) to form H₂O₂. By tailoring the electronic and structural properties of photocatalysts, researchers have achieved enhanced light absorption, efficient charge separation and selective two-electron pathways. Advances in catalyst design span inorganic semiconductors, polymeric frameworks and single-atom sites, with performance metrics such as apparent quantum yield and solar-to-chemical conversion efficiency guiding optimisation. The ability to produce H₂O₂ under mild conditions without sacrificial reagents offers a sustainable alternative to the anthraquinone process, reducing energy consumption and carbon emissions. Practical applications include on-site generation of disinfectants, chemical synthesis of high-value oxidants and integration into solar-fuel systems. Recent work has also explored seawater as a feedstock and coupling selective oxidation reactions to boost overall efficiency. Continued developments hold promise for decentralised H₂O₂ production, contributing to greener industrial processes and the circular carbon economy.

Research from Nature Portfolio

Mechanistic analysis of polymeric carbon nitride frameworks has revealed that strategic incorporation of cyanaminate and pyridinic nitrogen moieties enhances photon absorption, promotes charge separation and creates selective two-electron ORR sites, achieving apparent quantum yields exceeding 25 % at 380 nm. Building on this insight, an inorganic Mo-doped BiVO₄ system was engineered with facet-specific CoOx and Pd cocatalysts to overcome radical-induced degradation; this design delivered a solar-to-chemical conversion efficiency of 0.29 % across the full spectrum and an apparent quantum yield of 5.8 % at 420 nm. More recently, high-loading Ni single-atom sites embedded in carbon nitride have been shown to undergo dynamic structural evolution under reaction conditions, forming high-valent intermediates that lower the energy barrier for *OOH formation and suppress O–O bond cleavage, resulting in an apparent quantum yield of 10.9 % and a solar-to-chemical conversion efficiency of 0.82 % in pure water.

Photocatalytic Production of Hydrogen Peroxide publication trend

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

Technical terms

Photocatalysis: Acceleration of a chemical reaction by a light-activated catalyst that absorbs photons to drive redox processes.

Photocatalyst: A material that harnesses light energy to generate charge carriers for initiating chemical transformations.

Oxygen reduction reaction (ORR): A half-reaction in which dioxygen is reduced, ideally via a two-electron pathway, to form hydrogen peroxide.

Water oxidation reaction (WOR): A half-reaction in which water is oxidised by two electrons to produce oxygen and protons.

Two-electron pathway: A selective reaction route in ORR or WOR that transfers exactly two electrons per molecule of reactant, enabling H₂O₂ formation.

Apparent quantum yield (AQY): The ratio of charge carriers contributing to chemical production to incident photons, expressed as a percentage.

Solar-to-chemical conversion efficiency (SCC): The fraction of solar energy converted into chemical energy stored in reaction products under defined illumination conditions.

References

1. Mechanistic analysis of multiple processes controlling solar-driven H2O2 synthesis using engineered polymeric carbon nitride. Nature Communications (2021).
2. Overall photosynthesis of H2O2 by an inorganic semiconductor. Nature Communications (2022).
3. Developing Ni single-atom sites in carbon nitride for efficient photocatalytic H2O2 production. Nature Communications (2023).
4. Cooperative tungsten centers in polymeric carbon nitride for efficient overall photosynthesis of hydrogen peroxide. Energy & Environmental Science (2024).
5. Molecularly Engineered Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis. Angewandte Chemie International Edition (2022).
6. Molecular Level Modulation of Anthraquinone‐containing Resorcinol‐formaldehyde Resin Photocatalysts for H2O2 Production with Exceeding 1.2 % Efficiency. Angewandte Chemie International Edition (2023).
7. Seawater usable for production and consumption of hydrogen peroxide as a solar fuel. Nature Communications (2016).
8. Efficient photocatalytic hydrogen peroxide generation coupled with selective benzylamine oxidation over defective ZrS3 nanobelts. Nature Communications (2021).
9. Production of hydrogen peroxide as a sustainable solar fuel from water and dioxygen. Energy & Environmental Science (2013).