Enhanced redox kinetics for hydrogen peroxide photosynthesis at high-concentration by encapsulating porphyrin metal–organic frameworks with phenolic resin†

Photocatalytic hydrogen peroxide (H₂O₂) production (PHP) represents a promising strategy for substituting the anthraquinone process, yet the sluggish redox kinetics cause strong oxidizing superoxide intermediate rapid accumulation, resulting in poor reaction performance and stability. Herein, we report an interface-adapted all-organic step-scheme (S-scheme) photocatalyst based on Hf-based porphyrin metal–organic frameworks (Hf-PMOFs) and benzoxazine-based 3-aminophenol-formaldehyde (APF) resin, realizing a record-high H₂O₂ yield of 2995.13 μmol h⁻¹ g⁻¹ using porphyrin-based photocatalysts in pure water and a quantum efficiency of 4.53% under 420 nm. The concentration of the obtained H₂O₂ solution reaches 6.93 mM in the continuous test, meeting the potential for on-site photosynthesis. This achievement results from the encapsulation of APF to provide channels for charge transfer and modulate the surface electronic structure to eliminate the reaction energy barrier of the *OOH intermediate, accelerating the conversion of the superoxide intermediate. We show that the PHP can be performed by utilizing domestic water sources, suggesting its wide applicability. Furthermore, we construct a floatable platform based on Hf-PMOF/APF to in situ supply H₂O₂ for Fenton reaction under light irradiation towards tetracycline hydrochloride degradation. This empirical evidence confirms that encapsulating porphyrin-based photocatalysts with resin can enhance charge dynamics and optimize the redox capability of photocatalytic systems towards advancing the development of practical photocatalytic applications.