Donor–Acceptor Type Hypercrosslinked Organic Polymers for Highly Efficient Photosynthesis of H₂O₂

Artificial photosynthesis for photocatalytic H₂O₂ synthesis has emerged as a highly promising sustainable alternative. Donor–acceptor (D–A) organic polymers stand out among catalytic materials due to their exceptional structural tunability and environmental benignity—key advantages for practical applications. However, integrating D–A motifs into π-conjugated frameworks (e.g., conjugated microporous polymers, CMPs) often alters the photoelectrochemical properties of the monomers through strong π–π interactions and extended conjugation, limiting catalytic performance. Herein, 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN)-based donor–acceptor (D–A) hypercrosslinked organic polymer (HOP) are reported, synthesized via Friedel-Crafts alkylation with dimethoxymethane (DMM) as the crosslinker. The optimal 4CzIPN-based HOP (DMM-15) achieves a H₂O₂ production rate of 2.31 mmol g⁻¹ h⁻¹ in pure water (≈12.8-fold higher than Scholl-coupled 4CzIPN-CMPs) and also performs well under outdoor sunlight. Mechanistic studies reveal DMM-introduced ─OCH₃ enhances hydrophilicity and optimize electronic structure, thereby favoring the two-electron ORR pathway for efficient H₂O₂ generation. This work provides a new design paradigm for artificial photosynthesis materials. © 2026 Wiley-VCH GmbH.