Efficient H₂O₂ photosynthesis in pure water enabled by multivariate hydrogen-bonded organic framework

The global demand for hydrogen peroxide (H₂O₂) necessitates a shift from the energy-intensive anthraquinone process toward sustainable, solar-driven synthesis. Although metal-organic frameworks (MOFs) have emerged as promising photocatalysts, their reliance on metal nodes often leads to high costs and undesirable H₂O₂ decomposition. To address these limitations, this work reports a metal-free mixed-linker hydrogen-bonded organic framework (HOF) incorporating a biomimetic energy-transfer system. By co-assembling pyrene-based 1,3,6,8-Tetra (4'-Carboxyphenyl) Pyrene (TBAPy) and porphyrin-based 5,10,15,20-Tetrakis (4carboxyphenyl) porphyrin (TCPP) ligands, a synergistic architecture is constructed in which TBAPy functions as a light-harvesting antenna that efficiently transfers excitation energy to redox-active TCPP sites. Density functional theory (DFT) calculations combined with experimental investigations demonstrate that this intraframework energy transfer aligns the electronic structure, promotes efficient charge separation, enhances O₂ adsorption, and facilitates the formation of the key intermediate (*OOH) during the oxygen reduction reaction. As a result, the optimized 7.5TCPP-TBAPy HOF achieves an exceptional H₂O₂ production rate of 730.45 μmol g^-1 h^-1 under visible-light irradiation in pure water, representing a 3.6-fold enhancement over the single-linker TCPP HOF and more than a 13.7-fold improvement compared with the TBAPy HOF. This work presents the first integration of TBAPy and TCPP within a HOF for photocatalytic H₂O₂ synthesis and establishes molecular energy-channel engineering as an effective strategy for achieving high-efficiency, metal-free solar chemical production.