Coupling Electron Transfer and Redox Site in Boranil Covalent Organic Framework Toward Boosting Photocatalytic Water Oxidation.

The efficient polymeric semiconducting photocatalyst for solar-driven sluggish kinetics with multielectron transfer oxygen evolution has spurred scientific interest. However, existing photocatalysts limited by π-conjugations, visible-light harvest, and charge transfer often compromise the O production rate. Herein, we introduced an alternative strategy involving a boranil functionalized-based fully π-conjugated ordered donor and acceptor (D-A) covalent organic frameworks (Ni-TAPP-COF-BF ) photocatalyst. The co-catalyst-free Ni-TAPP-COF-BF exhibits an excellent ~11-fold photocatalytic water oxidation rate, reaching 1404 μmol g  h under visible light irradiation compared to pristine Ni-TAPP-COF (123 μmol g  h ) alone and surpasses to reported organic frameworks counterpart. Both experimental and theoretical results demonstrate that the push/pull mechanism (metalloporphyrin/BF ) is responsible for the appropriate light-harvesting properties and extending π-conjugation through chelating BF moieties. This strategy benefits in narrowing band structure, improving photo-induced charge separation, and prolonged charge recombination. Further, the lower spin magnetic moment of M-TAPP-COF-BF and the closer d-band center of metal sites toward the Fermi level lead to a lower energy barrier for *O intermediate. Reveal the potential of the functionalization strategy and opens up an alternative approach for engineering future photocatalysts in energy conversion applications.