Hole-confining covalent organic frameworks for photosynthesis of H2O2 and H2 from pure water

doi:10.1016/S1872-2067(26)65148-0

Abstract

Abstract:

Covalent organic frameworks (COFs) have emerged as promising candidates for photocatalysis, however, their efficiency in converting water into value-added chemicals is often severely constrained by sluggish water-oxidation kinetics. Herein, we demonstrate a strategy of confining photogenerated holes at specific water oxidation active sites in COFs to enhance simultaneous H₂ and H₂O₂ co-generation from water. We designed three hydrazone-linked COFs capable of driving overall water splitting without the use of sacrificial agents. Mechanistic studies reveal that the capability to confine photogenerated holes at hydrazone linkages directly correlates with superior water-splitting activity. Specifically, the accumulation of holes at these thermodynamically preferred water-adsorption sites, coupled with electron delocalization, results in a unique spatial charge separation. This configuration not only significantly suppresses recombination to extend excited-state lifetimes but also creates hole-rich local environments that accelerate water oxidation kinetics. Consequently, the optimal COF achieves H₂ and H₂O₂ production rates of 311.2 and 278.6 μmol·g^-1·h^-1, respectively. This work establishes the spatial accumulation of photogenerated holes as a pivotal, engineerable design principle for advancing COF-based photocatalytic water splitting.

Key words: Covalent organic frameworks, Photocatalysis, Hole accumulation, Overall water splitting, H₂ and H₂O₂ production

Zeng Li, Mingfei Yu, Liuyi Li, Yan Yu. Hole-confining covalent organic frameworks for photosynthesis of H₂O₂ and H₂ from pure water[J]. Chinese Journal of Catalysis, 2026, 91: 263-273.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65148-0

https://www.cjcatal.com/EN/Y2026/V91/I12/263

Figures/Tables 6

Fig. 1. (a) Schematic illustration of TFT-COF, TFB-COF, and TFS-COF. PXRD patterns of the three COFs with the experimental profiles in orange, Pawley-refined in purple (AA stacking), predicted in red, differences in sky blue, and the Bragg positions in brown for TFT-COF (Rwp=6.76%) (b), TFB-COF (Rwp=3.99%) (c), and TFS-COF (Rwp=4.26%) (d).

Fig. 2. UV-vis DRS (a), band alignments (b), transient photocurrent spectra (c), EIS plots (d), profiles of fluorescence lifetime (e), and EPR spectra (f) under dark and light conditions.

Fig. 3. KPFM images of TFT-COF (a), TFB-COF (b), and TFS-COF (c) under dark and illumination. In-situ XPS spectra of N 1s for TFT-COF (d), TFB-COF (e), and TFS-COF (f). TAS spectra

Fig. 4. (a) Electron-hole distributions of excited TFT-COF, TFB-COF, and TFS-COF. Orange and blue represent the increase and decrease in electron density, respectively. (b) Corresponding heatmap of electrons and holes. (c) Water adsorption enthalpy. (d) Corresponding electronic charge transfer between water molecules and the framework in the excited state. (e) Schematic illustration of electron and hole distributions. (f) Radar chart comparing key properties of the three COFs.

Fig. 5. (a) Photocatalytic water splitting activity of TFT-COF, TFB-COF, and TFS-COF. (b) H218O isotope experiment of TFT-COF. (c) Wavelength-dependent AQY of water splitting for TFT-COF. (d) Recycling test of water splitting for the TFT-COF.

Fig. 6. In-situ DRIFTS spectra (a) and EPR DMPO-•OH signal (b) in aqueous solution of Pt-loaded TFT-COF. (c) DFT calculated Gibbs free energy profiles for water splitting. (d) Schematic representation of photocatalytic water decomposition of the Pt-loaded TFT-COF.

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Hole-confining covalent organic frameworks for photosynthesis of H₂O₂ and H₂ from pure water

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