Designing hydrogen-bonds in covalent organic frameworks: accelerating proton-coupled electron transfer for enhanced photocatalytic H2O2 synthesis

doi:10.1016/S1872-2067(26)64975-3

Abstract

Abstract:

The photocatalytic efficiency of covalent organic frameworks (COFs) toward sustainable H₂O₂ synthesis via oxygen reduction reaction (ORR) is intrinsically constrained by compromised proton-coupled electron transfer (PCET) dynamics, where retarded water oxidation reaction kinetics and exogenous proton donor dependence create a dual kinetic-thermodynamic constraint. This work presents a precision hydrogen‒bond engineering strategy through the radio-frequency plasma modification of COF linkages, establishing a hydrogen‒bond strength gradient (OH···N vs. SH···N) to probe the structure-function interplay that modulates PCET pathways. Systematic investigations reveal that hydrogen‒bond strengthening at imine linkages enables dual functionality: creating both dynamic proton reservoirs and more accessible proton conduction pathways. This synergistic regulation reduces the energy barrier for direct 2e^‒ ORR by 19.6% while suppressing high-energy intermediates in stepwise pathways, as confirmed by experiments and density functional theory calculations. The optimized SH-COF with appropriately stronger hydrogen bonds achieves exceptional photocatalytic H₂O₂ production: 2.97 and 4.70 times that of corresponding OH-COF and pristine COF, respectively. Integrated crystal orbital Hamilton population analysis quantitatively correlates hydrogen‒bond strength with charge transfer efficiency, establishing a relationship between hydrogen‒bond energy and PCET kinetics. Our findings not only demonstrate plasma modification as an effective strategy for post-synthetic hydrogen‒bond tuning but fundamentally advance the understanding of how hydrogen-bond thermodynamics govern PCET mechanisms.

Key words: Covalent organic framework, Hydrogen-bond, Hydrogen peroxide, Photocatalysis, Oxygen reduction reaction, Proton-coupled electron transfer

Ran Sun, Yuqi Zhang, Kunge Hou, Yujie Tan, Xingang Liu, Jianyuan Hou, Weixuan Zhao, Andrew E. H. Wheatley, Renxi Zhang. Designing hydrogen-bonds in covalent organic frameworks: accelerating proton-coupled electron transfer for enhanced photocatalytic H₂O₂ synthesis[J]. Chinese Journal of Catalysis, 2026, 84: 274-287.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64975-3

https://www.cjcatal.com/EN/Y2026/V84/I5/274

Figures/Tables 6

Fig. 1. (a) The synthetic routes to, and molecular structures of, COF, OH-COF and SH-COF. PXRD patterns of COF (b), OH-COF (c), and SH-COF (d) with experimental data and simulated patterns. Pawley refined profiles and corresponding refinement differences are included for comparison.

Fig. 2. N2 adsorption-desorption isotherms (a), FTIR spectra (b), thermogravimetric analysis (c), and N 1s (d), and C 1s (e) high-resolution XPS spectra of COFs prepared in this work. (f) The S 2p high-resolution XPS spectrum of SH-COF. (g) Water contact angle and image. (h) TEM image of SH-COF. (i) HAADF-STEM electron image and EDS mapping for C, N, S in SH-COF.

Fig. 3. UV-vis DRS spectra (a), Tauc plots (b), VB-XPS data (c), Mott-Schottky plots (d), energy band structures (e), PL emission spectra (f), TRPL spectra (g), transient photocurrent responses (h), and EIS Nyquist curves (i) of COF, OH-COF and SH-COF.

Fig. 4. (a) Time-dependent H2O2 photogeneration over COF, OH-COF and SH-COF in pure H2O without the addition of sacrificial agents and using the reaction conditions: 25 mg photocatalyst, 50 mL H2O, 298 K. (b) Comparison of photocatalytic H2O2 production for COF, OH-COF and SH-COF under different atmospheres (Ar, Air, O2). (c) Wavelength-dependent AQY values and the UV-vis spectrum of SH-COF. (d) Cycling stability of H2O2 production of SH-COF, the concentration of H2O2 obtained in the fifth cycle was still 3708.2 μmol g?1. (e) The comparison of the photocatalytic H2O2 production for SH-COF at different O2 concentrations. (f) The effects of sacrificial reagents on production rate of H2O2 for SH-COF. (g) EPR spectra obtained in the presence of DMPO as an electron-trapping agent. (h) The LSV curves for SH-COF measured on a RDE at different rotating speeds. (i) Electron transfer number (n) obtained by RDE measurements.

Fig. 5. (a) The HOMOs and LUMOs of COF, OH-COF and SH-COF with an iso-surface level of 1.0×10?8 eV ??3. (b) The ICOHP of hydrogen bonds in OH-COF and SH-COF. Bader charges of N and C atoms in the linkage positions of COF (c), OH-COF (d), and SH-COF (e), highlighting the length of hydrogen bonds in OH-COF and SH-COF.

Fig. 6. In-situ DRIFTS spectra of COF (a), OH-COF (b), and SH-COF (c) collected at different irradiation times during the photocatalytic process in an O2 atmosphere. (d) Isotope labeling experiment for SH-COF in H218O system after visible light irradiation for 20 h. (e) The reaction coordinates for 2e- ORR to H2O2 under U = 0 eV. (f) The reaction coordinates for 4e? WOR to O2 under U = 0 eV. (g) A summary of reaction mechanisms.

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Designing hydrogen-bonds in covalent organic frameworks: accelerating proton-coupled electron transfer for enhanced photocatalytic H₂O₂ synthesis

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