Long-term photocatalytic hydrogen peroxide production by hydroquinone-buffered covalent organic frameworks

doi:10.1016/S1872-2067(25)64676-6

Abstract

Abstract:

Photocatalytic hydrogen peroxide (H₂O₂) production offers a sustainable route to convert water and oxygen into H₂O₂ using solar energy. However, achieving long-term stability in photocatalysts remains a critical challenge due to mismatched kinetics between oxygen reduction (ORR) and water oxidation (WOR), which leads to hole accumulation and oxidative degradation. Here, we report a redox-mediated strategy to address this bottleneck by designing a hydroquinone-embedded covalent organic framework (Tz-QH-COF) that enables reversible hole buffering and kinetic balance. The hydroquinone (QH) units act as dynamic hole reservoirs, capturing excess holes during ORR and converting to benzoquinone (Q), which is regenerated to QH via WOR, thereby preventing oxidative decomposition. This reversible QH/Q cycle, directly visualized through in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, ensures unmatched stability, achieving continuous H₂O₂ production for 528 h (22 d) with an accumulated yield of 18.6 mmol L^-1—the highest reported duration for organic photocatalysts. Density functional theory calculations reveal that the QH units exhibit a strong oxygen adsorption energy and favorable two-electron ORR/WOR pathways with low energy barriers. The synergy between experimental and theoretical insights elucidates a redox-mediated charge-balance mechanism, advancing the design of robust photocatalysts for solar-driven H₂O₂ synthesis.

Key words: Covalent organic frameworks, Hole buffer, Reversible redox chemistry, Hydroquinone-quinone transformation, Long-term photocatalytic hydrogen, peroxide production

Chang Shu, Xiaoju Yang, Peixuan Xie, Xuan Yang, Bien Tan, Xiaoyan Wang. Long-term photocatalytic hydrogen peroxide production by hydroquinone-buffered covalent organic frameworks[J]. Chinese Journal of Catalysis, 2025, 73: 300-310.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64676-6

https://www.cjcatal.com/EN/Y2025/V73/I6/300

Figures/Tables 6

Fig. 1. (a) The chemical structures of the Tz-QH-COF with the reversible redox chemistry of QH/Q. C: grey; H: white; N: blue and O: red. Pawley refinements against the PXRD patterns of Tz-QH-COF (b) and Tz-ph-COF (c). Experimental diffraction patterns (black), Pawley refinement profile (orange), simulated structural model pattern (blue) and residual (purpure).

Fig. 2. FT-IR spectra (a) and Solid-state 13C CP-MAS NMR spectra (b) of the COFs. (c) Nitrogen adsorption-desorption isotherms for the COFs. (d) The water contact angle of the COFs.

Fig. 3. (a) Solid-state UV-vis absorption spectra of the COFs. (b) Energy levels of the COFs. (c) Time-resolved PL spectra of the COFs. Temperature-dependent PL spectra (inset) and corresponding fitting curves of Tz-QH-COF (d) and Tz-Ph-COF (e). (f) TA spectra of COFs under 350 nm excitation pumping wavelength.

Fig. 4. (a) Photocatalytic H2O2 production performances for Tz-QH-COF and Tz-ph-COF (10 mg catalyst in 20 mL water under visible light (λ > 420 nm for 1 h). (b) EQE of Tz-QH-COF at various incident light wavelengths. (c) Long-term photocatalytic experiment for Tz-QH-COF (50 mg catalyst in 50 ml water under visible light, λ > 420 nm; switching the atmosphere from O2 to N2 every 24 h). (d) Photocatalytic long-term stability of Tz-QH-COF compared with other reported materials (all materials are summarized in Table S1). 1H-NMR spectroscopy of filtered photocatalytic reaction solution of Tz-QH-COF in DMSO-d6 after 528 h (e) and Tz-Ph-COF in DMSO-d6 after 72 h (f) (inset: picture of the filtrated catalysts dissolved in DMSO-d6).

Fig. 5. In situ ATR-SEIRAS spectra collected on the surfaces of Tz-QH-COF in O2- (a,b) and N2- (c,d)saturated DI-H2O with the light irradiation (a,c) and without the light irradiation(b,d).

Fig. 6. Free energy diagrams of transformation from QH form to Q form through ORR pathway (a) and transformation from Q form to QH form through WOR pathway (b). (c) Proposed reaction mechanism toward H2O2 production on reversible QH/Q transformation.

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