Efficient H2O2 photosynthesis through linker engineering of benzotrithiophene-based covalent organic frameworks

doi:10.1016/S1872-2067(25)64925-4

Abstract

Abstract:

The photogenerated carrier separation efficiency and material wettability are of critical importance for aqueous-phase photocatalytic reactions, achieving both simultaneously poses a significant challenge owing to the inherent interdependencies and trade-offs involved. In this work, a series of isoreticular benzotrithiophene-based covalent organic frameworks (COFs) were successfully synthesized by incorporating diverse hydrophobic and hydrophilic functional groups (-OH, -F, -H) onto their skeletons, thereby modulating their characteristic charge separation and transport as well as their wettability, and systematically studied their photocatalytic H₂O₂ production performance in O₂-saturated water under visible-light irradiation. Remarkably, the synthesized hydrophilic BTT-BD-OH-COF demonstrates the highest H₂O₂ production rate of 6105 μmol g^-1 h^-1 in the absence of any sacrificial agent in pure water, attributed to its extended light absorption range, improved hydrophilicity, and enhanced photo-induced charge separation and transport efficiency. Combined experimental results and the density functional theory calculations elucidate the reaction mechanism, revealing the overall H₂O₂ photosynthesis via both oxygen reduction reaction and water oxidation reaction dual pathways. This study demonstrates that functional-group-mediated linker engineering is a powerful approach for significantly enhancing the efficiency of COF-based photocatalysts.

Key words: Covalent organic frameworks, Photocatalysis, Hydrogen peroxide, Linker engineering, Benzotrithiophene

Ke-Hui Xie, Cong-Xue Liu, Yan Geng, Jing-Lan Kan, Guang-Bo Wang, Yu-Bin Dong. Efficient H₂O₂ photosynthesis through linker engineering of benzotrithiophene-based covalent organic frameworks[J]. Chinese Journal of Catalysis, 2026, 83: 271-281.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64925-4

https://www.cjcatal.com/EN/Y2026/V83/I4/271

Figures/Tables 5

Fig. 1. Schematic synthesis of the COFs (a). The experimental as well as simulated PXRD patterns of BTT-BD-OH-COF (b), BTT-BD-COF (c), and BTT-BD-F-COF (d) with the AA eclipsed stacking mode.

Fig. 2. The solid state 13C CP/MAS NMR spectrum of BTT-BD-OH-COF (a). High resolution N 1s (b), S 2p (c), O 1s (d) XPS spectra of BTT-BD-OH-COF. The N2 adsorption-desorption isotherm of BTT-BD-OH-COF was measured at 77 K, a standard temperature for such analyses, to characterize its porosity. (e) The inset figure illustrates the pore size distribution of BTT-BD-OH-COF, derived from NLDFT. (f) Water contact angle measurements of BTT-BD-X-COFs.

Fig. 3. (a) The UV-vis DRS of the COFs. (b) The Tauc plots of the COFs for band gap calculation. (c) The M-S plot of BTT-BD-OH-COF. (d) The energy band alignment of the COFs, as determined experimentally. (e) Comparative analysis of the photocurrent responses in the COFs. (f) The EIS Nyquist plots of the COFs. (g) The PL spectra of the COFs. (h) The TRPL spectra of the COFs. (i) The distributions of the photo-excited electrons and holes of BTT-BD-OH-COF (blue and green represent electrons and holes, respectively).

Fig. 4. (a) Time-dependent H2O2 production curves of all the COFs under visible-light irradiation over 2 h. (b) The AQYs of BTT-BD-OH-COF at different wavelengths (450, 475, 520, 550, 600, 650 nm). (c) The Kf and Kd rate constants of H2O2 for all the COFs. (d) Recyclability of BTT-BD-OH-COF for photocatalytic hydrogen peroxide production. (e) The comparison of hydrogen peroxide generation rates of COFs under different atmosphere conditions. (f) The control experiments showing the H2O2 production performance of COFs under O2 atmosphere conditions. ρ-BQ: 1,4-benzoquinone.

Fig. 5. (a) The EPR spectra of BTT-BD-OH-COF in dark and light with DMPO as the spin-trap agent. (b) The time-dependent photocatalytic O2 evolution profiles of BTT-BD-F-COF over 4 h. (c,d) The isotopic experiments with BTT-BD-F-COF as the photocatalyst in H218O. (e) RRDE voltammograms of BTT-BD-OH-COF with a potential of -0.23 V vs. Ag/AgCl on Pt ring electrode to detect O2. (f) RRDE voltammograms of BTT-BD-OH-COF with a potential of +0.60 V vs. Ag/AgCl on Pt ring electrode to detect H2O2. (g) The corresponding ESP map of BTT-BD-OH-COF model. (h) The ΔG diagram for ORR pathway into H2O2 over the COFs. (i) The ΔG diagram for the WOR pathway into H2O2 over BTT-BD-OH-COF and BTT-BD-COF.

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Efficient H₂O₂ photosynthesis through linker engineering of benzotrithiophene-based covalent organic frameworks

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