Cyano-functionalized covalent organic frameworks for enhanced photocatalytic hydrogen peroxide production via microenvironment engineering

doi:10.1016/S1872-2067(26)64952-2

Abstract

Abstract:

Covalent organic frameworks (COFs) have garnered considerable attention for their potential in photocatalytic hydrogen peroxide (H₂O₂) generation. However, their limited photocatalytic efficiency, resulting from rapid photogenerated carrier recombination and weak oxygen adsorption, remains a critical challenge, especially in systems without sacrificial agents. Herein, we present a cyano-functionalized COF, BTT-CN-COF, synthesized by Schiff-base condensation of benzotrithiophene-2,5,8-tricarbaldehyde and 2,5-diaminobenzonitrile monomers. Incorporating the electron-withdrawing cyano groups into the COF creates a strongly polarized microenvironment that redistributes π-electron structure. This modulation enhances material hydrophilicity, reduces exciton binding energy to accelerate charge separation, prolongs photogenerated carrier lifetime, and favors a Yeager-type oxygen adsorption configuration, thereby enhancing photocatalytic performance. Consequently, BTT-CN-COF achieves an impressive H₂O₂ production rate of 3711 μmol g⁻¹ h⁻¹ under sacrificial-agent-free conditions and retains high stability for at least 20 h, surpassing the cyano-free analogue COF (BTT-Ph-COF) and numerous reported COF-based photocatalysts. Mechanism studies reveal that H₂O₂ generation primarily proceeds via a sequential two-step single-electron oxygen reduction reaction, accompanied by a direct two-electron water oxidation reaction.

Key words: Photocatalytic hydrogen peroxide production, Covalent organic frameworks, Cyano-functionalized material, Microenvironment engineering, Photocatalytic oxygen reduction reaction

Wenao Xie, Zhifang Jia, Chang Shu, Tingxia Wang, Jianhong Xi, Jiaxuan Cai, Xiangyang Song, Yu Che, Xiaoyan Wang, Kewei Wang, Bien Tan. Cyano-functionalized covalent organic frameworks for enhanced photocatalytic hydrogen peroxide production via microenvironment engineering[J]. Chinese Journal of Catalysis, 2026, 83: 282-293.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64952-2

https://www.cjcatal.com/EN/Y2026/V83/I4/282

Figures/Tables 5

Fig. 1. Synthesis and structures of the COFs (top, C: grey; H: white; N: blue; and S: yellow). PXRD patterns of BTT-Ph-COF (a) and BTT-CN-COF (b). Experimental diffraction patterns (pink), Pawley refinement profile (orange), simulated structural model pattern (blue), and residual (green). Reflection positions are shown by tick marks.

Fig. 2. Characterizations of BTT-Ph-COF and BTT-CN-COF. FT-IR (a) and CP-MAS 13C NMR spectra (b) of BTT-Ph-COF and BTT-CN-COF. N2 adsorption-desorption isotherms of BTT-CN-COF (c) and BTT-Ph-COF (d) (The insets show the pore size distributions of the COFs). (e) XPS of BTT-CN-COF in the N 1s region. (f) SEM image of BTT-CN-COF. (g) HRTEM image of BTT-CN-COF with crystal lattice spacing (insets). (h) EDX elemental mapping of C, N, and S from TEM. (i) Water contact angles for BTT-Ph-COF and BTT-CN-COF.

Fig. 3. Optical properties and photocatalytic production of H2O2. UV-vis DRS (a) and energy levels (b) of BTT-Ph-COF and BTT-CN-COF. (c) Time-dependent photocatalytic H2O2 production performance of COFs (5 mg catalyst in 50 mL water under visible light; λ > 420 nm; 300 W xenon lamp; O2). (d) Photocatalytic H2O2 production performance of BTT-CN-COF with different catalyst dosages (50 mL water; λ > 420 nm; 300 W xenon lamp; O2; 1 h). (e) Photocatalytic cycle performance of BTT-CN-COF (50 mg catalyst in 50 mL water under visible light, λ > 420 nm, 4 h for each cycle). (f) AQY of BTT-CN-COF at various incident light wavelengths. (g) Photocatalytic performance comparison of BTT-CN-COF with the reported photocatalysts.

Fig. 4. Photoelectric properties and reaction mechanism. (a) TPR spectra of COFs. TD-PL spectra (inset) and corresponding fitting curves of BTT-Ph-COF (b) and BTT-CN-COF (c). (d) TRPL spectra of BTT-Ph-COF and BTT-CN-COF. fs-TAS of BTT-CN-COF (e) and BTT-Ph-COF (f) under 350 nm excitation. (g) Photocatalytic H2O2 production performance using different quenching agents (KBrO3 under N2 atmosphere, and no scavenger, p-BQ, and BnOH under O2 atmosphere). (h) EPR experiments for BTT-CN-COF and BTT-Ph-COF using DMPO as a spin-trapping agent. (i) In-situ ATR-SEIRAS spectra vs. illumination time for the photocatalytic system of BTT-CN-COF.

Fig. 5. O2 adsorption sites and configurations on BTT-CN-COF (a) and BTT-Ph-COF (b). (c) The adsorption energies of O2 at optimum sites of BTT-CN-COF. (d) Free-energy diagrams for the reduction of O2 to H2O2 on the BTT-CN-COF and BTT-Ph-COF. (e) Proposed mechanism for photocatalytic H2O2 production on the surface of BTT-CN-COF.

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