Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O2 reduction centers

doi:10.1016/S1872-2067(24)60210-X

Abstract

Abstract:

Emerging as lamellar materials, covalent triazine frameworks (CTFs) exhibited great potential for photocatalysis, but their photocatalytic performance is always hindered by the prone recombination of photogenerated carriers. To overcome this obstacle, a 1D/2D step-scheme (S-scheme) heterojunction is constructed for photocatalytic synthesis of H₂O₂. The S-scheme heterojunction fabricated with CTF and ZnO effectively enhances light absorption, redox capabilities, and charge carrier separation and transfer. In particular, the CTF is decorated with benzothiadiazole and triazine groups as dual O₂ reduction active centers, boosting photocatalytic H₂O₂ production. The optimal ZC-10 hybrid delivers a maximum H₂O₂ generation rate of 12000 μmol g⁻¹ h⁻¹, 10.3 and 164 times higher than those of zinc oxide nanorods and CTFs, respectively. Moreover, the charge transfer mechanism in the S-scheme heterojunction is well investigated with in situ spectroscopic measurements and theoretical calculations.

Key words: Covalent triazine frameworks, Photocatalytic H₂O₂ production, S-scheme heterojunction, Dual O₂ reduction centers

Bingquan Xia, Gaoxiong Liu, Kun Fan, Rundong Chen, Xin Liu, Laiquan Li. Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O₂ reduction centers[J]. Chinese Journal of Catalysis, 2025, 69: 315-326.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60210-X

https://www.cjcatal.com/EN/Y2025/V69/I2/315

Figures/Tables 7

Fig. 1. Synthetic process, XRD spectra, and FT-IR spectra. (a) Synthetic procedure of ZnO/CTF samples. XRD patterns (b) and FT-IR spectra (c) of ZnO, CTF, and ZC composites.

Fig. 2. TEM images of the prepared photocatalysts: ZnO nanorods (a), CTF (b) and ZC-10 (c). High-resolution TEM (d), HAADF image (e) and elemental mappings of Zn (f), O (g), C (h), N (i), and S (j) elements in ZC-10.

Fig. 3. Photoelectrochemical characterizations. (a) UV-vis DRS spectra for ZC hybrids, CTF and ZnO; Mott-Schottky plots for ZnO (b) and CTF (c). (d) Proposed energy diagrams for ZnO and CTF.

Fig. 4. XPS spectra and photocatalytic activities. Zn 2p (a) and O 1s (b) spectra for ZnO and ZC-10. N 1s (c) and S 2p (d) spectra for CTF and ZC-10. (e) Performance tests of as-prepared samples for photocatalytic H2O2 production. (f) Comparison of the H2O2 production capability of ZnO, CTF and ZC-X under simulated irradiation for 1 h.

Fig. 5. Side view of the optimized CTF/ZnO: Side view (a) and top view (b) of the charge density difference of CTF/ZnO with an isosurface of 4.2 × 10?3 e ??3. (The charge accumulation is shown as the yellow region, and the charge depletion is shown as the cyan region). (c,d) Under dark and illuminated conditions, the KPFM images of ZC-10. (e,f) Under dark and illuminated conditions, the surface potential scanning curves of ZC-10. PL spectra (g), TRPL spectra (h), and EIS spectra (i) of the samples.

Fig. 6. EPR was utilized to test for ?O2?, ?OH, and 1O2, DRIFTS spectrum, DFT-calculated data, and a schematic diagram of the photocatalytic process. (a) EPR signals of DMPO-?O2? on ZnO, CTF, and ZC-10 in O2-saturated methanol. (b) EPR trapping experiments of TEMP-1O2 in H2O dispersions of ZC-10. (c) EPR signals of DMPO-?OH on ZnO, CTF, and ZC-10 in water. (d) DRIFTs spectrum of ZC-10 in H2O2 photosynthesis. (e) ?O2? and 1O2 conversion pathways for the O2 reduction to H2O2 on the Triazine site and benzothiadiazole site with DFT-calculated Gibbs free energy. (f) Schematic illustration of the photocatalytic production of H2O2 through the ORR pathways.

Fig. 7. Schematic illustration of S-scheme charges transfer mechanism between ZnO and CTF. Ev and Ef respectively stand for vacuum energy level and fermi energy level.

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Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O₂ reduction centers

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