Constructing S-scheme heterojunction between porphyrinyl covalent organic frameworks and Nb2C MXene for photocatalytic H2O2 production

doi:10.1016/S1872-2067(24)60247-0

Abstract

Abstract:

We have developed a novel S-scheme heterojunction photocatalyst for the photocatalytic production of hydrogen peroxide (H₂O₂) via a two-electron (2e⁻) oxygen reduction reaction. This S-scheme heterojunction Tph-Dha-COF@Nb₂C was fabricated via the in-situ solvothermal growth of Tph-Dha-COF nanostructures on amino-functionalized Nb₂C MXene nanoflakes (Nb₂C-NH₂). The integration of Nb₂C significantly extended the visible light absorption of Tph-Dha-COF into the near-infrared region for photocatalytic H₂O₂ production. The Tph-Dha-COF@Nb₂C composite demonstrated efficient charge separation, rapid electron transfer, and enhanced oxygen adsorption. Consequently, the Tph-Dha-COF@Nb₂C heterojunction exhibited a high H₂O₂ production rate of 1833 μmol g^‒1 h^‒1 without sacrificial agents. In-situ Fourier transformed infrared spectroscopy and density functional theory calculations revealed the photocatalytic H₂O₂ production mechanism. The generated H₂O₂ demonstrated enhanced antibacterial activity. This work presents the first application of Nb₂C in the photocatalytic synthesis of H₂O₂ and provides a novel strategy for constructing COF-based heterojunctions for photocatalytic H₂O₂ generation and wastewater treatment.

Key words: Photocatalysis, H₂O₂, Covalent organic framework, Nb₂C MXene, S-scheme heterojunction

Mingyang Xu, Zhenzhen Li, Rongchen Shen, Xin Zhang, Zhihong Zhang, Peng Zhang, Xin Li. Constructing S-scheme heterojunction between porphyrinyl covalent organic frameworks and Nb₂C MXene for photocatalytic H₂O₂ production[J]. Chinese Journal of Catalysis, 2025, 70: 431-443.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60247-0

https://www.cjcatal.com/EN/Y2025/V70/I3/431

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the preparation of the Tph-Dha-COF@Nb2C heterojunction. XRD patterns (b) and FT-IR spectra (c) of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C. FE-SEM (d), TEM and HR-TEM (e,f), and EDS mapping (g) images of Tph-Dha-COF@Nb2C.

Fig. 2. The high-resolution C 1s (a), N 1s (b), Nb 3d (c) and O 1s (d) of Tph-Dha-COF@Nb2C. N2 adsorption-desorption isotherms (e) and pore size distribution curves (f) of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C.

Fig. 3. (a) UV-vis diffuse reflectance spectroscopy of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C. Tauc plot (b), Mott-Schottky measurement (c) and energy band structures (d) of Nb2C-NH2 and Tph-Dha-COF. Transient photocurrent (e) and EIS spectra (f) of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C.

Fig. 4. UPS spectra in the normalized secondary electron cutoff energy (Ecutoff) regions (a) and calculated Φ stemming based on UPS spectra (b) of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C. In-situ XPS spectra of Nb 3d (c), C 1s (d), N 1s (e), and O 1s (f) of Tph-Dha-COF@Nb2C. (g) Charge transfer mechanism at the interface generated between Tph-Dha-COF and Nb2C-NH2.

Fig. 5. (a) Photocatalytic production of H2O2 for Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C under continuous O2 condition. (b) Photocatalytic reaction of Tph-Dha-COF@Nb2C under different atmosphere. (c) Photocatalytic synthesis performance of H2O2 compared with COFs and COF based catalysts in other literature (Table S2 for details). (d) Photocatalytic H2O2 generation of Tph-Dha-COF@Nb2C for 5 h. The effect of photocatalyst concentration on the H2O2 production (e) and five consecutive cycles (f) of Tph-Dha-COF@Nb2C for H2O2 generation. (g) AQY of Tph-Dha-COF@Nb2C at 365, 420, 450, 500, 600 nm bandpass filters. (h) SCC of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C at λ > 420 nm. (i) Photocatalytic H2O2 production over Tph-Dha-COF@Nb2C in the presence of different sacrificial agents.

Fig. 6. EPR spectra of ?O2? (a) and ?OH (b) for Tph-Dha-COF@Nb2C under different stimulation. (c) Kouteckly-Levich plots obtained by RDE tests in phosphate buffer (pH = 7) solution. (d) In-situ DRIFT spectra of Tph-Dha-COF@Nb2C under UV-vis irradiation at different times. (e) Free energy diagrams of Nb2C-NH2, Tph-Dha-COF and Tph-Dha-COF@Nb2C for the photosynthesis of H2O2 2e? ORR pathway. (f) Proposed 2e? ORR mechanism of H2O2 generation on Tph-Dha-COF@Nb2C.

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Constructing S-scheme heterojunction between porphyrinyl covalent organic frameworks and Nb₂C MXene for photocatalytic H₂O₂ production

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