Organic-inorganic DVA-COF@TiO2 S-scheme heterojunction for highly selective photocatalytic reduction of CO2 to CO

doi:10.1016/S1872-2067(26)65190-X

Abstract

Abstract:

Photocatalytic reduction of CO₂ to produce high-value-added hydrocarbon fuels is expected to solve the severe predicament of energy shortage and the environmental governance challenges. Here, in-situ growth strategy is applied to couple TiO₂ nanoparticles with spherical covalent organic framework (DVA-COF) to form a DVA-COF@TiO₂ S-scheme heterojunction photocatalyst for CO₂ reduction. The as-prepared DVA-COF@TiO₂ S-scheme photocatalyst exhibited the enhanced photocatalytic CO₂ reduction rate (12.46 μmol g^-1 h^-1) and CO selectivity (92.22%). The S-scheme charge transfer mechanism was investigated by in-situ irradiated X-ray photoelectron spectroscopy, electron paramagnetic resonance, density functional theory calculation, and femtosecond transient absorption spectroscopy. In-situ diffuse reflectance Fourier transform infrared spectroscopy and free energy calculations have unveiled the process of photocatalytic CO₂ reduction and the reasons of the improved CO product selectivity of the heterojunction photocatalysts. This study provides a critical theoretical reference for the development of the novel organic-inorganic S-scheme heterojunction photocatalysts with higher CO selectivity, which is expected to inject strong power into the practical application of sustainable artificial photosynthesis technology.

Key words: DVA-covalent organic frameworks, TiO₂, S-scheme heterojunction, Photocatalytic, CO₂ reduction, Mechanism

Tengyuan Gao, Aoyu Shu, Xiufan Liu, Xinhe Wu, Guohong Wang. Organic-inorganic DVA-COF@TiO₂ S-scheme heterojunction for highly selective photocatalytic reduction of CO₂ to CO[J]. Chinese Journal of Catalysis, 2026, 90: 197-209.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65190-X

https://www.cjcatal.com/EN/Y2026/V90/I11/197

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Fig. 1. (a) Schematic representation for preparing samples. (b) SEM image of DVAT200. TEM (c,d) and HRTEM (e,f) images of DVAT200. (g) HAADF image of DVAT200 and the corresponding EDS maps of C, N, O, Ti. (h) The experimental and simulated XRD patterns of DVA-COF. (i) XRD patterns of TiO2, DVA-COF, and DVATx. (j) FT-IR spectra of DVA, TAPB, and DVA-COF. (k) FT-IR spectra of DVA-COF, TiO2, and DVAT200.

Fig. 2. (a) The photocatalytic CO2 reduction performance of TiO2, DVA-COF, and DVATx. (b) Product selectivity of different samples. (c) Time courses of CO2 reduction in the cycle tests. Photocurrent (d) and electrical impedance (e) plots of TiO2, DVA-COF, and DVAT200. (f) TRPL plots of DVA-COF and DVAT200. (g,h) The differential charge densities side view of DVA-COF@TiO2 hybrid.

Fig. 3. (a) UV-vis DRS spectra of DVA-COF, TiO2, and DVAT200. (b) Tauc plots of DVA-COF and TiO2. (c) Mott-Schottky plots of TiO2 and DVA-COF. (d) Valence spectra of TiO2 and DVA-COF. XPS high-resolution spectra of N 1s (e) and Ti 2p (f). EPR signals of DMPO-•OH (g) and DMPO-•O2- (h) for DVA-COF, TiO2, and DVAT200. (i) Band diagrams and the charge carrier transfer mechanism of DVA-COF@TiO2

Fig. 4. 2D pseudocolor plots of DVA-COF (a), TiO2 (b), and DVAT200 hybrid (c). Fs-TA spectra of DVA-COF (d), TiO2 (e), and DVAT200 COF heterojunction (f) at indicated delay times under 325 nm pump pulse with average pump power at ~75 mW. Normalized fs-TA decay kinetics curves of TiO2 at 460 nm (g) and DVAT200 hybrid at 460 nm (h). (i) Schematic for the decay pathways of photogenerated electrons in DVAT200 heterojunction.

Fig. 5. The adsorption energies of CO2 at the surface of DVAT200 (a), DVA-COF (b), and TiO2 (c). Charge density difference side view and Bader charge calculation results of DVAT200 (d), DVA-COF (e), and TiO2 (f).

Fig. 6. The in-situ DRIFT spectra and 2D pseudocolor of DVA-COF (a,b) and DVAT200 (c,d).

Fig. 7. (a) Free energy diagrams of photocatalytic CO2 reduction to CO at DVAT200 and DVA-COF. (b) Key steps of photocatalytic CO2 reduction to CO on DVA-COF and DVATx. (c) Key steps of photocatalytic CO2 reduction on DVATx and DVA-COF.

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Organic-inorganic DVA-COF@TiO₂ S-scheme heterojunction for highly selective photocatalytic reduction of CO₂ to CO

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