Boosting CO2 photoreduction by synergistic optimization of multiple processes through metal vacancy engineering

doi:10.1016/S1872-2067(24)60074-4

Abstract

Abstract:

The photoreduction of greenhouse gas CO₂ using photocatalytic technologies not only benefits environmental remediation but also facilitates the production of raw materials for chemicals. However, the efficiency of CO₂ photoreduction remains generally low due to the challenging activation of CO₂ and the limited light absorption and separation of charge. Defect engineering of catalysts represents a pivotal strategy to enhance the photocatalytic activity for CO₂, with most research on metal oxide catalysts focusing on the creation of anionic vacancies. The exploration of metal vacancies and their effects, however, is still underexplored. In this study, we prepared an In₂O₃ catalyst with indium vacancies (V_In) through defect engineering for CO₂ photoreduction. Experimental and theoretical calculations results demonstrate that V_In not only facilitate light absorption and charge separation in the catalyst but also enhance CO₂ adsorption and reduce the energy barrier for the formation of the key intermediate *COOH during CO₂ reduction. Through metal vacancy engineering, the activity of the catalyst was 7.4 times, reaching an outstanding rate of 841.32 µmol g^‒1 h^‒1. This work unveils the mechanism of metal vacancies in CO₂photoreduction and provides theoretical guidance for the development of novel CO₂ photoreduction catalysts.

Key words: Photocatalyst, CO₂ photoreduction, Indium oxide, Metal vacancy, Defect

Jinlong Wang, Dongni Liu, Mingyang Li, Xiaoyi Gu, Shiqun Wu, Jinlong Zhang. Boosting CO₂ photoreduction by synergistic optimization of multiple processes through metal vacancy engineering[J]. Chinese Journal of Catalysis, 2024, 63: 202-212.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60074-4

https://www.cjcatal.com/EN/Y2024/V63/I8/202

Figures/Tables 8

Scheme 1. Scheme depicting the synthesis of In2O3 with In vacancies.

Fig. 1. HRTEM images of In2O3 (a) and In2?xO3-20 (e). HAADF-STEM (b) and corresponding elemental mapping of In (c) and O (d) of In2O3. (f) HAADF-STEM and corresponding elemental mapping of In (g) and O (h) of In2?xO3-20.

Fig. 2. (a) XRD patterns of In2O3 and In2?xO3 samples. (b) Raman spectra of In2O3 and In2?xO3 samples. (c) FTIR spectra of In2O3 and In2?xO3-20. (d) In 3d high resolution XPS spectra of In2O3 and In2?xO3-20.

Fig. 3. (a) The UV-vis DRS spectra. (b) Corresponding Tauc plotsusing (αhν)1/2 (Kubelka-Munk parameter) as a function versus the photon energy. Mott-Schottky plots (c) and VB and CB edge potentials and bandgap values (d) of In2O3, In2?xO3-10, In2?xO3-20 and In2?xO3-30.

Fig. 4. (a) Time dependent conversion rates of CO2 to CO of In2O3, In2?xO3-10, In2?xO3-20, In2?xO3-30. (b) Carbon monoxide generation rate of the samples. (c) Reusability of In2?xO3-20 during the process of photocatalytic CO2 reduction. (d) Comparative testing of In2?xO3-20 under different conditions.

Fig. 5. (a) PL spectra of In2O3, In2?xO3-10, In2?xO3-20, In2?xO3-30. Time-resolved fluorescence decay spectra (b), transient photocurrent response density (c) and Nyquist plots of EIS (d) of the samples.

Fig. 6. In situ DRIFTS spectra of CO2 and H2O interaction with In2O3 (a), In2?xO3-20 (b) in the dark and light.

Fig. 7. (a) CO2 adsorption energy on different sites. (b) C=O bond length of adsorbed CO2 on different sites. (c) Bond angle of adsorbed CO2 on different sites. (d,e) Top and side view of charge density difference of In2O3 with CO2 adsorption. (f,g) Top and side view of Charge density difference of In2?xO3 with CO2 adsorption, the topological construction represents electron accumulation (purple) and depletion (green), and the isosurface level is 0.002 e ??3. (h) Gibbs free energy diagrams for the conversion of CO2 into CO on In2O3 and In2?xO3. The blue, and yellow ball represent In, O atom, respectively.

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Boosting CO₂ photoreduction by synergistic optimization of multiple processes through metal vacancy engineering

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