Atomically dispersed Ba sites as electron promoters to enhance the performance for photoreduction of CO2

doi:10.1016/S1872-2067(24)60226-3

Abstract

Abstract:

The highly photocatalytic conversion of CO₂ into valuable products is a promising method for mitigating the global greenhouse effect and increasing the energy supply. However, the utilization of electron-deficient active sites to activate CO₂ leads to lower photocatalytic efficiency and selectivity. One effective strategy to improve CO₂ photoreduction performance is making precise adjustments to the electronic structure of the photocatalyst. Herein, the defective TiO₂ modified with Cu, Ba, and CuBa metal sites is synthesized via a simple photo-deposition method and applied for photoreduction of CO₂. Among the prepared catalysts, Cu₁Ba₃/TiO₂-SBO (TiO₂-SBO: TiO₂ with surface and bulk oxygen vacancies) has been demonstrated to possess excellent photocatalytic conversion of CO₂, with the activity levels of the CO and CH₄ that are 8 and 6 times higher than the bare TiO₂-SBO, and the electron selectivity of CO is up to 53%. The results reveal that oxygen vacancies and CuBa bimetallic sites have a synergistic ability to facilitate the separation of photogenerated carriers. Furthermore, the electron-donor Ba metal enables modulation of the electronic structure of Cu co-catalysts, generating electron-rich Cu metal sites that accelerate the activation of CO₂. Meanwhile, the theoretical calculations prove that the Cu₁Ba₃/TiO₂-SBO has the stronger CO₂ adsorption energy, and its strengthened binding of *COOH and the markedly reduced formation energy of CO and *CO intermediates boost the conversion of COOH to CO and enhance the selectivity of CO. Thereby, the defective TiO₂ modified with CuBa bimetal represents a more effective measure for CO₂ reduction into valuable products.

Key words: Defective TiO₂, CuBa bimetal, Cu co-catalyst, Photoreduction of CO₂, Photocatalytic mechanism

Lina Zhang, Guowei Liu, Xinyan Deng, Qiuye Li, Jianjun Yang. Atomically dispersed Ba sites as electron promoters to enhance the performance for photoreduction of CO₂[J]. Chinese Journal of Catalysis, 2025, 70: 341-352.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60226-3

https://www.cjcatal.com/EN/Y2025/V70/I3/341

Figures/Tables 12

Fig. 1. TEM and HRTEM images of TiO2-SBO (a,c), Cu1Ba3/TiO2-SBO (b,d) as well as mapping diagram of Cu1Ba3/TiO2-SBO (e).

Fig. 2. XRD (a) and Raman (b) plots of TiO2-SBO, Cu/TiO2-SBO, Ba/TiO2-SBO and Cu1Ba3/TiO2-SBO samples.

Fig. 3. XANES spectra at the Cu K-edge of Cu1Ba3/TiO2-SBO, Cu foil, Cu2O and CuO (a) as well as Ba L3-edge of Cu1Ba3/TiO2-SBO and BaO (c). EXAFS spectra at Cu K-edge of Cu1Ba3/TiO2-SBO, Cu foil, Cu2O and CuO (b) as well as Ba L3-edge of Cu1Ba3/TiO2-SBO and BaO (d).

Fig. 4. XPS spectra of as synthesised samples. Ti 2p (a,c) and O 1s (b,d) of TiO2-SBO and Cu1Ba3/TiO2-SBO samples. (e) Cu 2p of Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO. (f) Ba 3d of Ba/TiO2-SBO and Cu1Ba3/TiO2-SBO.

Fig. 5. (a) CO-DRIFTS spectra of Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO. Differential charge density for Cu/TiO2-SBO (b) and Cu1Ba3/TiO2-SBO (c).

Fig. 6. (a) Photocatalytic CO2 reduction performance of all samples: (1) TiO2-SBO; (2) Cu/TiO2-SBO; (3) Ba/TiO2-SBO; (4) Cu1Ba1/TiO2-SBO; (5) Cu1Ba3/TiO2-SBO; (6) Cu0.5Ba3.5/TiO2-SBO. (b) Comparative activity of Cu1Ba3/A-TiO2 and Cu1Ba3/TiO2-SBO. (c) Cyclic stabilization tests of Cu1Ba3/TiO2-SBO. (d) The activity comparison of Cu1Ba3/Al2O3, Cu1Ba3/SiO2, and Cu1Ba3/TiO2-SBO in different atmospheres (under CO2 and without CO2).

Fig. 7. UV-vis absorption spectra (a), photocurrent (I-t) plots (b), PL (c) and electrochemical impedance spectra (d) of TiO2-SBO, Cu/TiO2-SBO, Ba/TiO2-SBO, and Cu1Ba3/TiO2-SBO samples.

Fig. 8. The CO2 Physisorption isotherms (a) and CO2-TPD plots (b) of the prepared samples. The details of the synthesized photocatalysts are available in Fig. 6(a).

Fig. 9. In situ XPS of Ti 2p (a), Cu 2p (b), and Ba 3d (c) for Cu1Ba3/TiO2-SBO.

Fig. 10. In situ DRIFTS plots of TiO2-SBO (a), Cu/TiO2-SBO (b), Ba/TiO2-SBO (c), and Cu1Ba3/TiO2-SBO (d).

Fig. 11. First-principles calculations of the CO step (a) and*CO step (c) over Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO. (b) The adsorption energy of *COOH on Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO, where the cyan, pink, gray, blue and green balls represent the Ti, O, C, Cu, and Ba atoms, respectively.

Scheme 1. The mechanism and reaction pathways of photocatalytic CO2 conversion for Cu1Ba3/TiO2-SBO.

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Atomically dispersed Ba sites as electron promoters to enhance the performance for photoreduction of CO₂

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