High-density Au-OV synergistic sites boost tandem photocatalysis for CO2 hydrogenation to CH3OH

doi:10.1016/S1872-2067(24)60205-6

Abstract

Abstract:

The production of renewable methanol (CH₃OH) via the photocatalytic hydrogenation of CO₂ is an ideal method to ameliorate energy shortages and mitigate CO₂ emissions: however, the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift (RWGS) reaction. Herein, we present a novel approach for the synthesis of CH₃OH via photocatalytic CO₂ hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy (O_V)-rich molybdenum dioxide (MoO₂), resulting in a remarkable selectivity of 43.78%. The active sites in the Au/MoO₂ catalyst are high-density Au-oxygen vacancies, which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation. This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO₂ to CH₃OH.

Key words: CO₂ hydrogenation, Tandem catalysis, Methanol, Au/MoO₂, Photocatalysis

Xingjuan Li, Yuhao Guo, Qinhui Guan, Xiao Li, Lulu Zhang, Weiguang Ran, Na Li, Tingjiang Yan. High-density Au-O_V synergistic sites boost tandem photocatalysis for CO₂ hydrogenation to CH₃OH[J]. Chinese Journal of Catalysis, 2025, 69: 303-314.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60205-6

https://www.cjcatal.com/EN/Y2025/V69/I2/303

Figures/Tables 7

Fig. 1. (a) Schematic illustration of the synthesis of MoOx. (b) XRD patterns of Au/MoOx. High-resolution Au 4f (c), Mo 3d (d) and O 1s (e) XPS spectra of Au/MoOx.

Fig. 2. SEM images of Au/MoO3 (a), Au/MoO3-x (b) and Au/MoO2 (c). TEM images and corresponding particle size distributions of Au/MoO3 (d), Au/MoO3-x (e) and Au/MoO2 (f). HR-TEM images of Au/MoO3 (g), Au/ MoO3-x (h) and Au/MoO2 (i).

Fig. 3. Photocatalytic CO2 hydrogenation performances. CO production rate of MoO3 (a), MoO3-x (b), MoO2 (c) with and without solar irradiation at various reaction temperatures. CH3OH (top) and CO (bottom) production rate over Au/MoO3 (d), Au/MoO3-x (e), Au/MoO2 (f) at various reaction temperatures with and without solar irradiation.

Fig. 4. Long-term performance of Au/MoO3 (20 h) (a), Au/MoO3-x (20 h) (b) and Au/MoO2 (25 h) (c) in catalyzing the hydrogenation of CO2 at 225 °C with light irradiation. (d) Long-term (20 h) performance of Au/MoO3, Au/MoO3-x and Au/MoO2 in catalyzing the hydrogenation of CO at 225 °C with light irradiation.

Fig. 5. (a) UV-vis absorption spectra of MoOx and Au/MoOx. (b) Energy band diagram of Au/MoO2. In situ XPS spectra of Au/MoO2 with and without irradiation: Au 4f (c) and (d) Mo 3d spectra. Transient photocurrent response curves (e) and EIS Nyquist plots (f) MoO2 and Au/MoOx.

Fig. 6. CO2 adsorption isotherms (a), CO2-TPD spectra (b), CO-TPD spectra (c) and H2-TPD spectra (d) of MoO2 and the Au/MoOx catalysts.

Fig. 7. In situ DRIFTS of CO2 hydrogenation on Au/MoO3 (a), Au/MoO3-x (b), Au/MoO2 (c) and MoO2 (d) catalysts under light irradiation at 225 °C. (e) Proposed mechanism of methanol synthesis on Au/MoO2 via tandem CO2 hydrogenation.

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High-density Au-O_V synergistic sites boost tandem photocatalysis for CO₂ hydrogenation to CH₃OH

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