Role of Y2O3 in Cu/ZnO/Y2O3 catalysts for CO2 hydrogenation to methanol

doi:10.1016/S1872-2067(24)60220-2

Abstract

Abstract:

CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO₂ hydrogenation, but it early deactivates and its methanol yield still needs to improve. In this study, Y₂O₃ was introduced to Cu/ZnO using a one-pot hydrothermal method, and exhibits a synergistic effect of ZnO and Y₂O₃ on enhancing methanol yield and the stability. We found that the interaction between Y₂O₃ and ZnO results in abundant oxygen vacancies formation, thereby enhancing CO₂ adsorption and activation. Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO^*, and the introduction of Y₂O₃ to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation, thus enhancing the methanol yield on Cu/ZnO/Y₂O₃.

Key words: Methanol yield, Oxygen vacancies, Kinetics, Fourier transformed infrared, Intermediate

Ziguo Cai, Xuefeng Yu, Penglong Wang, Huifang Wu, Ruifeng Chong, Limin Ren, Tao Hu, Xiang Wang. Role of Y₂O₃ in Cu/ZnO/Y₂O₃ catalysts for CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2025, 70: 410-419.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60220-2

https://www.cjcatal.com/EN/Y2025/V70/I3/410

Figures/Tables 9

Fig. 1. Performance of CuZnY-2 catalyst at 200-260 °C (a,b) and Cu/ZnO/Y2O3 catalysts with different ratios of ZnO to Y2O (c,d)3 at 240 °C in a mixture flow of H2/CO2/Ar = 3:1:1 under a pressure of 3 MPa with a GHSV of 9000 mL gcat.-1 h-1.

Fig. 2. SEM images of CuZn (a), CuY (b) and CuZnY-2 (c,d) catalysts. SEM-EDS elemental mapping images of (e-h) CuZnY-2 catalyst shown in (d).

Fig. 3. (a) XRD patterns of catalysts. (b) Raman spectra of calcined oxides and reduced catalysts. (c) Raman spectra of calcined, reduced, re-oxidation and re-reduction CuZnY-2. (d) O 1s XPS spectra of catalysts.

Fig. 4. (a) H2-TPR of CuZn-ox, CuZnY-2-ox and CuY-ox. (b) Cu 2p XPS spectra of CuZn, CuZnY-2 and CuY catalysts.

Fig. 5. Arrhenius plots for CH3OH formation (a) and CO formation (b), and H2 (c) and CO2 (d) reaction orders for CH3OH formation rate over CuY, CuZn and CuZnY-2 catalysts.

Fig. 6. (a) CO2-TPD of catalysts. (b) Proportion of moderate basic sites.

Fig. 7. In situ DRIFTS spectra collected when the feed gas was switched from Ar to CO2 over CuZnY-2 (Cu loading is 5%) catalyst at 240 °C and ambient pressure.

Fig. 8. In situ DRIFTS spectra collected at 240 °C and 1 bar when the feed gas was switched from H2 to CO2 (a), and then to H2 (c) over CuZnY-2 (Cu loading is 5%) catalyst. (b,d) Evolution of HCOO* species (2883 cm-1) and CH3O* species (2828 cm-1) with reaction time. (e) Scheme of reaction pathway for CO2 hydrogenation to methanol over Cu/ZnO/Y2O3.

Fig. 9. A 100-h test of CuZn and CuZnY-2 in CO2 hydrogenation at 240 °C in a mixture flow of H2/CO2/Ar = 3:1:1 under a pressure of 3 MPa with a GHSV of 9000 mL gcat-1 h-1.

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Role of Y₂O₃ in Cu/ZnO/Y₂O₃ catalysts for CO₂ hydrogenation to methanol

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