Precise tailoring of Cu-ZrO2 interfaces for CO2 hydrogenation to methanol

doi:10.1016/S1872-2067(26)65168-6

Abstract

Abstract:

The rational design of metal-oxide interfaces is crucial for efficient CO₂ hydrogenation to methanol. Here, highly dispersed ZrO₂ coating was precisely modulated on the Cu/Al₂O₃ via atomic layer deposition, obtaining a uniform and well-defined Cu-ZrO₂ interfaces. Compared with traditional methods, the optimized Cu/Al₂O₃@2ZrO₂-A catalyst exhibited significantly enhanced CO₂ conversion and methanol selectivity, achieving a methanol space-time yield of 0.537 g_MeOH g-_cat^-1 h^-1 and 9.59 g-_MeOH g_Cu^-1 h^-1 at 240 °C, along with long-term stability over 400 h. Structural and electronic characterizations revealed that uniform Cu-ZrO₂ interfaces with highly dispersed and vacancy-rich ZrO₂ coating were achieved on the Cu/Al₂O₃@2ZrO₂-A catalyst, demonstrating high CO₂ adsorption and activation. In situ spectroscopic studies demonstrated that the uniform and robust Cu-ZrO₂ interface with oxygen vacancy-rich ZrO₂ coating could enhance the formation and transformation of formate intermediate. This work provides a potentially efficient strategy for precisely modulating the interface for other challenging reactions.

Key words: CO₂ hydrogenation, Methanol, Cu-ZrO₂ interface, Atomic layer deposition, Oxygen vacancies

Jie Zhao, Guangyuan Xu, Si Chen, Huan Yan. Precise tailoring of Cu-ZrO₂ interfaces for CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2027, 92: 316-327.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65168-6

https://www.cjcatal.com/EN/Y2027/V92/I1/316

Figures/Tables 7

Scheme 1. Schematic illustration of the catalyst preparation procedure

Fig. 1. (a) Catalytic performance of Cu/Al2O3@xZrO2-A catalysts with different ALD cycles in CO2 hydrogenation to methanol. (b) Comparison of the methanol STY over the Cu/Al2O3, Cu/Al2O3@ZrO2-L and Cu/Al2O3@2ZrO2-A catalysts at 220-300 °C. (c) Methanol selectivity as a function of CO2 conversion at different reaction temperatures over Cu/Al2O3, Cu/Al2O3@ZrO2-L and Cu/Al2O3@2ZrO2-A. (d) Comparison of the catalytic performance of the optimized Cu/Al2O3@2ZrO2-A catalyst with representative Cu-based catalysts reported in the literature under their optimum conditions. (e) Long-term stability of Cu/Al2O3 and Cu/Al2O3@2ZrO2-A. Standard reaction conditions: T = 240 °C, p = 5.0 MPa, CO2:H2 = 1:3, GHSV = 9000 mL g-1 h-1.

Fig. 2. HR-TEM images of Cu/Al2O3@2ZrO2-A (a), Cu/Al2O3@8ZrO2-A (b), and Cu/Al2O3@16ZrO2-A (c). (d) XRD patterns of the prepared catalysts. HAADF-STEM and EDS elemental mapping of Cu/Al2O3@2ZrO2-A (e) and Cu/Al2O3@ZrO2-L (f).

Fig. 3. CO2-TPD profiles (a) and EPR spectra (b) of Cu/Al2O3, Cu/Al2O3@ZrO2-L and Cu/Al2O3@2ZrO2-A after H2 reduction at 300 °C for 2 h. (c) EPR spectra of Cu/Al2O3@2ZrO2-A after H2 reduction followed by CO2 exposure. (d) O 1s XPS spectra of Cu/Al2O3, Cu/Al2O3@ZrO2-L and Cu/Al2O3@2ZrO2-A after H2 reduction at 300 °C for 2 h.

Fig. 4. H2-TPR profiles (a), Cu 2p (b), and Zr 3d (c) XPS spectra of Cu/Al2O3, Cu/Al2O3@ZrO2-L and Cu/Al2O3@2ZrO2-A. (d) In-situ CO-DRIFTS of reduced catalysts obtained upon CO adsorption at 25 °C and following Ar purge.

Fig. 5. In-situ DRIFTS analysis of the reaction pathway and surface intermediate evolution during CO2 hydrogenation. Time-dependent DRIFTS spectra collected over Cu/Al2O3@2ZrO2-A under reaction conditions (240 °C, 0.1 MPa, CO2:H2 = 1:3) for 45 min (a,b), Cu/Al2O3@ZrO2-L (c,d), and Cu/Al2O3 (e,f).

Fig. 6. In-situ DRIFTS spectra recorded after switching the feed gas from reaction mixture (CO2:H2 = 1:3) to 10% H2/Ar for 45 min over Cu/Al2O3@2ZrO2-A (a), Cu/Al2O3@ZrO2-L (b), and Cu/Al2O3 (c). (d) Temporal evolution of the formate band intensity (≈ 1590 cm-1). (e) Proposed reaction mechanism illustrating the synergistic role of oxygen-vacancy-rich ZrO2 and the interfacial electronic modulation at the Cu-ZrO2 interface

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Precise tailoring of Cu-ZrO₂ interfaces for CO₂ hydrogenation to methanol

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