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The role of Cu1–O3 species in single-atom Cu/ZrO2 catalyst for CO2 hydrogenation

Abstract

Copper-based catalysts for the hydrogenation of CO2 to methanol have attracted much interest. The complex nature of these catalysts, however, renders the elucidation of their structure–activity properties difficult. Here we report a copper-based catalyst with isolated active copper sites for the hydrogenation of CO2 to methanol. It is revealed that the single-atom Cu–Zr catalyst with Cu1–O3 units contributes solely to methanol synthesis around 180 °C, while the presence of small copper clusters or nanoparticles with Cu–Cu structural patterns are responsible for forming the CO by-product. Furthermore, the gradual migration of Cu1–O3 units with a quasiplanar structure to the catalyst surface is observed during the catalytic process and accelerates CO2 hydrogenation. The highly active, isolated copper sites and the distinguishable structural pattern identified here extend the horizon of single-atom catalysts for applications in thermal catalytic CO2 hydrogenation and could guide the further design of high-performance copper-based catalysts to meet industrial demand.

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Fig. 1: Characterization of different Cu/ZrO2 catalysts.
Fig. 2: Catalytic performance of different copper-based catalysts.
Fig. 3: Electronic property and structure of CAZ-1.
Fig. 4: Morphology and crystal structure of different Cu/a-ZrO2 catalysts.
Fig. 5: Migration of Cuδ+ species to the surface.
Fig. 6: Characterization and evolution of reactive intermediates.
Fig. 7: Mechanism analysis of CO2 hydrogenation to CH3OH/CO on isolated Cuδ+ (1 < δ < 2) cation.
Fig. 8: Schematic diagram for CO2 hydrogenation reaction on different types of copper species.

Data availability

Data presented in the main figures of the manuscript and Supplementary Information are publicly available through the Zenodo repository (https://zenodo.org/deposit/6874758); all other relevant raw data are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

Code availability

The software code of LASP and NN potential used within the article is available from the corresponding author upon request or on the website http://www.lasphub.com.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China under grant numbers 22172032, 21902027, 51701201 and U19B2003, the National Key Research and Development Program of China under grant number 2018YFA0208600, the Natural Science Foundation of Fujian Province under grant numbers 2020J05121 and 2020J01443, and the DNL Cooperation Fund, CAS (DNL201903). The X-ray experiment was supported by BL14W1, Shanghai Synchrotron Radiation Facility (j21sr0041). We thank the staff at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facility and M. Shakouri at the Canadian Light Source for assistance with the EXAFS and XANES measurements.

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Authors and Affiliations

Authors

Contributions

L.T. conceived and designed the experiments. H.Z. performed the catalyst synthesis, characterization and performance experiments. Z.L. and S.M. contributed to the DFT calculation and wrote the related section of the manuscript. R.Y., K.X., Y.C., K.J., Y.F., C.Z. and X.L. assisted with the synthesis and performance testing of the catalysts. Y.T. and L.W. helped to analyse the XPS and XAS data. Q.J. conducted the HAADF-STEM experiments. P.H. and Y.W. assisted with the in situ DRIFT experiments. Data were discussed among all coauthors. L.T. and H.Z. wrote the manuscript.

Corresponding authors

Correspondence to Zhipan Liu or Li Tan.

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Peer review information

Nature Catalysis thanks Xiaodong Wen, Shohei Tada and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–33 and Tables 1–9.

Supplementary Data 1

All the relevant structure of CAZ-1.

Supplementary Data 2

Gibbs free energy profile of CO2 hydrogenation to CH3OH/CO for CAZ-1 catalyst.

Supplementary Data 3

The variations of reaction intermediates concentrations during microkinetics simulation on CAZ-1 catalyst.

Supplementary Data 4

The variations of reaction rate during microkinetics simulation on CAZ-1 catalyst.

Supplementary Data 5

Source data of Supplementary Information.

Source data

Source Data Fig. 1

HAADF-STEM and TEM images, k2-weighted Fourier transform spectra and wavelet transform spectroscopy.

Source Data Fig. 2

Activity

Source Data Fig. 3

Cu K-edge XANES spectra, first derivative of the XANES spectra and fitting results of k2-weighted EXAFS data.

Source Data Fig. 4

HAADF-STEM images and in situ XRD.

Source Data Fig. 5

TOF-SIMS images and semiquantitative analysis.

Source Data Fig. 6

In situ DRIFT.

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Zhao, H., Yu, R., Ma, S. et al. The role of Cu1–O3 species in single-atom Cu/ZrO2 catalyst for CO2 hydrogenation. Nat Catal 5, 818–831 (2022). https://doi.org/10.1038/s41929-022-00840-0

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