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Following the structure of copper-zinc-alumina across the pressure gap in carbon dioxide hydrogenation

Abstract

Copper-zinc-alumina catalysts are used industrially for methanol synthesis from feedstock containing carbon monoxide and carbon dioxide. The high performance of the catalyst stems from synergies that develop between its components. This important catalytic system has been investigated with a myriad of approaches, however, no comprehensive agreement on the fundamental source of its high activity has been reached. One potential source of disagreement is the considerable variation in pressure used in studies to understand a process that is performed industrially at pressures above 20 bar. Here, by systematically studying the catalyst state during temperature-programmed reduction and under carbon dioxide hydrogenation with in situ and operando X-ray absorption spectroscopy over four orders of magnitude in pressure, we show how the state and evolution of the catalyst is defined by its environment. The structure of the catalyst shows a strong pressure dependence, especially below 1 bar. As pressure gaps are a general problem in catalysis, these observations have wide-ranging ramifications.

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Fig. 1: Pressure dependence as the source of differing opinions on CZA catalysts.
Fig. 2: Composition of the copper and zinc phases during reduction in hydrogen.
Fig. 3: Structure of the CZA catalyst as a function of hydrogen pressure.
Fig. 4: Reduction kinetics of the CZA catalyst.
Fig. 5: Structure under catalytic conditions.

Data availability

All data generated or analysed during this study are included in this published article (and its Supplementary Information files) or can be obtained from the authors on reasonable request.

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Acknowledgements

We thank H. Frey, D. Cartagenova, I. Sadykov and M. Ghosalya for support during the beamtime experiments; Z. Jovanovic for discussion on the kinetics; F. Krumeich for the provided electron microscopy. The authors also thank A. Clark for providing access to the ProXAS program for qXAS spectra calibration, normalization and SIMPLISIMA-LCF analysis. Part of this work was performed at the Swiss Light Source, Paul Scherrer Institute, Switzerland. We acknowledge the Swiss Light Source for providing synchrotron radiation beamtime at the SuperXAS beamline. A.B. and J.A.v.B. acknowledge the SNSF project 200021_178943. M.W. acknowledges funding from the SNSF project 200021_181053. M.A.N. acknowledges Shell Global Solutions for the part funding of his position.

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A.B. wrote the manuscript. A.B., M.Z. and O.S. conducted the experiments and performed the data analysis. M.A.N. contributed the EXAFS analysis. A.B., M.W. and J.A.v.B. designed the study. All authors participated in discussions and writing the manuscript.

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Correspondence to Marc G. Willinger or Jeroen A. van Bokhoven.

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Peer review information Nature Catalysis thanks Janis Timoshenko and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Notes 1–5, Figs. 1–22 and Tables 1–4.

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Beck, A., Zabilskiy, M., Newton, M.A. et al. Following the structure of copper-zinc-alumina across the pressure gap in carbon dioxide hydrogenation. Nat Catal 4, 488–497 (2021). https://doi.org/10.1038/s41929-021-00625-x

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