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Chemical gradients in automotive Cu-SSZ-13 catalysts for NOx removal revealed by operando X-ray spectrotomography

Nature Catalysis volume 4, pages 46–53 (2021)Cite this article

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Abstract

Nitrogen oxide (NOx) emissions are a major source of pollution, demanding ever-improving performance from catalytic after-treatment systems. However, catalyst development is often hindered by limited understanding of the catalyst at work, exacerbated by widespread use of model catalysts rather than technical catalysts, and by global rather than spatially resolved characterization tools. Here we combine operando X-ray absorption spectroscopy with microtomography to perform three-dimensional chemical imaging of the chemical state of copper species in a Cu-SSZ-13 washcoated monolith catalyst during NOx reduction. Gradients in copper oxidation state and coordination environment, resulting from an interplay of NOx reduction with adsorption–desorption of NH3 and mass transport phenomena, were revealed at micrometre spatial resolution while simultaneously determining catalytic performance. Crucially, direct three-dimensional visualization of complex reactions on non-model catalysts is feasible only by the use of operando X-ray spectrotomography, which can improve our understanding of structure–activity relationships, including the observation of mass and heat transport effects.

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Fig. 1: Operando spectrotomography of a Cu-SSZ-13 catalyst at work.
Fig. 2: 3D view of the chemical gradient in a Cu-SSZ-13 washcoat.
Fig. 3: Revealing the chemical state of Cu in a Cu-SSZ-13 washcoat.

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Data availability

Raw data were generated at the Swiss Light Source of the Paul Scherrer Institut (Switzerland). The collected and cleaned imaging data acquired before tomographic reconstruction that support the findings of this study are stored in KITopen, the central repository of the Karlsruhe Institute of Technology, and are freely available with the following DOIs: 200 °C dataset, https://doi.org/10.5445/IR/1000122874; 300 °C dataset, https://doi.org/10.5445/IR/1000122890; 350 °C dataset, https://doi.org/10.5445/IR/1000122892; 400 °C dataset, https://doi.org/10.5445/IR/1000122893; NH3 reference dataset, https://doi.org/10.5445/IR/1000122894; NO reference dataset, https://doi.org/10.5445/IR/1000122895. Additional data, including reconstructed and treated spectrotomography datasets, are available from the authors upon reasonable request. Source Data for Figs. 1–3 are provided with the paper.

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Acknowledgements

This work was supported by the German Federal Ministry of Education and Research (BMBF) projects MicTomoCat (no. 05K16VK1) and COSMIC (no. 05K19VK4), and the German Research Foundation project (no. GR 3987/5-1). Spectrotomography experiments were performed at beamline microXAS of the Swiss Light Source. We acknowledge the Paul Scherrer Institut, Villigen, Switzerland for provision of synchrotron radiation beamtime at beamline microXAS, and thank M. Birri, B. Meyer and D. Grolimund for technical assistance and scientific discussions. Additional energy-dispersive spectrotomography experiments were performed on beamline ID24 at the European Synchrotron Radiation Facility, Grenoble, France. We thank F. Perrin and S. Pasternak for technical assistance. Furthermore we thank T. Bergfeldt (IAM-AWP, Karlsruhe Institute of Technology) for elemental analysis of the ion-exchanged zeolite; we thank M. Casapu from the Karlsruhe Institute of Technology for discussions on NH3-SCR, P. Lott for assistance during beamtime and D. Yuda for assistance with design of the reaction set-up. D.Z. additionally thanks the Deutsche Bundesstiftung Umwelt for the scholarship provided. T.L.S. thanks the BMBF and project COSMIC for funding.

Author information

Author notes

  1. Debora Motta Meira

    Present address: Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA

  2. Debora Motta Meira

    Present address: Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada

  3. Sakura Pascarelli

    Present address: European XFEL GmbH, Schenefeld, Germany

Authors and Affiliations

  1. Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany

    Johannes Becher, Dmitry E. Doronkin, Deniz Zengel, Jan-Dierk Grunwaldt & Thomas L. Sheppard

  2. Paul Scherrer Institut, Villigen, Switzerland

    Dario Ferreira Sanchez

  3. Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen, Germany

    Dmitry E. Doronkin, Jan-Dierk Grunwaldt & Thomas L. Sheppard

  4. European Synchrotron Radiation Facility, Grenoble, France

    Debora Motta Meira & Sakura Pascarelli

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Contributions

T.L.S., D.M.M., D.E.D. and J.-D.G. conceived and designed the experiments. J.B. and T.L.S. designed the spectrotomography set-up. J.B. and D.Z. synthesized the materials. J.B., D.F.S., D.E.D., D.M.M., S.P., J.-D.G. and T.L.S. contributed to preparation of beamtime proposals for access to synchrotron radiation. J.B., D.F.S., D.E.D., D.Z., D.M.M., S.P. and T.L.S. performed the experiments and acquired the data. D.F.S. and J.B. prepared code for processing of the raw data. J.B., D.F.S., D.E.D. and T.L.S performed analysis of the processed data and, with J.-D.G., interpreted the data. J.B., T.L.S. and D.E.D. drafted the manuscript, and all authors contributed to revision of the manuscript. J.-D.G. and T.L.S. were responsible for acquisition of funding.

Corresponding authors

Correspondence to Jan-Dierk Grunwaldt or Thomas L. Sheppard.

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The authors declare no competing interests.

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Peer review information Nature Catalysis thanks Jianjun Chen 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, Discussion, Note 1, References, Figs. 1–18 and Tables 1–3.

Source data

Source Data Fig. 1

Percentage NO conversion versus time and temperature during ammonia SCR.

Source Data Fig. 2

Example of Cu K XANES data derived from operando spectrotomography.

Source Data Fig. 3

Cu XANES data from operando spectrotomography under SCR conditions from 200 to 400 °C and related linear combination fitting of XANES.

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Becher, J., Sanchez, D.F., Doronkin, D.E. et al. Chemical gradients in automotive Cu-SSZ-13 catalysts for NOx removal revealed by operando X-ray spectrotomography. Nat Catal 4, 46–53 (2021). https://doi.org/10.1038/s41929-020-00552-3

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