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Identification of active Zr–WOx clusters on a ZrO2 support for solid acid catalysts

Nature Chemistry volume 1, pages 722–728 (2009)Cite this article

Abstract

Tungstated zirconia is a robust solid acid catalyst for light alkane (C4–C8) isomerization. Several structural models for catalytically active sites have been proposed, but the topic remains controversial, partly because of the absence of direct structural imaging information on the various supported WOx species. High-angle annular dark-field imaging of WO3/ZrO2 catalysts in an aberration-corrected analytical electron microscope allows, for the first time, direct imaging of the various species present. Comparison of the relative distribution of these WOx species in materials showing low and high catalytic activities has allowed the deduction of the likely identity of the catalytic active site—namely, subnanometre Zr–WOx clusters. This information has subsequently been used in the design of new catalysts, in which the activity of a poor catalyst has been increased by two orders of magnitude using a synthesis procedure that deliberately increases the number density of catalytically relevant active species.

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Figure 1: Electron microscopy characterization of a low-activity WZrOH catalyst.
Figure 2: Electron microscopy characterization of a high-activity WZrOH catalyst.
Figure 4: Electron microscopy characterization of an inactive model WZrO2 catalyst.
Figure 5: STEM–HAADF imaging of post-impregnated catalysts.
Figure 3: STEM–XEDS analysis of a highly active WZrOH catalyst.

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Acknowledgements

This work was supported by the National Science Foundation's Nanoscale Interdisciplinary Research Team (NSF-NIRT) program under grant no. 0609018. Two of the authors (M.S.W. and W.V.K.) acknowledge additional support from SABIC Americas.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Lehigh University, 18015, Pennsylvania, Bethlehem, USA

    Wu Zhou & Christopher J. Kiely

  2. Department of Chemical Engineering, Operando Molecular Spectroscopy and Catalysis Laboratory, Lehigh University, Bethlehem, 18015, Pennsylvania, USA

    Elizabeth I. Ross-Medgaarden & Israel E. Wachs

  3. Department of Chemical and Biomolecular Engineering, Rice University, Houston, 77005, Texas, USA

    William V. Knowles & Michael S. Wong

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  1. Wu Zhou
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  2. Elizabeth I. Ross-Medgaarden
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  5. Israel E. Wachs
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  6. Christopher J. Kiely
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Contributions

W.Z. devised and carried out the electron microscopy experiments. E.I.R. carried out catalytic performance measurements and prepared the post-impregnation catalyst samples. W.V.K. and M.S.W. prepared some of the catalyst materials. C.J.K. and I.E.W. supervised the project. W.Z. and C.J.K. wrote the paper.

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Correspondence to Christopher J. Kiely.

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Zhou, W., Ross-Medgaarden, E., Knowles, W. et al. Identification of active Zr–WOx clusters on a ZrO2 support for solid acid catalysts. Nature Chem 1, 722–728 (2009). https://doi.org/10.1038/nchem.433

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