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Epitaxial Stabilization of Face Selective Catalysts

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Abstract

Selective, active, and robust catalysts are necessary for the efficient utilization of new feedstocks. Face-selective catalysts can precisely modify catalytic properties, but are often unstable under reaction conditions, changing shape and losing selectivity. Herein we report a method for synthesizing stable heterogeneous catalysts in which the morphology and selectivity can be tuned precisely and predictably. Using nanocrystal supports, we epitaxially stabilize specific active phase morphologies. This changes the distribution of active sites of different coordination, which have correspondingly different catalytic properties. Specifically, we utilize the different interfacial free-energies between perovskite titanate nanocube supports with different crystal lattice dimensions and a platinum active phase. By substituting different sized cations into the support, we change the lattice mismatch between the support and the active phase, thereby changing the interfacial free-energy, and stabilizing the active phase in different morphologies in a predictable manner. We correlate these changes in active phase atomic coordination with changes in catalytic performance (activity and selectivity), using the hydrogenation of acrolein as a test reaction. The method is general and can be applied to many nanocrystal supports and active phase combinations.

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Notes

  1. For completeness, changing the lattice mismatch is not the only way to change the interfacial free-energy and therefore the degree of wetting. Changing the bonding interactions or the composition of the interface will also change the interfacial free-energy. For example, changing to a more oxophilic active phase metal would increase the bond strength and lower the interfacial free-energy. By maintaining the same active phase and substituting one chemically similar cation in the support we minimize such effects in order isolate the effect of the change in lattice mismatch. Preliminary catalytic results on a sample of Pt on commercial SrTiO3 (non-nanocrystal) showed a lower selectivity than either the SrTiO3 or Ba0.5Sr0.5TiO3 support. These should have the same bonding effects as nanocrystal SrTiO3, and support our hypothesis that the structural effect is paramount. However, at this time we cannot completely rule out the possibility that bonding effects make some contribution in addition to the structural effects.

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Acknowledgments

The authors thank Mihai Anitescu for assistance with the statistical analysis. This work was funded in part by Institute for Atom-efficient Chemical Transformations, an Energy Frontier Research Center, funded through the U.S. Department of Energy, Office of Basic Energy Sciences; and in part by the Northwestern University Institute for Catalysis in Energy Processing, funded through the US Department of Energy, Office of Basic Energy Science (award number DE-FG02-03-ER15457). The electron microscopy was accomplished at the Electron Microscopy Center for Materials Research at Argonne National Laboratory, a U.S. Department of Energy Office of Science Laboratory operated under Contract No. DE-AC02-06CH11357 by UChicago Argonne, LLC.

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Authors and Affiliations

  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    James A. Enterkin, Peter C. Stair, Christopher L. Marshall & Kenneth R. Poeppelmeier

  2. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Robert M. Kennedy, Peter C. Stair & Kenneth R. Poeppelmeier

  3. Energy Systems Division, Argonne National Laboratory, Lemont, IL, USA

    Junling Lu & Jeffrey W. Elam

  4. Electron Microscopy Center, Argonne National Laboratory, Lemont, IL, USA

    Russell E. Cook

  5. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Laurence D. Marks

Authors
  1. James A. Enterkin
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  2. Robert M. Kennedy
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  3. Junling Lu
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  4. Jeffrey W. Elam
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  5. Russell E. Cook
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  6. Laurence D. Marks
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  7. Peter C. Stair
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  8. Christopher L. Marshall
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  9. Kenneth R. Poeppelmeier
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Corresponding author

Correspondence to Christopher L. Marshall.

Additional information

James A. Enterkin and Robert M. Kennedy contributed equally to this work.

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Enterkin, J.A., Kennedy, R.M., Lu, J. et al. Epitaxial Stabilization of Face Selective Catalysts. Top Catal 56, 1829–1834 (2013). https://doi.org/10.1007/s11244-013-0118-y

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  • DOI: https://doi.org/10.1007/s11244-013-0118-y

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