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Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts

Nature Chemistry volume 9, pages 120–127 (2017)Cite this article

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Abstract

The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal–support interactions can be exploited to optimize metal active-site properties are lacking. Here we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCOx) on reducible oxide supports (TiO2 and Nb2O5) that induce oxygen-vacancy formation in the support and cause HCOx-functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO2-reduction selectivity.

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Figure 1: Control of CO2 reduction selectivity on Rh via catalyst pre-treatment.
Figure 2: Infrared analysis of selectivity switch.
Figure 3: Identifying the mechanism of A-SMSI formation.
Figure 4: Visualizing SMSI and A-SMSI states.
Figure 5: Relating SMSI and A-SMSI behaviour.
Figure 6: SMSI and A-SMSI overlayer structure and behaviour.

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Acknowledgements

P.C. acknowledges funding from the University of California, Riverside, and the National Science Foundation (NSF), Grant No. CHE-1301019. G.W.G. and X.P. acknowledge the NSF, Grants No. CBET-1159240 and No. DMR-0723032. XAS measurements were performed on Beamline 2-2, which was supported in part by the Synchrotron Catalysis Consortium, US Department of Energy Grant No. DE-SC0012335. A. V. Dudchenko is acknowledged for his efforts in Arduino automation of the packed-bed reactor experimental apparatus.

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Authors and Affiliations

  1. Department of Chemical and Environmental Engineering, University of California, Riverside, 92521, California, USA

    John C. Matsubu, Leo DeRita & Phillip Christopher

  2. Department of Chemical Engineering and Materials Science, University of California, Irvine, Irvine, 92697, California, USA

    Shuyi Zhang, George W. Graham & Xiaoqing Pan

  3. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, 48109, Michigan, USA

    Shuyi Zhang & George W. Graham

  4. Department of Chemical Engineering, Columbia University, 10027, New York, USA

    Nebojsa S. Marinkovic & Jingguang G. Chen

  5. Chemistry Department, Brookhaven National Laboratory, Upton, 11973, New York, USA

    Jingguang G. Chen

  6. Department of Physics and Astronomy, University of California, Irvine, Irvine, 92697, California, USA

    Xiaoqing Pan

  7. Program in Materials Science, University of California, Riverside, Riverside, 92521, California, USA

    Phillip Christopher

  8. UCR Center for Catalysis, University of California, Riverside, Riverside, 92521, California, USA

    Phillip Christopher

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Contributions

J.C.M. and P.C. developed the project, analysed the data and wrote the paper. J.C.M. performed all the catalyst synthesis, catalyst testing and DRIFTS analysis. L.D. assisted with FTIR data collection. S.Z. performed STEM experiments. G.W.G. and X.P. assisted with STEM data analysis. N.M. and J.G.C. performed and analysed the XAS experiments. P.C. oversaw the project.

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Correspondence to Phillip Christopher.

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Matsubu, J., Zhang, S., DeRita, L. et al. Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts. Nature Chem 9, 120–127 (2017). https://doi.org/10.1038/nchem.2607

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