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Tuning of catalytic sites in Pt/TiO2 catalysts for the chemoselective hydrogenation of 3-nitrostyrene

Nature Catalysis volume 2, pages 873–881 (2019)Cite this article

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An Author Correction to this article was published on 03 August 2020

An Author Correction to this article was published on 11 November 2019

This article has been updated

Abstract

The catalytic activities of supported metal nanoparticles can be tuned by appropriate design of synthesis strategies. Each step in a catalyst synthesis method can play an important role in preparing the most efficient catalyst. Here we report the careful manipulation of the post-synthetic heat treatment procedure—together with control over the metal loading—to prepare a highly efficient 0.2 wt% Pt/TiO2 catalyst for the chemoselective hydrogenation of 3-nitrostyrene. For Pt/TiO2 catalysts with 0.2 and 0.5 wt% loading levels, reduction at 450 °C induces the coverage of TiOx over Pt nanoparticles through a strong metal–support interaction, which is detrimental to their catalytic activities. However, this can be avoided by following calcination treatment with reduction (both at 450 °C), allowing us to prepare an exceptionally active catalyst. Detailed characterization has revealed that the peripheral sites at the Pt/TiO2 interface are the most likely active sites for this hydrogenation reaction.

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Fig. 1: The hydrogenation pathways of 3-NS.
Fig. 2: The effect of heat treatment on activity.
Fig. 3: Representative HAADF–STEM images and the derived particle size distributions of the unused Pt/TiO2 catalysts, binned according to the Mackay model.
Fig. 4: XPS data.
Fig. 5: XANES spectra.
Fig. 6: CO DRIFTS spectra.
Fig. 7: The correlation between peripheral Pt sites and catalytic activity.

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Data availability

Information on the data supporting the results presented here, including how to access them, can be found in the Cardiff University data catalogue at https://doi.org/10.17035/d.2019.0079744472.

Change history

  • 11 November 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

  • 03 August 2020

    A Correction to this paper has been published: https://doi.org/10.1038/s41929-020-00500-1

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Acknowledgements

M.M. and A.J.B. acknowledge MAXNET Energy consortium for funding. A.J.B. also acknowledges the EPRSC Centre for Doctoral Training in Catalysis (grant no. EP/L016443/1). M.S. and Q.H. thank Cardiff University for their respective University Research Fellowships and RQ acknowledges Chinese Scholarship Council (CSC) funding for his stay at Cardiff University. C.J.K. gratefully acknowledges funding from the National Science Foundation Major Research Instrumentation programme (grant no. MRI/DMR-1040229). S.M.A. thanks the Saudi Arabian government for his PhD scholarship. The authors thank the UK Catalysis Hub for allocating beamtime slots through the UK Catalysis Hub BAG allocation for X-ray acquisition of the absorption spectroscopic data at the Diamond synchrotron facility (sp15151). We are also indebted to P. Wells for acquisition of the X-ray absorption spectroscopic data at the Diamond synchrotron facility. We thank Y. Odarchenko for his assistance during CO chemisorption measurements. The authors thank the Diamond Light Source for access to the electron Physical Science Imaging Centre (ePSIC instrument E01 and proposal no. MG22776), which contributed to the results presented here.

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Authors and Affiliations

  1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, UK

    Margherita Macino, Alexandra J. Barnes, David J Morgan, Simon J. Freakley, Nikolaos Dimitratos, Christopher J. Kiely, Qian He, Meenakshisundaram Sankar & Graham J. Hutchings

  2. Department of Materials Science and Engineering, Lehigh University, Bethlehem, PA, USA

    Sultan M. Althahban & Christopher J. Kiely

  3. Department of Mechanical Engineering, Jazan University, Jazan, Saudi Arabia

    Sultan M. Althahban

  4. State Key Laboratory of Clean Energy Utilization, College of Energy Engineering, Zhejiang University, Hangzhou, China

    Ruiyang Qu & Xiang Gao

  5. Institute for Thermal Power Engineering, Zhejiang University, Hangzhou, China

    Ruiyang Qu & Xiang Gao

  6. School of Chemistry, University of Glasgow, Glasgow, UK

    Emma K. Gibson

  7. Department of Industrial Chemistry “Toso Montanari”, Alma Mater Studiorum–University of Bologna, Bologna, Italy

    Nikolaos Dimitratos

  8. UK Catalysis Hub, Research Complex at Harwell (RCaH), Rutherford Appleton Laboratory, Harwell Oxon, UK

    Andrew M. Beale

  9. Department of Chemistry, University College London, London, UK

    Andrew M. Beale

  10. Department of Chemistry, University of Liverpool, Liverpool, UK

    Donald Bethell

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Contributions

M.M., A.J.B. and R.Q. performed the catalyst preparation and catalyst testing under the supervision of M.S., N.D., S.F. and X.G. S.M.A., Q.H. and C.J.K. carried out electron microscopy studies of the catalyst. D.J.M. performed the XPS characterization of the catalysts. E.G. and A.M.B. analysed the X-ray absorption spcectroscopy data. D.B. suggested the kinetics experiments presented in this article. M.S. conceived this idea and supervised the project. G.J.H. directed this project. All authors contributed to the data analysis and drafting of this manuscript.

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Correspondence to Meenakshisundaram Sankar or Graham J. Hutchings.

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Macino, M., Barnes, A.J., Althahban, S.M. et al. Tuning of catalytic sites in Pt/TiO2 catalysts for the chemoselective hydrogenation of 3-nitrostyrene. Nat Catal 2, 873–881 (2019). https://doi.org/10.1038/s41929-019-0334-3

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