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Platinum incorporation into titanate perovskites to deliver emergent active and stable platinum nanoparticles

Nature Chemistry volume 13, pages 677–682 (2021)Cite this article

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Abstract

Platinum functions exceptionally well as a nanoparticulate catalyst in many important fields, such as in the removal of atmospheric pollutants, but it is scarce, expensive and not always sufficiently durable. Here, we report a perovskite system in which 0.5 wt% Pt is integrated into the support and its subsequent conversion through exsolution to achieve a resilient catalyst. Owing to the instability of most Pt oxides at high temperatures, a thermally stable platinum oxide precursor, barium platinate, was used to preserve the platinum as an oxide during the solid-state synthesis in an approach akin to the Trojan horse legend. By tailoring the procedure, it is possible to produce a uniform equilibrated structure with active emergent Pt nanoparticles strongly embedded in the perovskite surface that display better CO oxidation activity and stability than those of conventionally prepared Pt catalysts. This catalyst was further evaluated for a variety of reactions under realistic test environments—CO and NO oxidation, diesel oxidation catalysis and ammonia slip reactions were investigated.

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Fig. 1: Explanation of the Trojan horse concept and characterization of the Pt-doped perovskite materials, which confirms Pt incorporation into the perovskite lattice.
Fig. 2: Electron microscopy characterization of emergent Pt NPs from the tailored perovskite materials based on Pt@LCT.
Fig. 3: X-ray absorption spectroscopic characterization of emergent Pt NPs from different treatments of Pt@LCT and comparison with relevant standards.
Fig. 4: Investigation of the catalytic functionality for CO oxidation at the perovskite catalysts with emergent Pt NPs and a comparison with relevant standards.
Fig. 5: Investigation of catalyst performance when measured under simulated car exhaust environments.

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Data availability

All underlying data is available on the St Andrews PURE website at https://doi.org/10.17630/3f58e258-5b0d-4e12-9742-e89bb844b062.

References

  1. Farrauto, R. J. Low-temperature oxidation of methane. Science 337, 659–660 (2012).

    Article  CAS  Google Scholar 

  2. Zhang, Z. et al. Thermally single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation. Nat. Comm. 8, 16100 (2017).

    Article  CAS  Google Scholar 

  3. Jones, J. et al. Thermally single-atom platinum-on-ceria catalysts via atom trapping. Science 353, 150–154 (2016).

    Article  CAS  Google Scholar 

  4. Nie, L. et al. Activation of surface lattice oxygen in single-atom Pt/CeO2 for low-temperature CO oxidation. Science 358, 1419–1423 (2017).

    Article  CAS  Google Scholar 

  5. Winkler, S. L. et al. Vehicle criteria pollutant (PM, NOx, CO, HCs) emissions: how low should we go? npj Clim. Atmos. Sci. 1, 26 (2018).

    Article  Google Scholar 

  6. Hwang, J. et al. Perovskites in catalysis and electrocatalysis. Science 358, 751–756 (2017).

    Article  CAS  Google Scholar 

  7. Kim, C. H., Qi, G., Dahlberg, K. & Li, W. Strontium-doped perovskites rival. Science 327, 1624–1627 (2010).

    Article  CAS  Google Scholar 

  8. Tanaka, H., Taniguchi, M., Uenishi, M., Kajita, N. & Tan, I. Self‐regenerating Rh‐ and Pt‐based perovskite catalysts for automotive‐emissions control. Angew. Chem. 45, 5998–6002 (2006).

    Article  CAS  Google Scholar 

  9. Jarrige, I. et al. Toward optimizing the performance of self-regenerating Pt-based perovskite catalysts. ACS Catal. 5, 1112–1118 (2015).

    Article  CAS  Google Scholar 

  10. Nishihata, Y. et al. Self-regeneration of a Pd-perovskite catalyst for automotive emissions control. Nature 418, 164–167 (2002).

    Article  CAS  Google Scholar 

  11. Zhang, S. et al. New atomic-scale insight into self-regeneration of Pt-CaTiO3 catalysts: incipient redox-induced structures revealed by a small-angle tilting STEM technique. J. Phys. Chem. C 121, 17348–17353 (2017).

    Article  CAS  Google Scholar 

  12. Malamis, S. A. et al. Comparison of precious metal doped and impregnated perovskite oxides for TWC application. Catal. Today 258, 535–542 (2015).

    Article  CAS  Google Scholar 

  13. Katz, M. B. et al. Self-regeneration of Pd-LaFeO3 catalysts: new insight from atomic-resolution electron microscopy. J. Am. Chem. Soc. 133, 18090–18093 (2011).

    Article  CAS  Google Scholar 

  14. Neagu, D., Tsekouras, G., Miller, D. N., Ménard, H. & Irvine, J. T. S. In situ growth of nanoparticles through control of non-stoichiometry. Nat. Chem. 5, 916–923 (2013).

    Article  CAS  Google Scholar 

  15. Neagu, D. et al. Demonstration of chemistry at a point through restructuring and catalytic activation at anchored nanoparticles. Nat. Commun. 8, 1855 (2017).

    Article  Google Scholar 

  16. Neagu, D. et al. Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution. Nat. Commun. 6, 8120 (2015).

    Article  Google Scholar 

  17. Gao, Y., Wang, J., Lyu, Y.-Q., Lam, K. & Ciucci, F. In situ growth of Pt3Ni nanoparticles on an A-site deficient perovskite with enhanced activity for the oxygen reduction reaction. J. Mater. Chem. A 5, 6399–6404 (2017).

    Article  CAS  Google Scholar 

  18. Nur, A. S. M. et al. Phase-dependent formation of coherent interface structure between PtO2 and TiO2 and its impact on thermal decomposition behavior. J. Phys. Chem. C 122, 662–669 (2018).

    Article  CAS  Google Scholar 

  19. Haradem, P. S., Chamberland, B. L., Katz, L. & Gleizes, A. A structural model for barium platinum oxide, Ba3Pt2O7. J. Solid State Chem. 21, 217–223 (1977).

    Article  CAS  Google Scholar 

  20. Sakthivel, C., Keerthana, L. & Prabha, I. Current status of platinum based nanoparticles: physicochemical properties and selected applications—a review. Johnson Matthey Technol. Rev. 63, 122–133 (2019).

    Article  CAS  Google Scholar 

  21. Myung, J.-H., Neagu, D., Miller, D. N. & Irvine, J. T. S. Switching on electrocatalytic activity in solid oxide cells. Nature 537, 528–531 (2016).

    Article  CAS  Google Scholar 

  22. Jeon, Y. et al. Hollow fibers networked with perovskite nanoparticles for H2 production from heavy oil. Sci. Rep. 3, 2902 (2013).

    Article  Google Scholar 

  23. ACE Tech Team. Aftertreatment Protocols for Catalyst Characterization and Performance Evaluation: Low-Temperature Oxidation Catalyst Test Protocol (USDRIVE, 2015); https://cleers.org/wp-content/uploads/2015_LTAT-Oxidation-Catalyst-Characterization-Protocol.pdf

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Acknowledgements

We acknowledge useful discussions with M. Fowles and J. Fisher from Johnson Matthey. We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. Funding was from Johnson Matthey, EPSRC for a CASE PhD studentship, EPSRC for a Critical Mass project EP/R023522/1 and electron microscopy provision EP/R023751/1 and EP/L017008/1. We dedicate this work to our esteemed co-author and colleague David Wails who tragically died in the attacks in Reading, UK, on 20 June 2020. David was a talented scientist who had dedicated his career to advancing sustainable catalysis and mentoring early career researchers.

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Author notes

  1. These authors contributed equally: Maadhav Kothari, Yukwon Jeon.

Authors and Affiliations

  1. School of Chemistry, University of St Andrews, St Andrews, UK

    Maadhav Kothari, Yukwon Jeon, David N. Miller & John T. S. Irvine

  2. Department of Environmental and Energy Engineering, Yonsei University, Wonju, Korea

    Yukwon Jeon

  3. Johnson Matthey Technology Centre, Sonning Common, Reading, UK

    Andrea Eva Pascui, John Kilmartin & David Wails

  4. School of Physical Sciences, University of Kent, Canterbury, UK

    Silvia Ramos & Alan Chadwick

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  1. Maadhav Kothari
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Contributions

M.K. and Y.J. designed and carried out the experiments, and wrote the manuscript. D.N.M. collected the TEM and energy dispersive X-ray data. S.R. and A.C. analysed the XANES/EXAFS results. A.E.P. and J.K. carried out the conventional catalyst tests at Johnson Matthey and D.W. and J.F. analysed the results. J.T.S.I. supervised the whole study and revised the manuscript. All the authors discussed the results and commented on the manuscript.

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Correspondence to John T. S. Irvine.

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The authors declare no competing interests.

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Peer review information Nature Chemistry thanks Abhaya Datye and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–11 and Tables 1–4.

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Kothari, M., Jeon, Y., Miller, D.N. et al. Platinum incorporation into titanate perovskites to deliver emergent active and stable platinum nanoparticles. Nat. Chem. 13, 677–682 (2021). https://doi.org/10.1038/s41557-021-00696-0

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