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Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production

Nature Catalysis volume 3, pages 376–385 (2020)Cite this article

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Abstract

The worldwide replacement of the toxic mercuric chloride catalyst in vinyl chloride manufacture via acetylene hydrochlorination is slowed by the limited durability of alternative catalytic systems at high space velocities. Here, we demonstrate that platinum single atoms on carbon carriers are substantially more stable (up to 1,073 K) than their gold counterparts (up to 473 K), enabling facile and scalable preparation and precise tuning of their coordination environment by simple temperature control. By combining kinetic analysis, advanced characterization, and density functional theory, we assess how the Pt species determines the catalytic performance and thereby identify Pt(ii)−Cl as the active site, being three times more active than Pt nanoparticles. We show that Pt single atoms exhibit outstanding stability in acetylene hydrochlorination and surpass the space–time yields of their gold-based analogues after 25 h time-on-stream, qualifying them as a candidate for sustainable vinyl chloride production.

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Fig. 1: Synthesis and characterization of carbon-supported Pt catalysts.
Fig. 2: Stability of Pt and Au single atoms on carbon carriers.
Fig. 3: Activity descriptors for Pt catalysts.
Fig. 4: Relationship between the stability of the single-atom species and their ability to adsorb and activate acetylene.
Fig. 5: Reaction pathway for acetylene hydrochlorination over distinct Pt sites.
Fig. 6: Catalyst stability and deactivation.
Fig. 7: Coke formation over the AC or NC carrier.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request. The DFT structures can be retrieved from the ioChem-BD database56.

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Acknowledgements

This work was supported by an ETH research grant (ETH-40 17-1) and the Swiss National Science Foundation (project no. 200021–169679). E.F. thanks MINECO La Caixa Severo Ochoa for a predoctoral grant through Severo Ochoa Excellence Accreditation 2014–2018 (SEV 2013 0319). We thank BSC-RES for providing generous computational resources. We thank the Scientific Centre for Optical and Electron Microscopy (ScopeM) at ETH Zurich for the use of their facilities and the Micromeritics Grant Program for the award of the 3Flex instrument.

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Author notes

  1. These authors contributed equally: Selina K. Kaiser, Edvin Fako.

Authors and Affiliations

  1. Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland

    Selina K. Kaiser, Gabriele Manzocchi, Frank Krumeich & Javier Pérez-Ramírez

  2. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona, Spain

    Edvin Fako & Núria López

  3. Empa, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland

    Roland Hauert

  4. Paul Scherrer Institut, Villigen, Switzerland

    Adam H. Clark & Olga V. Safonova

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Contributions

J.P.-R. conceived and coordinated all stages of this research. S.K.K. prepared and characterized the catalysts, and performed and analysed the steady-state tests with support from G.M.; E.F. and N.L. conducted the DFT calculations. F.K. performed the microscopic analysis. R.H. conducted the XPS analysis. O.V.S. and A.H.C. conducted the XAS analysis. The data were discussed among all the authors. S.K.K., E.F., N.L. and J.P.-R. wrote the paper with feedback from the other authors.

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Correspondence to Javier Pérez-Ramírez.

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Supplementary Tables 1–8, Figs. 1–20, discussion, references

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Kaiser, S.K., Fako, E., Manzocchi, G. et al. Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production. Nat Catal 3, 376–385 (2020). https://doi.org/10.1038/s41929-020-0431-3

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