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Performance descriptors of nanostructured metal catalysts for acetylene hydrochlorination

Nature Nanotechnology volume 17, pages 606–612 (2022)Cite this article

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Abstract

Controlling the precise atomic architecture of supported metals is central to optimizing their catalytic performance, as recently exemplified for nanostructured platinum and ruthenium systems in acetylene hydrochlorination, a key process for vinyl chloride production. This opens the possibility of building on historically established activity correlations. In this study, we derived quantitative activity, selectivity and stability descriptors that account for the metal-dependent speciation and host effects observed in acetylene hydrochlorination. To achieve this, we generated a platform of Au, Pt, Ru, Ir, Rh and Pd single atoms and nanoparticles supported on different types of carbon and assessed their evolution during synthesis and under the relevant reaction conditions. Combining kinetic, transient and chemisorption analyses with modelling, we identified the acetylene adsorption energy as a speciation-sensitive activity descriptor, further determining catalyst selectivity with respect to coke formation. The stability of the different nanostructures is governed by the interplay between single atom–support interactions and chlorine affinity, promoting metal redispersion or agglomeration, respectively.

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Fig. 1: Synthesis and characterization of M/C catalysts.
Fig. 2: Speciation stability analysis via density functional theory.
Fig. 3: Speciation performance analysis of M/C catalysts in acetylene hydrochlorination.
Fig. 4: Kinetic analysis of M/C catalysts in acetylene hydrochlorination.
Fig. 5: Performance descriptor for M/C catalysts in acetylene hydrochlorination.
Fig. 6: Stability and deactivation of M/C catalysts in acetylene hydrochlorination.

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Data availability

The experimental and DFT data supporting the findings of this study are accessible at the ioChem-BD database at https://doi.org/10.19061/iochem-bd-1-222 and https://doi.org/10.19061/iochem-bd-1-204, respectively46. Source data are provided with this paper.

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Acknowledgements

This work was supported by ETH (research grant no. ETH-40 17-1) and the Swiss National Science Foundation (project no. 200021-169679). This publication was created as part of NCCR Catalysis (grant no. 180544), a National Centre of Competence in Research funded by the Swiss National Science Foundation. E.F. thanks MINECO La Caixa Severo Ochoa for a predoctoral grant through Severo Ochoa Excellence Accreditation 2014–2018 (SEV 2013 0319) and BSC-RES for providing generous computational resources. We thank R. Hauert and S. Büchele for conducting XPS and O.V. Safonova for performing XAS analyses. The Scientific Centre for Optical and Electron Microscopy (ScopeM) at ETH Zurich is acknowledged for the use of their facilities.

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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, Ivan Surin, Frank Krumeich & Javier Pérez-Ramírez

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

    Edvin Fako & Núria López

  3. Leibniz-Institut für Katalyse, Rostock, Germany

    Vita A. Kondratenko & Evgenii V. Kondratenko

  4. Paul Scherrer Institut, Villigen, Switzerland

    Adam H. Clark

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Contributions

J.P.-R. and N.L. conceived and coordinated all stages of this research. S.K.K. and I.S. synthesized the catalysts, contributed to their characterization and conducted the catalytic tests. F.K. and A.H.C. conducted electron microscopy and XAS analyses, respectively. E.V.K. and V.A.K performed temporal analysis of the products. E.F. and N.L. conducted the computational studies. All authors contributed to the writing of the manuscript.

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Correspondence to Núria López or Javier Pérez-Ramírez.

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Nature Nanotechnology thanks Jinlong Gong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Platform of carbon defects used to represent the NC and AC supports.

A variety of oxygen- (hydroxyl, epoxide, keto) and nitrogen- rich sites (pyrrolic, pyridinic, oxo-pyridinic) are considered to ensure high diversity in the available coordination motifs.

Extended Data Fig. 2 Comparison of formation energies of single-atom catalysts.

Formation energies of a, non-chlorinated single atoms and b, mono-chlorinated single atoms on AC and NC defects, referenced to the isolated gas-phase atom, the host containing the defect and 1/2Cl2.

Source data

Extended Data Fig. 3 Metal-only dependent variables as potential activity descriptors.

Physical properties of the examined metals including Pauling electronegativity (PE, conventionally labeled χ), Allred-Rochow electronegativity (ARE), first ionization potential (IE), cohesive energy (Ecoh), electron affinity (EA), melting point of the metallic phase (TM), adsorption of an isolated metal atom on pristine graphite (Eads), and the oxide decomposition temperature (Tox). The values are normalized so that the highest/lowest correspond to one/zero in the plots. The numerical set of values is provided in Supplementary Table 6.

Source data

Extended Data Fig. 4 Reaction profiles for acetylene hydrochlorination to vinyl chloride over most relevant catalysts.

Reaction profiles of a, Pt-supported single-atom species on AC and NC and the Pt(111) surface and b, AuCl single-atom species on the NC pyrrolic defect, the 4-fold coordinated Au-4 pyridinic defect, as well as the Au(111) surface.

Source data

Extended Data Fig. 5 Relationship between coking and pore blockage.

Linear correlation between the amount of coke deposits in the used catalysts, determined by TGA-MS (Supplementary Fig. 26) and the decrease in the total surface area (Supplementary Table 9), indicating that the former causes gradual pore blockage.

Source data

Supplementary information

Supplementary Information

Supplementary Discussions 1–7, Tables 1–11, Figs. 1–29 and references.

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Kaiser, S.K., Fako, E., Surin, I. et al. Performance descriptors of nanostructured metal catalysts for acetylene hydrochlorination. Nat. Nanotechnol. 17, 606–612 (2022). https://doi.org/10.1038/s41565-022-01105-4

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