Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination
Abstract Carbon supports are ubiquitous components of heterogeneous catalysts for acetylene hydrochlorination to vinyl chloride, from commercial mercury-based systems to more sustainable metal single-atom alternatives. Their potential co-catalytic role has long been postulated but never unequivocall...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-09-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-41344-0 |
| _version_ | 1797558003520503808 |
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| author | Vera Giulimondi Andrea Ruiz-Ferrando Georgios Giannakakis Ivan Surin Mikhail Agrachev Gunnar Jeschke Frank Krumeich Núria López Adam H. Clark Javier Pérez-Ramírez |
| author_facet | Vera Giulimondi Andrea Ruiz-Ferrando Georgios Giannakakis Ivan Surin Mikhail Agrachev Gunnar Jeschke Frank Krumeich Núria López Adam H. Clark Javier Pérez-Ramírez |
| author_sort | Vera Giulimondi |
| collection | DOAJ |
| description | Abstract Carbon supports are ubiquitous components of heterogeneous catalysts for acetylene hydrochlorination to vinyl chloride, from commercial mercury-based systems to more sustainable metal single-atom alternatives. Their potential co-catalytic role has long been postulated but never unequivocally demonstrated. Herein, we evidence the bifunctionality of carbons and metal sites in the acetylene hydrochlorination catalytic cycle. Combining operando X-ray absorption spectroscopy with other spectroscopic and kinetic analyses, we monitor the structure of single metal atoms (Pt, Au, Ru) and carbon supports (activated, non-activated, and nitrogen-doped) from catalyst synthesis, using various procedures, to operation at different conditions. Metal atoms exclusively activate hydrogen chloride, while metal-neighboring sites in the support bind acetylene. Resolving the coordination environment of working metal atoms guides theoretical simulations in proposing potential binding sites for acetylene in the support and a viable reaction profile. Expanding from single-atom to ensemble catalysis, these results reinforce the importance of optimizing both metal and support components to leverage the distinct functions of each for advancing catalyst design. |
| first_indexed | 2024-03-10T17:24:17Z |
| format | Article |
| id | doaj.art-530afc5bd7dc42cbba589391f8ef9596 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-10T17:24:17Z |
| publishDate | 2023-09-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-530afc5bd7dc42cbba589391f8ef95962023-11-20T10:14:06ZengNature PortfolioNature Communications2041-17232023-09-0114111210.1038/s41467-023-41344-0Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorinationVera Giulimondi0Andrea Ruiz-Ferrando1Georgios Giannakakis2Ivan Surin3Mikhail Agrachev4Gunnar Jeschke5Frank Krumeich6Núria López7Adam H. Clark8Javier Pérez-Ramírez9Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH ZurichInstitute of Chemical Research of Catalonia (ICIQ-CERCA)Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH ZurichInstitute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH ZurichLaboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH ZurichLaboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH ZurichLaboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH ZurichInstitute of Chemical Research of Catalonia (ICIQ-CERCA)Paul Scherrer InstituteInstitute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH ZurichAbstract Carbon supports are ubiquitous components of heterogeneous catalysts for acetylene hydrochlorination to vinyl chloride, from commercial mercury-based systems to more sustainable metal single-atom alternatives. Their potential co-catalytic role has long been postulated but never unequivocally demonstrated. Herein, we evidence the bifunctionality of carbons and metal sites in the acetylene hydrochlorination catalytic cycle. Combining operando X-ray absorption spectroscopy with other spectroscopic and kinetic analyses, we monitor the structure of single metal atoms (Pt, Au, Ru) and carbon supports (activated, non-activated, and nitrogen-doped) from catalyst synthesis, using various procedures, to operation at different conditions. Metal atoms exclusively activate hydrogen chloride, while metal-neighboring sites in the support bind acetylene. Resolving the coordination environment of working metal atoms guides theoretical simulations in proposing potential binding sites for acetylene in the support and a viable reaction profile. Expanding from single-atom to ensemble catalysis, these results reinforce the importance of optimizing both metal and support components to leverage the distinct functions of each for advancing catalyst design.https://doi.org/10.1038/s41467-023-41344-0 |
| spellingShingle | Vera Giulimondi Andrea Ruiz-Ferrando Georgios Giannakakis Ivan Surin Mikhail Agrachev Gunnar Jeschke Frank Krumeich Núria López Adam H. Clark Javier Pérez-Ramírez Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination Nature Communications |
| title | Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination |
| title_full | Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination |
| title_fullStr | Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination |
| title_full_unstemmed | Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination |
| title_short | Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination |
| title_sort | evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination |
| url | https://doi.org/10.1038/s41467-023-41344-0 |
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