From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts
The hydroformylation of alkenes is a cornerstone transformation for the chemical industry, central for both functionalizing and extending the carbon backbone of an alkene. In this study, silica‐supported crystalline rhodium sulfide nanoparticles are explored as heterogeneous catalysts in hydroformyl...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2025-01-01
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| Series: | Small Structures |
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| Online Access: | https://doi.org/10.1002/sstr.202400260 |
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| author | Arjun Neyyathala Edvin Fako Sandip De Daria Gashnikova Florian Maurer Jan‐Dierk Grunwaldt Stephan A. Schunk Schirin Hanf |
| author_facet | Arjun Neyyathala Edvin Fako Sandip De Daria Gashnikova Florian Maurer Jan‐Dierk Grunwaldt Stephan A. Schunk Schirin Hanf |
| author_sort | Arjun Neyyathala |
| collection | DOAJ |
| description | The hydroformylation of alkenes is a cornerstone transformation for the chemical industry, central for both functionalizing and extending the carbon backbone of an alkene. In this study, silica‐supported crystalline rhodium sulfide nanoparticles are explored as heterogeneous catalysts in hydroformylation reactions, and it is found that RhxSy systems (x = 17, y = 15 or x = 2, y = 3 with 1 wt% Rh on SiO2) greatly outperform metallic Rh nanoparticles. These systems prove to be exceptionally competitive when benchmarked against other cutting‐edge catalysts in terms of activity, with Rh17S15/SiO2 being the superior catalyst candidate. By employing local environment descriptors, unsupervised machine learning and density functional theory, the structure‐performance relationships are examined. The results highlight that the presence of S in close proximity to the catalytic site unlocks the tunability of the surface catalytic properties. This allows for the substrate affinity to be modulated, in particular for Rh17S15, with adsorption energies rivalling those of pristine Rh and improved spatial resolution. |
| format | Article |
| id | doaj-art-4c8b94fd4313408b9935cda7a64d799f |
| institution | Kabale University |
| issn | 2688-4062 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Small Structures |
| spelling | doaj-art-4c8b94fd4313408b9935cda7a64d799f2025-01-10T17:54:14ZengWiley-VCHSmall Structures2688-40622025-01-0161n/an/a10.1002/sstr.202400260From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation CatalystsArjun Neyyathala0Edvin Fako1Sandip De2Daria Gashnikova3Florian Maurer4Jan‐Dierk Grunwaldt5Stephan A. Schunk6Schirin Hanf7Institute for Inorganic Chemistry Karlsruhe Institute of Technology Engesserstr. 15 76131 Karlsruhe GermanyBASF SE Carl‐Bosch Str. 38 67056 Ludwigshafen GermanyBASF SE Carl‐Bosch Str. 38 67056 Ludwigshafen GermanyInstitute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr. 18/20 76131 Karlsruhe GermanyInstitute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr. 18/20 76131 Karlsruhe GermanyInstitute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr. 18/20 76131 Karlsruhe GermanyBASF SE Carl‐Bosch Str. 38 67056 Ludwigshafen GermanyInstitute for Inorganic Chemistry Karlsruhe Institute of Technology Engesserstr. 15 76131 Karlsruhe GermanyThe hydroformylation of alkenes is a cornerstone transformation for the chemical industry, central for both functionalizing and extending the carbon backbone of an alkene. In this study, silica‐supported crystalline rhodium sulfide nanoparticles are explored as heterogeneous catalysts in hydroformylation reactions, and it is found that RhxSy systems (x = 17, y = 15 or x = 2, y = 3 with 1 wt% Rh on SiO2) greatly outperform metallic Rh nanoparticles. These systems prove to be exceptionally competitive when benchmarked against other cutting‐edge catalysts in terms of activity, with Rh17S15/SiO2 being the superior catalyst candidate. By employing local environment descriptors, unsupervised machine learning and density functional theory, the structure‐performance relationships are examined. The results highlight that the presence of S in close proximity to the catalytic site unlocks the tunability of the surface catalytic properties. This allows for the substrate affinity to be modulated, in particular for Rh17S15, with adsorption energies rivalling those of pristine Rh and improved spatial resolution.https://doi.org/10.1002/sstr.202400260heterogeneous catalysishydroformylationrhodium sulfidestructural motifssupported nanoparticles |
| spellingShingle | Arjun Neyyathala Edvin Fako Sandip De Daria Gashnikova Florian Maurer Jan‐Dierk Grunwaldt Stephan A. Schunk Schirin Hanf From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts Small Structures heterogeneous catalysis hydroformylation rhodium sulfide structural motifs supported nanoparticles |
| title | From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts |
| title_full | From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts |
| title_fullStr | From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts |
| title_full_unstemmed | From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts |
| title_short | From Poison to Promotor: Spatially Isolated Metal Sites in Supported Rhodium Sulfides as Hydroformylation Catalysts |
| title_sort | from poison to promotor spatially isolated metal sites in supported rhodium sulfides as hydroformylation catalysts |
| topic | heterogeneous catalysis hydroformylation rhodium sulfide structural motifs supported nanoparticles |
| url | https://doi.org/10.1002/sstr.202400260 |
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