Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts
Abstract The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd8Au92 nanoparticles supported on silica using surface-sensitive techniques, we report that whe...
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| Language: | English |
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-61540-4 |
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| author | Kang Rui Garrick Lim Cameron J. Owen Selina K. Kaiser Prahlad K. Routh Montserrat Mendoza Kyoo-Chul K. Park Taek-Seung Kim Sadhya Garg Jules A. Gardener Lorenzo Russotto Christopher R. O’Connor Marianne Bijl Michael Aizenberg Christian Reece Jennifer D. Lee Anatoly I. Frenkel Boris Kozinsky Joanna Aizenberg |
| author_facet | Kang Rui Garrick Lim Cameron J. Owen Selina K. Kaiser Prahlad K. Routh Montserrat Mendoza Kyoo-Chul K. Park Taek-Seung Kim Sadhya Garg Jules A. Gardener Lorenzo Russotto Christopher R. O’Connor Marianne Bijl Michael Aizenberg Christian Reece Jennifer D. Lee Anatoly I. Frenkel Boris Kozinsky Joanna Aizenberg |
| author_sort | Kang Rui Garrick Lim |
| collection | DOAJ |
| description | Abstract The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd8Au92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H2–D2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation. |
| format | Article |
| id | doaj-art-531e4af293eb4a62a3ed29fbf85bcd7b |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-531e4af293eb4a62a3ed29fbf85bcd7b2025-08-20T04:03:03ZengNature PortfolioNature Communications2041-17232025-07-0116111210.1038/s41467-025-61540-4Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalystsKang Rui Garrick Lim0Cameron J. Owen1Selina K. Kaiser2Prahlad K. Routh3Montserrat Mendoza4Kyoo-Chul K. Park5Taek-Seung Kim6Sadhya Garg7Jules A. Gardener8Lorenzo Russotto9Christopher R. O’Connor10Marianne Bijl11Michael Aizenberg12Christian Reece13Jennifer D. Lee14Anatoly I. Frenkel15Boris Kozinsky16Joanna Aizenberg17Department of Chemistry and Chemical Biology, Harvard UniversityDepartment of Chemistry and Chemical Biology, Harvard UniversityDepartment of Chemistry and Chemical Biology, Harvard UniversityDepartment of Materials Science and Chemical Engineering, Stony Brook UniversityDepartment of Chemistry and Biochemistry, University of California, MercedDepartment of Mechanical Engineering, Northwestern UniversityRowland Institute at Harvard, Harvard UniversityJohn A. Paulson School of Engineering and Applied Sciences, Harvard UniversityCenter for Nanoscale Systems, Harvard UniversityJohn A. Paulson School of Engineering and Applied Sciences, Harvard UniversityRowland Institute at Harvard, Harvard UniversityJohn A. Paulson School of Engineering and Applied Sciences, Harvard UniversityJohn A. Paulson School of Engineering and Applied Sciences, Harvard UniversityRowland Institute at Harvard, Harvard UniversityDepartment of Chemistry and Chemical Biology, Harvard UniversityDepartment of Materials Science and Chemical Engineering, Stony Brook UniversityJohn A. Paulson School of Engineering and Applied Sciences, Harvard UniversityDepartment of Chemistry and Chemical Biology, Harvard UniversityAbstract The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd8Au92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H2–D2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation.https://doi.org/10.1038/s41467-025-61540-4 |
| spellingShingle | Kang Rui Garrick Lim Cameron J. Owen Selina K. Kaiser Prahlad K. Routh Montserrat Mendoza Kyoo-Chul K. Park Taek-Seung Kim Sadhya Garg Jules A. Gardener Lorenzo Russotto Christopher R. O’Connor Marianne Bijl Michael Aizenberg Christian Reece Jennifer D. Lee Anatoly I. Frenkel Boris Kozinsky Joanna Aizenberg Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts Nature Communications |
| title | Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts |
| title_full | Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts |
| title_fullStr | Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts |
| title_full_unstemmed | Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts |
| title_short | Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts |
| title_sort | nanoscale wetting controls reactive pd ensembles in synthesis of dilute pdau alloy catalysts |
| url | https://doi.org/10.1038/s41467-025-61540-4 |
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