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Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity

The prominent size effect of metal nanoparticles shapes decisively nanocatalysis, but entanglement of the corresponding geometric and electronic effects prevents exploiting their distinct functionalities. In this work, we demonstrate that in palladium (Pd)–catalyzed aerobic oxidation of benzyl alcoh...

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Autores principales: Wang, Hengwei, Gu, Xiang-Kui, Zheng, Xusheng, Pan, Haibin, Zhu, Junfa, Chen, Si, Cao, Lina, Li, Wei-Xue, Lu, Junling
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Association for the Advancement of Science 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6357750/
https://www.ncbi.nlm.nih.gov/pubmed/30746440
http://dx.doi.org/10.1126/sciadv.aat6413
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author Wang, Hengwei
Gu, Xiang-Kui
Zheng, Xusheng
Pan, Haibin
Zhu, Junfa
Chen, Si
Cao, Lina
Li, Wei-Xue
Lu, Junling
author_facet Wang, Hengwei
Gu, Xiang-Kui
Zheng, Xusheng
Pan, Haibin
Zhu, Junfa
Chen, Si
Cao, Lina
Li, Wei-Xue
Lu, Junling
author_sort Wang, Hengwei
collection PubMed
description The prominent size effect of metal nanoparticles shapes decisively nanocatalysis, but entanglement of the corresponding geometric and electronic effects prevents exploiting their distinct functionalities. In this work, we demonstrate that in palladium (Pd)–catalyzed aerobic oxidation of benzyl alcohol, the geometric and electronic effects interplay and compete so intensively that both activity and selectivity showed in volcano trends on the Pd particle size unprecedentedly. By developing a strategy of site-selective blocking via atomic layer deposition along with first principles calculations, we disentangle these two effects and unveil that the geometric effect dominates the right side of the volcano with larger-size Pd particles, whereas the electronic effect directs the left of the volcano with smaller-size Pd particles substantially. Selective blocking of the low-coordination sites prevents formation of the undesired by-product beyond the volcano relationship, achieving a remarkable benzaldehyde selectivity and activity at the same time for 4-nm Pd. Disentangling the geometric and electronic effects of metal nanoparticles opens a new dimension for rational design of catalysts.
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spelling pubmed-63577502019-02-11 Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity Wang, Hengwei Gu, Xiang-Kui Zheng, Xusheng Pan, Haibin Zhu, Junfa Chen, Si Cao, Lina Li, Wei-Xue Lu, Junling Sci Adv Research Articles The prominent size effect of metal nanoparticles shapes decisively nanocatalysis, but entanglement of the corresponding geometric and electronic effects prevents exploiting their distinct functionalities. In this work, we demonstrate that in palladium (Pd)–catalyzed aerobic oxidation of benzyl alcohol, the geometric and electronic effects interplay and compete so intensively that both activity and selectivity showed in volcano trends on the Pd particle size unprecedentedly. By developing a strategy of site-selective blocking via atomic layer deposition along with first principles calculations, we disentangle these two effects and unveil that the geometric effect dominates the right side of the volcano with larger-size Pd particles, whereas the electronic effect directs the left of the volcano with smaller-size Pd particles substantially. Selective blocking of the low-coordination sites prevents formation of the undesired by-product beyond the volcano relationship, achieving a remarkable benzaldehyde selectivity and activity at the same time for 4-nm Pd. Disentangling the geometric and electronic effects of metal nanoparticles opens a new dimension for rational design of catalysts. American Association for the Advancement of Science 2019-01-18 /pmc/articles/PMC6357750/ /pubmed/30746440 http://dx.doi.org/10.1126/sciadv.aat6413 Text en Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). http://creativecommons.org/licenses/by-nc/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (http://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.
spellingShingle Research Articles
Wang, Hengwei
Gu, Xiang-Kui
Zheng, Xusheng
Pan, Haibin
Zhu, Junfa
Chen, Si
Cao, Lina
Li, Wei-Xue
Lu, Junling
Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
title Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
title_full Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
title_fullStr Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
title_full_unstemmed Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
title_short Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
title_sort disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6357750/
https://www.ncbi.nlm.nih.gov/pubmed/30746440
http://dx.doi.org/10.1126/sciadv.aat6413
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