Cargando…
Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion
[Image: see text] Metal–support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized reactivity was mainly detected with small (1–5 nm) oxide-supported Au nanoparticles and correlated to highly reactive sites at the oxide–metal...
Autores principales: | , , , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2021
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9223368/ https://www.ncbi.nlm.nih.gov/pubmed/35756326 http://dx.doi.org/10.1021/acscatal.1c01987 |
_version_ | 1784733109480062976 |
---|---|
author | Dery, Shahar Mehlman, Hillel Hale, Lillian Carmiel-Kostan, Mazal Yemini, Reut Ben-Tzvi, Tzipora Noked, Malachi Toste, F. Dean Gross, Elad |
author_facet | Dery, Shahar Mehlman, Hillel Hale, Lillian Carmiel-Kostan, Mazal Yemini, Reut Ben-Tzvi, Tzipora Noked, Malachi Toste, F. Dean Gross, Elad |
author_sort | Dery, Shahar |
collection | PubMed |
description | [Image: see text] Metal–support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized reactivity was mainly detected with small (1–5 nm) oxide-supported Au nanoparticles and correlated to highly reactive sites at the oxide–metal interface. However, catalytically active sites are not necessarily restricted to the interface but reside as well on the Au surface. Uncovering the interconnection between reactive sites located at the interface and those situated at the metal surface is of crucial importance for understanding the reaction mechanism on Au nanoparticles. Herein, high-spatial-resolution IR nanospectroscopy measurements were conducted to map the localized reactivity in hydrogenation reactions on oxide-supported Au particles while using nitro-functionalized ligands as probes molecules. Comparative analysis of the reactivity pattern on single particles supported on various oxides revealed that oxide-dependent reactivity enhancement was not limited to the oxide–metal interface but was detected throughout the Au particle, leading to site-independent reactivity. These results indicate that reactive Au sites on both the oxide–metal interface and metal surface can activate the nitro groups toward hydrogenation reactions. The observed influence of oxide support (TiO(2) > SiO(2) > Al(2)O(3)) on the overall reactivity pattern specified that hydrogen dissociation occurred at the oxide–metal interface, followed by highly efficient intraparticle hydrogen atom diffusion to the interior parts of the Au particle. In contrast to Au particles, the oxide–metal interface had only a minor impact on the reactivity of supported Pt particles in which hydrogen dissociation and nitro group reduction were effectively activated on Pt sites. Single-particle measurements provided insights into the relative reactivity pattern of oxide-supported Au particles, revealing that the less-reactive Au metal sites can activate hydrogenation reactions in the presence of hydrogen atoms that diffuse from the Au/oxide boundary. |
format | Online Article Text |
id | pubmed-9223368 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-92233682022-06-24 Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion Dery, Shahar Mehlman, Hillel Hale, Lillian Carmiel-Kostan, Mazal Yemini, Reut Ben-Tzvi, Tzipora Noked, Malachi Toste, F. Dean Gross, Elad ACS Catal [Image: see text] Metal–support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized reactivity was mainly detected with small (1–5 nm) oxide-supported Au nanoparticles and correlated to highly reactive sites at the oxide–metal interface. However, catalytically active sites are not necessarily restricted to the interface but reside as well on the Au surface. Uncovering the interconnection between reactive sites located at the interface and those situated at the metal surface is of crucial importance for understanding the reaction mechanism on Au nanoparticles. Herein, high-spatial-resolution IR nanospectroscopy measurements were conducted to map the localized reactivity in hydrogenation reactions on oxide-supported Au particles while using nitro-functionalized ligands as probes molecules. Comparative analysis of the reactivity pattern on single particles supported on various oxides revealed that oxide-dependent reactivity enhancement was not limited to the oxide–metal interface but was detected throughout the Au particle, leading to site-independent reactivity. These results indicate that reactive Au sites on both the oxide–metal interface and metal surface can activate the nitro groups toward hydrogenation reactions. The observed influence of oxide support (TiO(2) > SiO(2) > Al(2)O(3)) on the overall reactivity pattern specified that hydrogen dissociation occurred at the oxide–metal interface, followed by highly efficient intraparticle hydrogen atom diffusion to the interior parts of the Au particle. In contrast to Au particles, the oxide–metal interface had only a minor impact on the reactivity of supported Pt particles in which hydrogen dissociation and nitro group reduction were effectively activated on Pt sites. Single-particle measurements provided insights into the relative reactivity pattern of oxide-supported Au particles, revealing that the less-reactive Au metal sites can activate hydrogenation reactions in the presence of hydrogen atoms that diffuse from the Au/oxide boundary. American Chemical Society 2021-07-21 2021-08-06 /pmc/articles/PMC9223368/ /pubmed/35756326 http://dx.doi.org/10.1021/acscatal.1c01987 Text en © 2021 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Dery, Shahar Mehlman, Hillel Hale, Lillian Carmiel-Kostan, Mazal Yemini, Reut Ben-Tzvi, Tzipora Noked, Malachi Toste, F. Dean Gross, Elad Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion |
title | Site-Independent Hydrogenation Reactions on Oxide-Supported
Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion |
title_full | Site-Independent Hydrogenation Reactions on Oxide-Supported
Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion |
title_fullStr | Site-Independent Hydrogenation Reactions on Oxide-Supported
Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion |
title_full_unstemmed | Site-Independent Hydrogenation Reactions on Oxide-Supported
Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion |
title_short | Site-Independent Hydrogenation Reactions on Oxide-Supported
Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion |
title_sort | site-independent hydrogenation reactions on oxide-supported
au nanoparticles facilitated by intraparticle hydrogen atom diffusion |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9223368/ https://www.ncbi.nlm.nih.gov/pubmed/35756326 http://dx.doi.org/10.1021/acscatal.1c01987 |
work_keys_str_mv | AT deryshahar siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT mehlmanhillel siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT halelillian siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT carmielkostanmazal siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT yeminireut siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT bentzvitzipora siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT nokedmalachi siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT tostefdean siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion AT grosselad siteindependenthydrogenationreactionsonoxidesupportedaunanoparticlesfacilitatedbyintraparticlehydrogenatomdiffusion |