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Title: Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion

Abstract

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 (TiO2 > SiO2 > Al2O3) on the overall reactivity pattern specified that hydrogen dissociation occurred at the oxide-metal interface, followed by highly efficient intraparticlemore » 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.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
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  1. Institute of Chemistry, The Hebrew University, Jerusalem 91904, Israel, The Center for Nanoscience and Nanotechnology, The Hebrew University, Jerusalem 91904, Israel
  2. Department of Chemistry, University of California, Berkeley, California 94720, United States
  3. Department of Chemistry, Bar Ilan University, Ramat Gan 5290002, Israel, Bar-Ilan Institute of Nanotechnology and Advanced Materials, Ramat Gan 5290002, Israel
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; European Research Council (ERC); Israeli Ministry of Energy; Azrieli foundation
OSTI Identifier:
1873589
Alternate Identifier(s):
OSTI ID: 1963426
Grant/Contract Number:  
AC02-05CH11231; 802769
Resource Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis Journal Volume: 11 Journal Issue: 15; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal−support interactions; IR nanospectroscopy; Au nanoparticles; metal oxide; hydrogenation; single-particle measurements

Citation Formats

Dery, Shahar, Mehlman, Hillel, Hale, Lillian, Carmiel-Kostan, Mazal, Yemini, Reut, Ben-Tzvi, Tzipora, Noked, Malachi, Toste, F. Dean, and Gross, Elad. Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion. United States: N. p., 2021. Web. doi:10.1021/acscatal.1c01987.
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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. United States. https://doi.org/10.1021/acscatal.1c01987
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Dery, Shahar, Mehlman, Hillel, Hale, Lillian, Carmiel-Kostan, Mazal, Yemini, Reut, Ben-Tzvi, Tzipora, Noked, Malachi, Toste, F. Dean, and Gross, Elad. Wed . "Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion". United States. https://doi.org/10.1021/acscatal.1c01987.
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@article{osti_1873589,
title = {Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion},
author = {Dery, Shahar and Mehlman, Hillel and Hale, Lillian and Carmiel-Kostan, Mazal and Yemini, Reut and Ben-Tzvi, Tzipora and Noked, Malachi and Toste, F. Dean and Gross, Elad},
abstractNote = {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 (TiO2 > SiO2 > Al2O3) 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.},
doi = {10.1021/acscatal.1c01987},
journal = {ACS Catalysis},
number = 15,
volume = 11,
place = {United States},
year = {Wed Jul 21 00:00:00 EDT 2021},
month = {Wed Jul 21 00:00:00 EDT 2021}
}
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