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Title: Alumina-supported sub-nanometer Pt10 clusters: Amorphization and role of the support material in a highly active CO oxidation catalyst

Abstract

Catalytic CO oxidation is unveiled on size-selected Pt10 clusters deposited on two very different ultrathin (≈0.5–0.7 nm thick) alumina films: (i) a highly ordered alumina obtained under ultra-high vacuum (UHV) by oxidation of the NiAl(110) surface and (ii) amorphous alumina obtained by atomic layer deposition (ALD) on a silicon chip that is a close model of real-world supports. Notably, when exposed to realistic reaction conditions, the Pt10/UHV-alumina system undergoes a morphological transition in both the clusters and the substrate, and becomes closely akin to Pt10/ALD-alumina, thus reconciling UHV-type surface-science and real-world experiments. The Pt10 clusters, thoroughly characterized via combined experimental techniques and theoretical analysis, exhibit among the highest CO oxidation activity per Pt atom reported for CO oxidation catalysts, due to the interplay of ultra-small size and support effects. Lastly, a coherent interdisciplinary picture then emerges for this catalytic system.

Authors:
 [1];  [2];  [2];  [3];  [2];  [1];  [4];  [4];  [1];  [5];  [3];  [6];  [6]; ORCiD logo [3]; ORCiD logo [7];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Consiglio Nazionale delle Ricerche, Pisa (Italy)
  3. Toyota Central R&D Labs. Inc., Nagakute (Japan)
  4. Univ. Rostock, Rostock (Germany)
  5. Toyota Motor Corp., Susono (Japan)
  6. Bhabha Atomic Research Centre, Mumbai (India)
  7. Consiglio Nazionale delle Ricerche, Pisa (Italy); California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1352556
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; CO oxidation; DFT calculations; HV and atmospheric pressure conditions; amorphous and crystalline alumina; subnanometer Pt clusters

Citation Formats

Yin, Chunrong, Negreiros, Fabio R., Barcaro, Giovanni, Beniya, Atsushi, Sementa, Luca, Tyo, Eric C., Bartling, Stephan, Meiwes-Broer, Karl-Heinz, Seifert, Sönke, Hirata, Hirohito, Isomura, Noritake, Nigam, Sandeep, Majumder, Chiranjib, Watanabe, Yoshihide, Fortunelli, Alessandro, and Vajda, Stefan. Alumina-supported sub-nanometer Pt10 clusters: Amorphization and role of the support material in a highly active CO oxidation catalyst. United States: N. p., 2017. Web. doi:10.1039/c6ta10989f.
Yin, Chunrong, Negreiros, Fabio R., Barcaro, Giovanni, Beniya, Atsushi, Sementa, Luca, Tyo, Eric C., Bartling, Stephan, Meiwes-Broer, Karl-Heinz, Seifert, Sönke, Hirata, Hirohito, Isomura, Noritake, Nigam, Sandeep, Majumder, Chiranjib, Watanabe, Yoshihide, Fortunelli, Alessandro, & Vajda, Stefan. Alumina-supported sub-nanometer Pt10 clusters: Amorphization and role of the support material in a highly active CO oxidation catalyst. United States. doi:10.1039/c6ta10989f.
Yin, Chunrong, Negreiros, Fabio R., Barcaro, Giovanni, Beniya, Atsushi, Sementa, Luca, Tyo, Eric C., Bartling, Stephan, Meiwes-Broer, Karl-Heinz, Seifert, Sönke, Hirata, Hirohito, Isomura, Noritake, Nigam, Sandeep, Majumder, Chiranjib, Watanabe, Yoshihide, Fortunelli, Alessandro, and Vajda, Stefan. Fri . "Alumina-supported sub-nanometer Pt10 clusters: Amorphization and role of the support material in a highly active CO oxidation catalyst". United States. doi:10.1039/c6ta10989f. https://www.osti.gov/servlets/purl/1352556.
@article{osti_1352556,
title = {Alumina-supported sub-nanometer Pt10 clusters: Amorphization and role of the support material in a highly active CO oxidation catalyst},
author = {Yin, Chunrong and Negreiros, Fabio R. and Barcaro, Giovanni and Beniya, Atsushi and Sementa, Luca and Tyo, Eric C. and Bartling, Stephan and Meiwes-Broer, Karl-Heinz and Seifert, Sönke and Hirata, Hirohito and Isomura, Noritake and Nigam, Sandeep and Majumder, Chiranjib and Watanabe, Yoshihide and Fortunelli, Alessandro and Vajda, Stefan},
abstractNote = {Catalytic CO oxidation is unveiled on size-selected Pt10 clusters deposited on two very different ultrathin (≈0.5–0.7 nm thick) alumina films: (i) a highly ordered alumina obtained under ultra-high vacuum (UHV) by oxidation of the NiAl(110) surface and (ii) amorphous alumina obtained by atomic layer deposition (ALD) on a silicon chip that is a close model of real-world supports. Notably, when exposed to realistic reaction conditions, the Pt10/UHV-alumina system undergoes a morphological transition in both the clusters and the substrate, and becomes closely akin to Pt10/ALD-alumina, thus reconciling UHV-type surface-science and real-world experiments. The Pt10 clusters, thoroughly characterized via combined experimental techniques and theoretical analysis, exhibit among the highest CO oxidation activity per Pt atom reported for CO oxidation catalysts, due to the interplay of ultra-small size and support effects. Lastly, a coherent interdisciplinary picture then emerges for this catalytic system.},
doi = {10.1039/c6ta10989f},
journal = {Journal of Materials Chemistry. A},
number = 10,
volume = 5,
place = {United States},
year = {2017},
month = {2}
}

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