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Title: Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis

Abstract

Scaling relationships in catalysis impose fundamental limitations on the catalyst maximal performance; therefore, there is a continuous hunt for ways of circumventing them. We show that, at the subnano-scale, scaling relationships can be broken through catalyst dynamics. Oxygen reduction reaction (ORR), which can be catalyzed by Pt nanoparticles, is used as our study case. Subnanometer gas-phase and graphene-deposited Pt n cluster catalysts are shown to exhibit poor correlation between binding energies of the intermediates, O, OH, and OOH, involved in the scaling relationships for ORR. The effect is due to the highly fluxional behavior of subnanometer clusters, which easily adapt their structures to the bound adsorbates and varying coverage and in some cases even reshape the structure upon changing environment. This fluxional behavior is also commonplace for clusters and contrasts them to extended surfaces, suggesting that breaking scaling relationships is likely a rule more than an exception in nanocluster catalysis.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry
  2. Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry; California NanoSystems Institute, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Los Angeles, CA (United States)
Sponsoring Org.:
US Air Force Office of Scientific Research (AFOSR); USDOD; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1492942
Alternate Identifier(s):
OSTI ID: 1594250; OSTI ID: 1755383
Grant/Contract Number:  
SC0019152; AFOSR FA9550-16-1-0141; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 10; Related Information: https://pubs.acs.org/doi/suppl/10.1021/acs.jpclett.8b03680/suppl_file/jz8b03680_si_001.pdf; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; catalysis; scaling relations; nanoclusters; fluxionality; ORR; Redox reactions; Platinum; Binding energy; Adsorption; Cluster chemistry

Citation Formats

Zandkarimi, Borna, and Alexandrova, Anastassia N. Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis. United States: N. p., 2019. Web. doi:10.1021/acs.jpclett.8b03680.
Zandkarimi, Borna, & Alexandrova, Anastassia N. Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis. United States. doi:https://doi.org/10.1021/acs.jpclett.8b03680
Zandkarimi, Borna, and Alexandrova, Anastassia N. Fri . "Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis". United States. doi:https://doi.org/10.1021/acs.jpclett.8b03680. https://www.osti.gov/servlets/purl/1492942.
@article{osti_1492942,
title = {Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis},
author = {Zandkarimi, Borna and Alexandrova, Anastassia N.},
abstractNote = {Scaling relationships in catalysis impose fundamental limitations on the catalyst maximal performance; therefore, there is a continuous hunt for ways of circumventing them. We show that, at the subnano-scale, scaling relationships can be broken through catalyst dynamics. Oxygen reduction reaction (ORR), which can be catalyzed by Pt nanoparticles, is used as our study case. Subnanometer gas-phase and graphene-deposited Pt n cluster catalysts are shown to exhibit poor correlation between binding energies of the intermediates, O, OH, and OOH, involved in the scaling relationships for ORR. The effect is due to the highly fluxional behavior of subnanometer clusters, which easily adapt their structures to the bound adsorbates and varying coverage and in some cases even reshape the structure upon changing environment. This fluxional behavior is also commonplace for clusters and contrasts them to extended surfaces, suggesting that breaking scaling relationships is likely a rule more than an exception in nanocluster catalysis.},
doi = {10.1021/acs.jpclett.8b03680},
journal = {Journal of Physical Chemistry Letters},
number = ,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}

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Cited by: 13 works
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Works referencing / citing this record:

Surface‐supported cluster catalysis: Ensembles of metastable states run the show
journal, May 2019

  • Zandkarimi, Borna; Alexandrova, Anastassia N.
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  • DOI: 10.1002/wcms.1420

Strategies to break linear scaling relationships
journal, October 2019


Solid-to-liquid phase transitions of sub-nanometer clusters enhance chemical transformation
journal, November 2019


Interface-confined triangular FeO x nanoclusters on Pt(111)
journal, December 2019

  • Zhou, Zhiwen; Liu, Ping; Yang, Fan
  • The Journal of Chemical Physics, Vol. 151, Issue 21
  • DOI: 10.1063/1.5129266