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:
-
[1];
[2]
- Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry
- 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. 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. 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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