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

Zandkarimi, Borna; Alexandrova, Anastassia N.

doi:10.1021/acs.jpclett.8b03680

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:

^[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:: 2019-01-11

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.

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                    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

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                    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.

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@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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DOI: https://doi.org/10.1021/acs.jpclett.8b03680

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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.
Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 9, Issue 6
DOI: 10.1002/wcms.1420

Strategies to break linear scaling relationships
journal, October 2019

Pérez-Ramírez, Javier; López, Núria
Nature Catalysis, Vol. 2, Issue 11
DOI: 10.1038/s41929-019-0376-6

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

Sun, Juan-Juan; Cheng, Jun
Nature Communications, Vol. 10, Issue 1
DOI: 10.1038/s41467-019-13509-3

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

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

Abstract

Citation Formats

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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

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journal, November 2019

Interface-confined triangular FeO _x nanoclusters on Pt(111)
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