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

doi:10.1021/acs.jpclett.8b03680

This content will become publicly available on January 11, 2020

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

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Abstract

Scaling relationships in catalysis impose fundamental limitations on the catalyst maximal performance; therefore, there is a continuous hunt for ways of circumventing them. In this study, 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 Ptn 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. Lastly, 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.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); US Air Force Office of Scientific Research (AFOSR)

Contributing Org.:: Univ. of California, Los Angeles, CA (United States)

OSTI Identifier:: 1492942

Grant/Contract Number:: SC0019152; FA9550-16-1-0141

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

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: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:10.1021/acs.jpclett.8b03680.

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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. In this study, 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 Ptn 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. Lastly, 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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