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

Journal Article · Fri Jan 11 00:00:00 EST 2019 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b03680· OSTI ID:1492942

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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)

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.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); USDOD; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: SC0019152; AFOSR FA9550-16-1-0141; AC02-05CH11231

OSTI ID:: 1492942

Alternate ID(s):: OSTI ID: 1594250; OSTI ID: 1755383

Journal Information:: Journal of Physical Chemistry Letters, Vol. 10; Related Information: https://pubs.acs.org/doi/suppl/10.1021/acs.jpclett.8b03680/suppl_file/jz8b03680_si_001.pdf; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 66 works

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

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