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Relativistic Effects in Platinum Nanocluster Catalysis: A Statistical Ensemble-Based Analysis
Indian Inst Technol Indore, Dept Chem, Indore 453552, India..
Indian Inst Kharagpur, Dept Chem, Kharagpur 721302, W Bengal, India..ORCID iD: 0000-0002-8116-5506
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory. Uppsala Univ, Dept Phys & Astron, Condensed Matter Theory Grp, S-75120 Uppsala, Sweden.;Indian Inst Technol Ropar, Dept Phys, Ropar 140001, Punjab, India..ORCID iD: 0000-0003-1231-9994
Indian Inst Technol Indore, Dept Chem, Indore 453552, India..ORCID iD: 0000-0002-9972-9947
2022 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 126, no 8, p. 1345-1359Article in journal (Refereed) Published
Abstract [en]

Nanoclusters are materials of paramount catalytic importance. Among various unique properties featured by nanoclusters, a pronounced relativistic effect can be a decisive parameter in governing their catalytic activity. A concise study delineating the role of relativistic effects in nanocluster catalysis is carried by investigating the oxygen reduction reaction (ORR) activity of a Pt-7 subnanometer cluster. Global optimization analysis shows the critical role of spin-orbit coupling (SOC) in regulating the relative stability between structural isomers of the cluster. An overall improved ORR adsorption energetics and differently scaled adsorption-induced structural changes are identified with SOC compared to a non-SOC scenario. Ab initio atomistic thermodynamics analysis predicted nearly identical phase diagrams with significant structural differences for high coverage oxygenated clusters under realistic conditions. Though inclusion of SOC does not bring about drastic changes in the overall catalytic activity of the cluster, it is having a crucial role in governing the rate-determining step, transition-state configuration, and energetics of elementary reaction pathways. Furthermore, a statistical ensemble-based approach illustrates the strong contribution of low-energy local minimum structural isomers to the total ORR activity, which is significantly scaled up along the activity improving direction within the SOC framework. The study provides critical insights toward the importance of relativistic effects in determining various catalytic activity relevant features of nanoclusters.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2022. Vol. 126, no 8, p. 1345-1359
National Category
Physical Chemistry Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-473198DOI: 10.1021/acs.jpca.1c09981ISI: 000773650300004PubMedID: 35188378OAI: oai:DiVA.org:uu-473198DiVA, id: diva2:1654263
Funder
Swedish Research Council, VR/2019-05317Available from: 2022-04-26 Created: 2022-04-26 Last updated: 2022-04-26Bibliographically approved

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Ahuja, Rajeev

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