Unraveling Multiscale Kinetics over Subnanometer Cluster Catalysts: H2 Desorption from Pt3(-H)2/γ-Al2O3(110)

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Author(s)Yan, George
Author(s)Vlachos, Dionisios G.
Date Accessioned2023-11-09T18:50:19Z
Date Available2023-11-09T18:50:19Z
Publication Date2023-08-18
DescriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.3c02014. This article will be embargoed until August 18, 2024.
AbstractDespite the attractiveness of highly dispersed supported metal catalysts due to the efficient usage of the active metal component, the structural complexity of subnanometer metal cluster active sites and the interconnectedness of reaction networks over many active site configurations elude detailed understanding. Here, we perform density functional theory (DFT) calculations and state-based kinetic simulations of the desorption of H2 from Pt3(-H)2 clusters supported on dehydroxylated γ-Al2O3(110), serving as a prototype of such coupled reaction networks. Different from ideal low Miller index metal surfaces and highly symmetric gas-phase clusters, we find many unique H binding sites on the supported Pt3 clusters, resulting in an ensemble of metastable Pt3(-H)2 cluster configurations interwoven within a network of H diffusion, active site restructuring, and H2 desorption elementary steps. Simulations and spectral analysis show that the catalyst and chemistry expose three principal time scales, corresponding to the diffusion of H, restructuring of Pt3(-H)2, and desorption of H2. Free energy span-based interpretations of the reaction pathways and sensitivity analysis of the eigenvalues uncover favorable Pt3(-H)2 restructuring and H2 desorption processes as being kinetically relevant at intermediate and long times. Interestingly, H2 desorption implicates catalyst restructuring as a prerequisite for forming more favorable desorption channels. We introduce simplified ensemble-based models and effective rate constants for the modeling of such multiscale reaction processes.
SponsorThe initial part of this work was supported by the Department of Energy’s Office of Energy Efficient and Renewable Energy’s Advanced Manufacturing Office under Award Number DE-EE0007888-9.5. The Delaware Energy Institute gratefully acknowledges the support and partnership of the State of Delaware toward the RAPID projects. The latter part was supported by the U.S. Dept. of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0022144. This research was also supported in part by the high-performance computing resources of the Information Technologies (IT) at the University of Delaware.
CitationYan, George, and Dionisios G. Vlachos. “Unraveling Multiscale Kinetics over Subnanometer Cluster Catalysts: H2 Desorption from Pt3(-H)2/γ-Al2O3(110).” ACS Catalysis 13, no. 16 (August 18, 2023): 10602–14. https://doi.org/10.1021/acscatal.3c02014.
ISSN2155-5435
URLhttps://udspace.udel.edu/handle/19716/33616
Languageen_US
PublisherACS Catalysis
Keywordssupported metal clusters
Keywordsrestructuring
Keywordsmicrokinetic modeling
Keywordstransient kinetics
Keywordssensitivity analysis
Keywordsquasi-equilibrium
TitleUnraveling Multiscale Kinetics over Subnanometer Cluster Catalysts: H2 Desorption from Pt3(-H)2/γ-Al2O3(110)
TypeArticle
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