Effect of Dynamic and Preferential Decoration of Pt Catalyst Surfaces by WOx on Hydrodeoxygenation Reactions

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Author(s)Marlowe, Justin
Author(s)Deshpande, Siddharth
Author(s)Vlachos, Dionisios G.
Author(s)Abu-Omar, Mahdi M.
Author(s)Christopher, Phillip
Date Accessioned2024-06-17T17:16:31Z
Date Available2024-06-17T17:16:31Z
Publication Date2024-05-22
DescriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © 2024 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/jacs.4c00931. This article will be embargoed until 05/22/2025.
AbstractCatalysts containing Pt nanoparticles and reducible transition-metal oxides (WOx, NbOx, TiOx) exhibit remarkable selectivity to aromatic products in hydrodeoxygenation (HDO) reactions for biomass valorization, contrasting the undesired aromatic hydrogenation typically observed for metal catalysts. However, the active site(s) responsible for the high selectivity remains elusive. Here, theoretical and experimental analyses are combined to explain the observed HDO reactivity by interrogating the organization of reduced WOx domains on Pt surfaces at sub-monolayer coverage. The SurfGraph algorithm is used to develop model structures that capture the configurational space (∼1000 configurations) for density functional theory (DFT) calculations of a W3O7 trimer on stepped Pt surfaces. Machine-learning models trained on the DFT calculations identify the preferential occupation of well-coordinated Pt sites (≥8 Pt coordination number) by WOx and structural features governing WOx–Pt stability. WOx/Pt/SiO2 catalysts are synthesized with varying W loadings to test the theoretical predictions and relate them to HDO reactivity. Spectroscopy- and microscopy-based catalyst characterizations identify the dynamic and preferential decoration of well-coordinated sites on Pt nanoparticles by reduced WOx species, consistent with theoretical predictions. The catalytic consequences of this preferential decoration on the HDO of a lignin model compound, dihydroeugenol, are clarified. The effect of WOx decoration on Pt nanoparticles for HDO involves WOx inhibition of aromatic ring hydrogenation by preferentially blocking well-coordinated Pt sites. The identification of preferential decoration on specific sites of late-transition-metal surfaces by reducible metal oxides provides a new perspective for understanding and controlling metal–support interactions in heterogeneous catalysis.
SponsorThis work was supported by the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award no. DE-SC0001004. Electron microscopy was performed at the MRL Shared Experimental Facilities, which are supported by the MRSEC Program of the NSF under award no. DMR 1720256, a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org). P.C. and M.A.O. both acknowledge the Mellichamp Academic Initiative in Sustainability at UCSB for support.
CitationMarlowe, Justin, Siddharth Deshpande, Dionisios G. Vlachos, Mahdi M. Abu-Omar, and Phillip Christopher. “Effect of Dynamic and Preferential Decoration of Pt Catalyst Surfaces by WO x on Hydrodeoxygenation Reactions.” Journal of the American Chemical Society 146, no. 20 (May 22, 2024): 13862–74. https://doi.org/10.1021/jacs.4c00931.
ISSN1520-5126
URLhttps://udspace.udel.edu/handle/19716/34504
Languageen_US
PublisherJournal of the American Chemical Society
Keywordsdensity functional theory
Keywordsgraph theory
Keywordsmachine learning
Keywordscatalysts
Keywordshydrodeoxygenation
Keywordsrestructuring
Keywordsplatinum
Keywordstungsten
Keywordsstructure-activity relationship
TitleEffect of Dynamic and Preferential Decoration of Pt Catalyst Surfaces by WOx on Hydrodeoxygenation Reactions
TypeArticle
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