Operando Unveiling of Hydrogen Spillover Mechanisms on Tungsten Oxide Surfaces

Li, Haoyi; Abdelgaid, Mona; Paudel, Jay R.; Holzapfel, Noah P.; Augustyn, Veronica; McKone, James R.; Mpourmpakis, Giannis; Crumlin, Ethan J.

doi:10.1021/jacs.4c13711

Title: Operando Unveiling of Hydrogen Spillover Mechanisms on Tungsten Oxide Surfaces

Journal Article · 18 January 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c13711 · OSTI ID:2524551

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Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of Pittsburgh, PA (United States)
North Carolina State University, Raleigh, NC (United States)
University of Pittsburgh, PA (United States); National Technical University of Athens (Greece)

Hydrogen spillover is an important process in catalytic hydrogenation reactions, facilitating H₂ activation and modulating surface chemistry of reducible oxide catalysts. This study focuses on the operando unveiling of platinum-induced hydrogen spillover on monoclinic tungsten trioxide (γ-WO₃), employing ambient pressure X-ray photoelectron spectroscopy, density functional theory calculations and microkinetic modeling to investigate the dynamic evolution of surface states at varied temperatures. At room temperature, hydrogen spillover results in the formation of W⁵⁺ and hydrogen intermediates (hydroxyl species and adsorbed water), facilitated by Pt metal clusters. With increasing temperature, water desorption, reverse hydrogen spillover and surface-to-bulk diffusion of hydrogen atoms compete with each other, leading initially to reoxidation and then further reduction of W atoms in the near-surface. The combined experimental results and simulations provide a comprehensive understanding of the mechanisms underlying hydrogen interaction with reducible metal oxides, lending insights of relevance to the design of enhanced hydrogenation catalysts.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0023465

OSTI ID:: 2524551

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 8 Vol. 147; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dissociation
Hydrogen
Metal clusters
Oxides
Platinum

Title: Operando Unveiling of Hydrogen Spillover Mechanisms on Tungsten Oxide Surfaces

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