Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Ptn Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species

Kumari, Simran; Masubuchi, Tsugunosuke; White, Henry S.; Alexandrova, Anastassia; Anderson, Scott L.; Sautet, Philippe

doi:10.1021/jacs.2c13063

Title: Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Pt_n Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species

Journal Article · Fri Mar 03 00:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c13063· OSTI ID:1963165

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Univ. of California, Los Angeles, CA (United States)
Univ. of Utah, Salt Lake City, UT (United States)

A combination of density functional theory (DFT) and experiments with atomically size-selected Pt_n clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Pt_n size on the electrocatalytic activity of Pt_n (n = 1, 4, 7, 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Pt_n size, such that Pt₇/ITO and Pt₈/ITO have roughly double the activity per Pt atom compared to atoms in the surface layer of polycrystalline Pt. Both DFT and experiment find that hydrogen under-potential deposition (H_upd) results in Pt_n/ITO (n = 4, 7, 8) adsorbing ~2 H atoms/Pt atom at the HER threshold potential, equal to ca. double the Hupd observed for Pt bulk or nanoparticles. Here, the cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt₁/ITO, where H adsorption at the HER threshold potential is energetically unfavorable. Theory combines global optimization with grand canonical approaches for the influence of potential, uncovering that several metastable structures contribute to HER, changing with the applied potential. It is hence critical to include reactions of the ensemble of energetically accessible Pt_nH_x/ITO structures to correctly predict the activity vs. Pt_n size and applied potential. For the small clusters, spillover of H_ads from the clusters to the ITO support is significant, resulting in a competing channel for loss of H_ads, particularly at slow potential scan rates.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020125; AC02-05CH11231

OSTI ID:: 1963165

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 10; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Ptn Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species

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Title: Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Pt_n Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species