Hydrogen Evolution on Electrode–Supported Ptn Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity

Zhang, Zisheng; Masubuchi, Tsugunosuke; Sautet, Philippe; Anderson, Scott L.; Alexandrova, Anastassia N.

doi:10.1002/anie.202218210

Hydrogen Evolution on Electrode–Supported Ptn Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity

Journal Article · Wed Mar 15 00:00:00 EDT 2023 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202218210· OSTI ID:1963166

Zhang, Zisheng ^[1]; Masubuchi, Tsugunosuke ^[2]; Sautet, Philippe ^[3]; Anderson, Scott L. ^[2]; Alexandrova, Anastassia N. ^[3]

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

We report the size-dependent activity and stability of supported Pt1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with sizedependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (~2 H/Pt). An ensemble-based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. Furthermore, the stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential- and adsorbate-coverage-dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0020125

OSTI ID:: 1963166

Alternate ID(s):: OSTI ID: 1983472

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 20 Vol. 62; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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