Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism

Adams, Ellen M.; Hao, Hongxia; Leven, Itai; Rüttermann, Maximilian; Wirtz, Hanna; Havenith, Martina; Head‐Gordon, Teresa

doi:10.1002/anie.202108766

Title: Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism

Journal Article · 03 October 2021 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202108766 · OSTI ID:1824239

Adams, Ellen M. ^[1]; Hao, Hongxia ^[2]; Leven, Itai ^[2]; Rüttermann, Maximilian ^[1]; Wirtz, Hanna ^[1];

^[1]; Head‐Gordon, Teresa ^[3]

Lehrstuhl für Physkalische Chemie II Ruhr Universität Bochum 44801 Bochum Germany
Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley California 94720 USA, Kenneth S. Pitzer Center for Theoretical Chemistry University of California Berkeley California 94720 USA, Department of Chemistry University of California Berkeley California 94720 USA
Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley California 94720 USA, Kenneth S. Pitzer Center for Theoretical Chemistry University of California Berkeley California 94720 USA, Department of Chemistry University of California Berkeley California 94720 USA, Department of Chemical and Biomolecular Engineering University of California Berkeley California 94720 USA, Department of Bioengineering University of California Berkeley California 94720 USA

Abstract The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W ₀ =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H ⁺ and Cl ⁻ ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.

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

Sponsoring Organization:: German Research Foundation (DFG); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1824239

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 48 Vol. 60; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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