Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism
Research output: Contribution to journal › Research article › Contributed › peer-review
Contributors
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 W0=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.
Details
Original language | English |
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Pages (from-to) | 25419-25427 |
Number of pages | 9 |
Journal | Angewandte Chemie - International Edition |
Volume | 60 |
Issue number | 48 |
Publication status | Published - 22 Nov 2021 |
Peer-reviewed | Yes |
Externally published | Yes |
External IDs
ORCID | /0000-0002-8120-8553/work/161409571 |
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Keywords
ASJC Scopus subject areas
Keywords
- confined water, Grotthuss mechanism, micelles, proton hopping, THz spectroscopy