Potential-specific structure at the hematite-electrolyte interface

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter; Rosso, Kevin M.

doi:10.1002/adfm.201705618

Title: Potential-specific structure at the hematite-electrolyte interface

Journal Article · Wed Feb 21 00:00:00 EST 2018 · Advanced Functional Materials (Online)

DOI:https://doi.org/10.1002/adfm.201705618· OSTI ID:1422282

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter; Rosso, Kevin M.

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe₂O₃) (110$$\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1422282

Report Number(s):: PNNL-SA-128852; 49381; KC0302060

Journal Information:: Advanced Functional Materials (Online), Vol. 28, Issue 8; Related Information: Article No. 1705618; ISSN 1616-3028

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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