Elucidating the Role of Electric Fields in Fe Oxidation via an Environmental Atom Probe

Lambeets, Sten V.; Cardwell, Naseeha; Onyango, Isaac; Wirth, Mark G.; Vo, Eric; Wang, Yong; Gaspard, Pierre; Ivory, Cornelius F.; Perea, Daniel E.; Visart de Bocarmé, Thierry; McEwen, Jean‐Sabin

doi:10.1002/ange.202423434

Title: Elucidating the Role of Electric Fields in Fe Oxidation via an Environmental Atom Probe

Journal Article · 20 March 2025 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202423434 · OSTI ID:2536793

^[1]; Cardwell, Naseeha ^[2]; Onyango, Isaac ^[2];

^[3]; Vo, Eric ^[1]; Wang, Yong ^[4];

^[5];

^[2];

^[3]; Visart de Bocarmé, Thierry ^[6];

^[7]

Physical and Computational Sciences Directorate Pacific Northwest National Laboratory 902 Battelle Blvd 99354 Richland WA United States of America
The Gene and Linda Voiland school of Chemical Engineering and Bioengineering Washington State University 1505 Stadium Way 99164 Pullman WA United States of America
Environmental Molecular Sciences Laboratory Pacific Northwest National Laboratory 902 Battelle Blvd 99354 Richland WA United States of America
The Gene and Linda Voiland school of Chemical Engineering and Bioengineering Washington State University 1505 Stadium Way 99164 Pullman WA United States of America, Institute for Integrated Catalysis Pacific Northwest National Laboratory 902 Battelle Blvd 99354 Richland WA United States of America
Centre for Nonlinear Phenomena and Complex Systems Université Libre de Bruxelles Campus Plaine CP231 B-1050 Brussels Belgium
Centre for Nonlinear Phenomena and Complex Systems Université Libre de Bruxelles Campus Plaine CP231 B-1050 Brussels Belgium, Chemistry of Surfaces, Interfaces and Nanomaterials Université Libre de Bruxelles Campus Plaine CP243 B-1050 Brussels Belgium
The Gene and Linda Voiland school of Chemical Engineering and Bioengineering Washington State University 1505 Stadium Way 99164 Pullman WA United States of America, Institute for Integrated Catalysis Pacific Northwest National Laboratory 902 Battelle Blvd 99354 Richland WA United States of America, Departments of Physics and Astronomy/Chemistry/Biological Systems Engineering Washington State University 99164 Pullman WA United States of America

Abstract We quantify the effects of intensely applied electric fields on the Fe oxidation mechanism. The specimen are pristine Fe single crystals exposing a variety of surface structures identified by field ion microscopy. These crystals are simultaneously exposed to low pressures of pure oxygen gas, on the order of 10 ⁻⁷ mbar, while applying intense electric fields on their surface of several tens of volts per nanometer. The local composition of the different surface structures is probed directly and in real time using an Environmental Atom Probe and successfully compared with first principles‐based models. We found that rough Fe{244} and Fe{112} facets are more reactive toward oxygen than compact Fe{024} and Fe{011} facets. Results demonstrate that the influence of an electric field on the oxidation kinetics depends on the timescales that are involved as the system evolves toward equilibrium. The initial oxidation kinetics show that strong increases in electric fields facilitate the formation of an oxide. However, as one approaches equilibrium, high field values mitigate this formation. Ultimately, this study elucidates how high externally applied electric fields can be used to dynamically exploit reaction dynamics at the nanoscale towards desired products in a catalytic reaction at mild reaction conditions.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0014560

OSTI ID:: 2536793

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 18 Vol. 137; ISSN 0044-8249

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

Country of Publication:: Germany

Language:: English

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