journal article·2021-07-27Open access

Electrochemical Oxidative Fluorination of an Oxide Perovskite

Nicholas H. Bashian, Mateusz Zuba, Ahamed Irshad, Shona M. Becwar, Julija Vinckeviciute, Warda Rahim, Kent J. Griffith, Eric T. McClure, Joseph K. Papp, Bryan D. McCloskey, David O. Scanlon, Bradley F. Chmelka, Anton Van der Ven, Sri R. Narayan, Louis F. J. Piper, Brent C. Melot

Chemistry of Materials· Volume 33· Issue 14

Abstract

We report on the electrochemical fluorination of the A-site vacant perovskite ReO3 using high-temperature solid-state cells as well as room-temperature liquid electrolytes. Using galvanostatic oxidation and electrochemical impedance spectroscopy, we find that ReO3 can be oxidized by approximately 0.5 equiv of electrons when in contact with fluoride-rich electrolytes. Results from our density functional theory calculations clearly rule out the most intuitive mechanism for charge compensation, whereby F-ions would simply insert onto the A-site of the perovskite structure. Operando X-ray diffraction, neutron total scattering measurements, X-ray spectroscopy, and solid-state 19F NMR with magic-angle spinning were, therefore, used to explore the mechanism by which fluoride ions react with the ReO3 electrode during oxidation. Taken together, our results indicate that a complex structural transformation occurs following fluorination to stabilize the resulting material. While we find that this process of fluorinating ReO3 appears to be only partially reversible, this work demonstrates a practical electrolyte and cell design that can be used to evaluate the mobility of small anions like fluoride that is robust at room temperature and opens new opportunities for exploring the electrochemical fluorination of many new materials.
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Research context

OpenAlex topics: Inorganic Fluorides and Related Compounds · Advanced Condensed Matter Physics · Thermal Expansion and Ionic Conductivity

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States

Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, United States

Department of Chemical Engineering, University of California, Santa Barbara, Santa Barbara, California 93106, United States

Materials Department, University of California, Santa Barbara, Santa Barbara, California 93106, United States

Thomas Young Centre, University College London, Gower Street, London WC1E 6BT, United Kingdom

Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom

Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States

Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom

The Faraday Institution, Quad One, Harwell Science and Innovation Campus, Quad One Becquerel Avenue Harwell, Didcot OX11 0RA, United Kingdom

Materials Science & Engineering, Binghamton University, Binghamton, New York 13902, United States

Funding

Engineering and Physical Sciences Research Council · Basic Energy Sciences · Research Corporation for Science Advancement · Faraday Institution · FP7 Ideas: European Research Council · Division of Materials Research

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