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

doi:10.1021/acs.chemmater.1c01594

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^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	5757-5768
Number of pages	12
Journal	Chemistry of Materials
Volume	33
Issue number	14
Early online date	7 Jul 2021
DOIs	https://doi.org/10.1021/acs.chemmater.1c01594
Publication status	Published - 27 Jul 2021

Bibliographical note

Funding Information:
N.H.B., A.I., S.M.B., J.V., E.T.M., B.F.C., A.V.d.V., S.R.N., and B.C.M. were all supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0019381. L.F.J.P. and B.C.M also gratefully acknowledge support from the Research Corporation for Science Advancement (RSCA) through an Advanced Energy Storage Scialog award that seeded the initial collaboration. W.R. and D.O.S. acknowledge funding by the Faraday Institution ( http://www.faraday.ac.uk , EP/S003053/1, grant no. FIRG003) and the use of the MICHAEL computing cluster. D.O.S. acknowledges support from the European Research Council, ERC (Grant 758345). Via our membership of the U.K.’s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202, EP/R029431), this work used the ARCHER U.K. National Supercomputing Service ( http://www.archer.ac.uk ). Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. This research used resources of the Advanced Light Source and the Molecular Foundry, which are the U.S. DOE Office of Science facilities at Lawrence Berkeley National Laboratory under Contract no. DE-AC02-05CH11231. The authors acknowledge Diamond Light Source for time on Beamline I09 under Proposal SI22250. The neutron pair distribution function measurements used resources at Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Material characterization made use of the MRL Shared Experimental Facilities at UCSB, which are supported by the MRSEC Program of the NSF under Award no. DMR 1720256, a member of the NSF-funded Materials Research Facilities Network. The content of the information does not necessarily reflect the position or the policy of the U.S. Government, and no official endorsement should be inferred. The authors thank Matthew Mecklenburg for his assistance with TEM and EELS measurements at the University of Southern California Core Center of Excellence in Nano Imaging, acknowledge and thank Prof. Clare Grey for preliminary discussions about NMR data collected on her NMR spectrometers, and also thank Sara Abdel Razek for assistance with the X-ray absorption/emission simulations.

Publisher Copyright:
© 2021 American Chemical Society.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.1c01594

Cite this

Bashian, N. H., Zuba, M., Irshad, A., Becwar, S. M., Vinckeviciute, J., Rahim, W., Griffith, K. J., McClure, E. T., Papp, J. K., McCloskey, B. D., Scanlon, D. O., Chmelka, B. F., Van Der Ven, A., Narayan, S. R., Piper, L. F. J., & Melot, B. C. (2021). Electrochemical Oxidative Fluorination of an Oxide Perovskite. Chemistry of Materials, 33(14), 5757-5768. https://doi.org/10.1021/acs.chemmater.1c01594

@article{d1f8ff45059141d789ee392b10987004,

title = "Electrochemical Oxidative Fluorination of an Oxide Perovskite",

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.",

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

note = "Funding Information: N.H.B., A.I., S.M.B., J.V., E.T.M., B.F.C., A.V.d.V., S.R.N., and B.C.M. were all supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0019381. L.F.J.P. and B.C.M also gratefully acknowledge support from the Research Corporation for Science Advancement (RSCA) through an Advanced Energy Storage Scialog award that seeded the initial collaboration. W.R. and D.O.S. acknowledge funding by the Faraday Institution ( http://www.faraday.ac.uk , EP/S003053/1, grant no. FIRG003) and the use of the MICHAEL computing cluster. D.O.S. acknowledges support from the European Research Council, ERC (Grant 758345). Via our membership of the U.K.{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202, EP/R029431), this work used the ARCHER U.K. National Supercomputing Service ( http://www.archer.ac.uk ). Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. This research used resources of the Advanced Light Source and the Molecular Foundry, which are the U.S. DOE Office of Science facilities at Lawrence Berkeley National Laboratory under Contract no. DE-AC02-05CH11231. The authors acknowledge Diamond Light Source for time on Beamline I09 under Proposal SI22250. The neutron pair distribution function measurements used resources at Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Material characterization made use of the MRL Shared Experimental Facilities at UCSB, which are supported by the MRSEC Program of the NSF under Award no. DMR 1720256, a member of the NSF-funded Materials Research Facilities Network. The content of the information does not necessarily reflect the position or the policy of the U.S. Government, and no official endorsement should be inferred. The authors thank Matthew Mecklenburg for his assistance with TEM and EELS measurements at the University of Southern California Core Center of Excellence in Nano Imaging, acknowledge and thank Prof. Clare Grey for preliminary discussions about NMR data collected on her NMR spectrometers, and also thank Sara Abdel Razek for assistance with the X-ray absorption/emission simulations. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = jul,

day = "27",

doi = "10.1021/acs.chemmater.1c01594",

language = "English",

volume = "33",

pages = "5757--5768",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "14",

}

Bashian, NH, Zuba, M, Irshad, A, Becwar, SM, Vinckeviciute, J, Rahim, W, Griffith, KJ, McClure, ET, Papp, JK, McCloskey, BD, Scanlon, DO, Chmelka, BF, Van Der Ven, A, Narayan, SR, Piper, LFJ & Melot, BC 2021, 'Electrochemical Oxidative Fluorination of an Oxide Perovskite', Chemistry of Materials, vol. 33, no. 14, pp. 5757-5768. https://doi.org/10.1021/acs.chemmater.1c01594

TY - JOUR

T1 - Electrochemical Oxidative Fluorination of an Oxide Perovskite

AU - Bashian, Nicholas H.

AU - Zuba, Mateusz

AU - Irshad, Ahamed

AU - Becwar, Shona M.

AU - Vinckeviciute, Julija

AU - Rahim, Warda

AU - Griffith, Kent J.

AU - McClure, Eric T.

AU - Papp, Joseph K.

AU - McCloskey, Bryan D.

AU - Scanlon, David O.

AU - Chmelka, Bradley F.

AU - Van Der Ven, Anton

AU - Narayan, Sri R.

AU - Piper, Louis F.J.

AU - Melot, Brent C.

N1 - Funding Information: N.H.B., A.I., S.M.B., J.V., E.T.M., B.F.C., A.V.d.V., S.R.N., and B.C.M. were all supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award no. DE-SC0019381. L.F.J.P. and B.C.M also gratefully acknowledge support from the Research Corporation for Science Advancement (RSCA) through an Advanced Energy Storage Scialog award that seeded the initial collaboration. W.R. and D.O.S. acknowledge funding by the Faraday Institution ( http://www.faraday.ac.uk , EP/S003053/1, grant no. FIRG003) and the use of the MICHAEL computing cluster. D.O.S. acknowledges support from the European Research Council, ERC (Grant 758345). Via our membership of the U.K.’s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202, EP/R029431), this work used the ARCHER U.K. National Supercomputing Service ( http://www.archer.ac.uk ). Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. This research used resources of the Advanced Light Source and the Molecular Foundry, which are the U.S. DOE Office of Science facilities at Lawrence Berkeley National Laboratory under Contract no. DE-AC02-05CH11231. The authors acknowledge Diamond Light Source for time on Beamline I09 under Proposal SI22250. The neutron pair distribution function measurements used resources at Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Material characterization made use of the MRL Shared Experimental Facilities at UCSB, which are supported by the MRSEC Program of the NSF under Award no. DMR 1720256, a member of the NSF-funded Materials Research Facilities Network. The content of the information does not necessarily reflect the position or the policy of the U.S. Government, and no official endorsement should be inferred. The authors thank Matthew Mecklenburg for his assistance with TEM and EELS measurements at the University of Southern California Core Center of Excellence in Nano Imaging, acknowledge and thank Prof. Clare Grey for preliminary discussions about NMR data collected on her NMR spectrometers, and also thank Sara Abdel Razek for assistance with the X-ray absorption/emission simulations. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/7/27

Y1 - 2021/7/27

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85111265110

U2 - 10.1021/acs.chemmater.1c01594

DO - 10.1021/acs.chemmater.1c01594

M3 - Article

AN - SCOPUS:85111265110

SN - 0897-4756

VL - 33

SP - 5757

EP - 5768

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 14

ER -

Electrochemical Oxidative Fluorination of an Oxide Perovskite

Abstract

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