In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction

Qijun Che; Iris C.G. van den Bosch; Phu T.P. Le; Masoud Lazemi; Emma van der Minne; Yorick A. Birkhölzer; Moritz Nunnenkamp; Matt L.J. Peerlings; Olga V. Safonova; Maarten Nachtegaal; Gertjan Koster; Christoph Baeumer; Petra de Jongh; Frank M.F. de Groot

doi:10.1021/acs.jpcc.3c07864

In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

Qijun Che, Iris C.G. van den Bosch, Phu T.P. Le, Masoud Lazemi, Emma van der Minne, Yorick A. Birkhölzer, Moritz Nunnenkamp, Matt L.J. Peerlings, Olga V. Safonova, Maarten Nachtegaal, Gertjan Koster, Christoph Baeumer, Petra de Jongh, Frank M.F. de Groot^*

^*Corresponding author for this work

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

Abstract

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO₃ and LaFeO₃/LaNiO₃ thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La_0.67Sr_0.33MnO₃ layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca₂Nb₃O₁₀ nanosheet-buffered 100 nm SiN_x membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiN_x membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO₃ film.

Original language	English
Pages (from-to)	5515-5523
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	128
Issue number	13
DOIs	https://doi.org/10.1021/acs.jpcc.3c07864
Publication status	Published - 4 Apr 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

Funding

Funders	Funder number
Horizon 2020 Framework Programme
European Commission
China Scholarship Council	202006990039
China Scholarship Council
H2020 Marie Skłodowska-Curie Actions	860553
H2020 Marie Skłodowska-Curie Actions
European Research Council	101040669
European Research Council
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	17621
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

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che-et-al-2024-in-situ-x-ray-absorption-spectroscopy-of-lafeo3-and-lafeo3-lanio3-thin-films-in-the-electrocatalyticFinal published version, 3.14 MBLicence: CC BY

Cite this

Che, Q., van den Bosch, I. C. G., Le, P. T. P., Lazemi, M., van der Minne, E., Birkhölzer, Y. A., Nunnenkamp, M., Peerlings, M. L. J., Safonova, O. V., Nachtegaal, M., Koster, G., Baeumer, C., de Jongh, P., & de Groot, F. M. F. (2024). In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction. Journal of Physical Chemistry C, 128(13), 5515-5523. https://doi.org/10.1021/acs.jpcc.3c07864

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title = "In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction",

abstract = "We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.",

author = "Qijun Che and {van den Bosch}, {Iris C.G.} and Le, {Phu T.P.} and Masoud Lazemi and {van der Minne}, Emma and Birkh{\"o}lzer, {Yorick A.} and Moritz Nunnenkamp and Peerlings, {Matt L.J.} and Safonova, {Olga V.} and Maarten Nachtegaal and Gertjan Koster and Christoph Baeumer and {de Jongh}, Petra and {de Groot}, {Frank M.F.}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

month = apr,

day = "4",

doi = "10.1021/acs.jpcc.3c07864",

language = "English",

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Che, Q, van den Bosch, ICG, Le, PTP, Lazemi, M, van der Minne, E, Birkhölzer, YA, Nunnenkamp, M, Peerlings, MLJ, Safonova, OV, Nachtegaal, M, Koster, G, Baeumer, C, de Jongh, P & de Groot, FMF 2024, 'In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction', Journal of Physical Chemistry C, vol. 128, no. 13, pp. 5515-5523. https://doi.org/10.1021/acs.jpcc.3c07864

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AU - Che, Qijun

AU - van den Bosch, Iris C.G.

AU - Le, Phu T.P.

AU - Lazemi, Masoud

AU - van der Minne, Emma

AU - Birkhölzer, Yorick A.

AU - Nunnenkamp, Moritz

AU - Peerlings, Matt L.J.

AU - Safonova, Olga V.

AU - Nachtegaal, Maarten

AU - Koster, Gertjan

AU - Baeumer, Christoph

AU - de Jongh, Petra

AU - de Groot, Frank M.F.

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Y1 - 2024/4/4

N2 - We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.

AB - We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.

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