In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction
Open Access
- 20 March 2024
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry C
- Vol. 128 (13) , 5515-5523
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.Keywords
Funding Information
- European Research Council (101040669)
- H2020 Marie Sklodowska-Curie Actions (860553)
- China Scholarship Council (202006990039)
- Nederlandse Organisatie voor Wetenschappelijk Onderzoek (17621)
This publication has 43 references indexed in Scilit:
- Interplay of surface and subsurface contributions in electrocatalysisCurrent Opinion in Electrochemistry, 2023
- Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water ElectrolysisACS Applied Materials & Interfaces, 2022
- Nickelate Superconductivity without Rare‐Earth Magnetism: (La,Sr)NiO2Advanced Materials, 2021
- Correlation between Oxygen Vacancies and Oxygen Evolution Reaction Activity for a Model Electrode: PrBaCo2O5+δAngewandte Chemie International Edition, 2021
- Strain‐Engineered Metal‐to‐Insulator Transition and Orbital Polarization in Nickelate Superlattices Integrated on SiliconAdvanced Materials, 2020
- Transition‐Metal Phosphides: Activity Origin, Energy‐Related Electrocatalysis Applications, and Synthetic StrategiesAdvanced Functional Materials, 2020
- Ni 3d – O 2p hybridization dependent magnetic properties of LaNiO3 thin filmsThin Solid Films, 2016
- Synthesis of KCa2Nb3O10 Crystals with Varying Grain Sizes and Their Nanosheet Monolayer Films As Seed Layers for PiezoMEMS ApplicationsACS Applied Materials & Interfaces, 2015
- Multiplet effects in X-ray spectroscopyCoordination Chemistry Reviews, 2005
- Electronic structure of 3d transition metal compounds: systematic chemical trends and multiplet effectsJournal of Electron Spectroscopy and Related Phenomena, 1993