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Surface Segregation Acts as Surface Engineering for the Oxygen Evolution Reaction on Perovskite Oxides in Alkaline Media

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    Surface Segregation Acts as Surface Engineering for the Oxygen Evolution Reaction on Perovskite Oxides in Alkaline Media
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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 12, 5256–5263
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    https://doi.org/10.1021/acs.chemmater.0c01396
    Published May 18, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    La1–xSrxCoO3-δ perovskites are potential catalysts for the anodic reaction of alkaline water electrolyzers, i.e., the oxygen evolution reaction (OER). It is well-known that La1–xSrxCoO3−δ perovskites can easily display strontium surface segregation, but how this influences the performance of La1–xSrxCoO3−δ perovskites as anodic electrode in alkaline water electrolyzers, particularly in terms of OER activity, has not been unveiled yet. This study focuses on La0.2Sr0.8CoO3−δ, which shows relatively high activity for the OER, and reveals the influence of the preparation temperature on the amount and morphology of segregated strontium-containing islands. Thin film samples were prepared at different temperatures by using pulsed laser deposition. Those samples were then characterized with synchrotron-based X-ray photoelectron spectroscopy “as prepared” and after being immersed in ultrapure water. We found that higher preparation temperatures enhance the segregation of strontium, which is then almost quantitatively removed by washing the samples with ultrapure water. After immersion in water, the samples expose a cobalt-rich surface. Investigating the OER activity as a function of the perovskite deposition temperature, it has been found that the higher the deposition temperature (i.e., the more extended the strontium segregation), the higher the OER activity. Such an effect has been linked to the higher amount of cobalt accessible after removing the strontium segregated islands.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c01396.

    • Voltammogram of bare STO and functionalized STO with gold frame (Figure S1); XRD plot of the sintered ceramic used for PLD and XRR used for deposition thickness calibration (Figure S2); fitting parameters of Sr 3d (Table S1), O 1s (Table S2), La 4d, Co 2p, and Co 3p (Table S3); calculated surface elemental ratio (Table S4); XPS spectra of O 1s (Figure S3); Sr 3d and Co 3p of all samples in bulk sensitive condition (Figure S4) and La 4d (Figure S5); supplementary SEM images (Figures S6 and S7); sketch describing the shadowing effect seen during XPS measurements (Figure S8); AFM images (Figures S10 and S11) and Tafel plot including LSCO_650 (Figure S12) (PDF)

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    This article is cited by 18 publications.

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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 12, 5256–5263
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.0c01396
    Published May 18, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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