The technology of hydrogen production by alkaline water electrolysis using renewable energy has the advantages of abundant energy sources and minimal environmental pollution. However, the oxygen evolution reaction (OER) catalyst in water electrolysis faces several challenges. One problem is the unstable supply of renewable energy, which leads to frequent starting and stopping of the electrolyzer. This intermittency exposes the anode catalyst to drastic potential changes that generate reverse currents, resulting in anode catalyst degradation. Therefore, there is a critical need for research on more durable electrocatalysts. In this study, we attempted to improve the stability of perovskite-type oxides by using fluorination chemistry for surface treatment. We prepared fluorine-treated LaNiO3 by calcination with polyvinylidene fluoride (PVDF) and analyzed the electronic structures of the prepared samples by X-ray absorption spectroscopy.LaNiO3 and PVDF, a fluorine additive, were mixed using a mortar. The mixture was then pelletized and sintered in a sealed vessel at 350 °C for 12 hours. This experimental condition was based on the fluorination reaction of HfO2 [1]. Four different PVDF-to-LaNiO3 mixing ratios were synthesized: 0% (pure LaNiO3), 2.5%, 5%, and 10% by weight. To confirm whether the catalyst surfaces were fluorinated, XRD and XAFS measurements were performed to analyze the changes in the crystal structure and the valence changes by the introduction of fluorine. For electrochemical measurements, a measuring cell for electrolysis was used[2], which is reported to be analyzable only with powder catalysts.A comparison of the X-ray diffraction (XRD) patterns of pure LaNiO3 and LaNiO3 treated with PVDF showed that the addition of PVDF shifted the XRD peak to lower angles. This shift confirms a structural expansion in the LaNiO3 crystal lattice due to the PVDF treatment. For a more detailed investigation, XAFS measurements were performed. Analysis in the F K-edge XAFS identified a distinct fluorine peak in the PVDF-treated LaNiO3 sample, indicating successful introduction of fluorine into the structure. In addition, in the Ni K-edge X-ray absorption near edge structure, the spectrum of the PVDF-added sample shifted to a lower energy compared to pure LaNiO3, indicating a reduction in nickel valence, likely due to fluorine incorporation. However, electrochemical measurements indicated a decrease in the initial OER activity of LaNiO3 treated with PVDF.[1] Steven Flynn, Chi Zhang, Kent J. Griffith, Jiahong Shen, Christopher Wolverton, Vinayak P. Dravid, and Kenneth R. Poeppelmeier, Inorganic Chemistry, 60(7), 4463-4474 (2021)[2] K. Nagasawa, T. Ishida, H. Kashiwagi, Y. Sano, and S. Mitsushima, Int. J. Hydrogen Energy, 46, 36619 (2021)
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