Magnier Lucile, Cossard Garance, Martin Vincent, Pascal Céline, Roche Virginie, Sibert Eric, Shchedrina Irina, Bousquet Richard, Parry Valérie, Chatenet Marian
Univ. Grenoble Alpes, CNRS, Grenoble INP (Institute of Engineering, Univ. Grenoble Alpes), SIMAP, Grenoble, France.
Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP (Institute of Engineering, Univ. Grenoble Alpes), LEPMI, Grenoble, France.
Nat Mater. 2024 Feb;23(2):252-261. doi: 10.1038/s41563-023-01744-5. Epub 2024 Jan 12.
NiFe-based oxo-hydroxides are highly active for the oxygen evolution reaction but require complex synthesis and are poorly durable when deposited on foreign supports. Herein we demonstrate that easily processable, Earth-abundant and cheap Fe-Ni alloys spontaneously develop a highly active NiFe oxo-hydroxide surface, exsolved upon electrochemical activation. While the manufacturing process and the initial surface state of the alloys do not impact the oxygen evolution reaction performance, the growth/composition of the NiFe oxo-hydroxide surface layer depends on the alloying elements and initial atomic Fe/Ni ratio, hence driving oxygen evolution reaction activity. Whatever the initial Fe/Ni ratio of the Fe-Ni alloy (varying between 0.004 and 7.4), the best oxygen evolution reaction performance (beyond that of commercial IrO) and durability was obtained for a surface Fe/Ni ratio between 0.2 and 0.4 and includes numerous active sites (high Ni/Ni capacitive response) and high efficiency (high Fe/Ni ratio). This knowledge paves the way to active and durable Fe-Ni alloy oxygen-evolving electrodes for alkaline water electrolysers.
镍铁基羟基氧化物对析氧反应具有高活性,但合成过程复杂,且沉积在异质载体上时耐久性较差。在此,我们证明了易于加工、储量丰富且廉价的铁镍合金能自发形成高活性的镍铁羟基氧化物表面,该表面在电化学活化时析出。虽然合金的制造工艺和初始表面状态不影响析氧反应性能,但镍铁羟基氧化物表面层的生长/组成取决于合金元素和初始原子铁/镍比,从而驱动析氧反应活性。无论铁镍合金的初始铁/镍比如何(在0.004至7.4之间变化),当表面铁/镍比在0.2至0.4之间时,可获得最佳析氧反应性能(超过商业氧化铱)和耐久性,且包含大量活性位点(高镍/镍电容响应)和高效率(高铁/镍比)。这一知识为碱性水电解槽的活性和耐用铁镍合金析氧电极铺平了道路。