Modulating the electronic structure of the electrocatalyst plays a vital role in boosting the electrocatalytic performance of the oxygen evolution reaction (OER). In this work, we introduced a one-step solvothermal method to fabricate 1,1-ferrocene dicarboxylic acid (FcDA)-decorated self-evolved nickel sulfide (Ni₃S₂) nanosheet arrays on a nickel foam (NF) framework (denoted as FcDA-Ni₃S₂/NF). Benefiting from the interconnected ultrathin nanosheet architecture, ligand dopants induced and facilitated in situ structural reconstruction, and the FcDA-decorated Ni₃S₂ (FcDA-Ni₃S₂/NF) outperformed its singly doped and undoped counterparts in terms of OER activity. The optimized FcDA-Ni₃S₂/NF self-supported electrode presents a remarkably low overpotential of 268 mV to achieve a current density of 10 mA cm^–2 for the OER and demonstrates robust electrochemical stability for 48 h in a 1.0 M KOH electrolyte. More importantly, in situ electrochemical Raman spectroscopy reveals the generation of catalytically active oxyhydroxide species (NiOOH) derived from the surface construction during the OER of pristine FcDA-Ni₃S₂/NF, contributing significantly to its superior electrocatalytic performance. This study concerns the modulation of electronic structure through ligand engineering and may provide profound insight into the design of cost-efficient OER electrocatalysts.

中文翻译：

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用于电催化析氧反应的自演化 Ni3S2 纳米片的配体诱导电子结构调制


调节电催化剂的电子结构对于提高析氧反应（OER）的电催化性能起着至关重要的作用。在这项工作中，我们引入了一种一步溶剂热法来制备1,1-二茂铁二甲酸（FcDA）修饰的自演化硫化镍（Ni ₃ S ₂ ）纳米片泡沫镍 (NF) 框架上的阵列（表示为 FcDA-Ni ₃ S ₂ /NF）。受益于互连的超薄纳米片结构，配体掺杂剂诱导并促进了原位结构重建，以及 FcDA 修饰的 Ni ₃ S ₂ (FcDA-Ni ₃ S ₂ /NF) 在 OER 活性方面​​优于其单掺杂和未掺杂的对应物。优化的 FcDA-Ni ₃ S ₂ /NF 自支撑电极具有 268 mV 的极低过电势，可实现 10 mA cm ^–2 的电流密度用于 OER，并在 1.0 M KOH 电解质中表现出 48 小时的强大电化学稳定性。更重要的是，原位电化学拉曼光谱揭示了原始 FcDA-Ni ₃ S ₂ /NF 的 OER 过程中源自表面结构的催化活性羟基氧化物 (NiOOH) 的生成，对其卓越的电催化性能做出了重大贡献。这项研究涉及通过配体工程调节电子结构，并可能为经济高效的 OER 电催化剂的设计提供深刻的见解。