Hu Yu-Wen, Sultana Fozia, Balogun M-Sadeeq, Xiong Tuzhi, Huang Yongchao, Xia Yu
College of Materials Science and Engineering, Hunan University, Changsha, 410082, China.
School of Chemistry and Chemical Engineering, University of South China, Hengyang, 421001, China.
Nanoscale. 2024 Feb 22;16(8):4325-4332. doi: 10.1039/d3nr05957j.
Nickel nitride (NiN) is a promising electrocatalyst for the hydrogen evolution reaction (HER) owing to its excellent metallic features and has been demonstrated to exhibit considerable activity for water oxidation. However, its undesirable characteristics as an HER electrocatalyst due to its poor unfavourable d-band energy level significantly limit its water dissociation kinetics. Herein, the HER electrocatalytic activity of NiN was prominently enhanced the simultaneous incorporation of bi-cations (vanadium (V) and iron (Fe), denoted as V-Fe-NiN). The optimized V-Fe-NiN displays impressive performance with an overpotential of 69 mV at 10 mA cm and good stability in 1.0 M KOH, which is remarkably better than pristine NiN, V-doped NiN, and Fe-doped NiN and considerably closer to a commercial Pt/C catalyst. Based on density functional theory (DFT) studies, V and Fe atoms not only serve as active sites for promoting water dissociation kinetics but also tune the electronic structure of NiN to achieve optimized hydrogen adsorption capabilities. This work presents an inclusive understanding of the rational designing of high-performance transition metal nitride-based electrocatalysts for hydrogen production. Its electrocatalytic performance can be significantly enhanced by doping transition metal cations.
氮化镍（NiN）由于其优异的金属特性，是一种很有前景的析氢反应（HER）电催化剂，并且已被证明对水氧化表现出可观的活性。然而，由于其不利的d带能级，它作为HER电催化剂具有不良特性，这显著限制了其水解离动力学。在此，通过同时引入双阳离子（钒（V）和铁（Fe），记为V-Fe-NiN），NiN的HER电催化活性得到显著提高。优化后的V-Fe-NiN表现出令人印象深刻的性能，在10 mA cm时过电位为69 mV，在1.0 M KOH中具有良好的稳定性，明显优于原始NiN、V掺杂NiN和Fe掺杂NiN，并且相当接近商业Pt/C催化剂。基于密度泛函理论（DFT）研究，V和Fe原子不仅作为促进水解离动力学的活性位点，还能调节NiN的电子结构以实现优化的氢吸附能力。这项工作全面理解了用于制氢的高性能过渡金属氮化物基电催化剂的合理设计。通过掺杂过渡金属阳离子可以显著提高其电催化性能。
