Lv Jiangnan, Yang Qianwen, Liang Tingting, Sun Xiaoting, Rong Wanting, Dai Qiqi, Gao Yizhi, Wang Lanfang, Xu Xiaohong, Liu Yang
Research Institute of Materials Science of Shanxi Normal University & Key Laboratory of Magnetic Molecules and Magnetic Information Materials of Ministry of Education, Taiyuan 030031, China.
Department of Materials Science, Fudan University, Shanghai 200433, China.
J Am Chem Soc. 2025 Aug 6;147(31):27708-27719. doi: 10.1021/jacs.5c06333. Epub 2025 Jul 22.
Electrocatalytic nitrate reduction reaction (NORR) is a promising route for both treating NO-containing wastewater and enabling sustainable ammonia (NH) synthesis. While two-dimensional (2D) transition metal dichalcogenides (TMDs) catalysts have been widely investigated as catalysts in various electrocatalytic reactions, their practical application in NORR remains hindered by inherently sluggish kinetics and insufficient stability. Metal-support interaction (MSI), which enhances charge transfer and stabilizes catalytic sites, offers a compelling strategy to address these challenges. Herein, we design an MSI-driven Ni-WS catalyst via a two-step strategy. The Ni-WS catalyst demonstrates outstanding NORR performance, achieving a Faradaic efficiency of 91.7% at -0.3 V with an NH yield rate of 23.3 mg h cm at -0.7 V. Significantly, the Ni-WS catalyst maintained an exceptional stability in a membrane electrode assembly (MEA), sustaining ≈32 mg h cm NH production over 100 h, surpassing most previously reported TMD-based catalysts. Density functional theory (DFT) calculations reveal that MSI between Ni metal and WS support induces interfacial charge redistribution, optimizes adsorption energy of key intermediates and lowers the energy barrier for the rate-determining step (*NH → *NH). Furthermore, the Zn-NO battery assembled with Ni-WS cathode exhibits remarkable performance. This work advances a two-step synthesis strategy for high-performance NORR electrocatalysts through targeted MSI modulation.
电催化硝酸盐还原反应（NORR）对于处理含NO废水和实现可持续氨（NH₃）合成而言是一条前景光明的途径。尽管二维（2D）过渡金属二硫属化物（TMDs）催化剂作为各种电催化反应的催化剂已得到广泛研究，但其在NORR中的实际应用仍受到固有缓慢动力学和稳定性不足的阻碍。金属-载体相互作用（MSI）可增强电荷转移并稳定催化位点，为应对这些挑战提供了一个极具吸引力的策略。在此，我们通过两步策略设计了一种由MSI驱动的Ni-WS₂催化剂。该Ni-WS₂催化剂展现出卓越的NORR性能，在-0.3 V时法拉第效率达到91.7%，在-0.7 V时NH₃产率为23.3 mg h⁻¹ cm⁻²。值得注意的是，Ni-WS₂催化剂在膜电极组件（MEA）中保持了出色的稳定性，在超过100小时内维持约32 mg h⁻¹ cm⁻²的NH₃产量，超过了大多数先前报道的基于TMDs的催化剂。密度泛函理论（DFT）计算表明，Ni金属与WS₂载体之间的MSI诱导了界面电荷重新分布，优化了关键中间体的吸附能，并降低了速率决定步骤（*NH₂OH → *NH₃）的能垒。此外，组装有Ni-WS₂阴极的Zn-NO电池表现出卓越的性能。这项工作通过有针对性的MSI调控，推进了高性能NORR电催化剂的两步合成策略。
