The electrochemical production of green and low-cost ammonia requests the development of high-performance electrocatalysts. In this work, the ampoule method was applied to modulate the surface of the zinc electrode by implanting defects and low-valent active sites. The N-doped ZnS electrocatalyst was thus generated by sulfurization with thiourea and applied for electrocatalytic nitrogen reduction reaction (ENRR). Given the rich sulfur vacancies and abundant Zn-N active sites on the surface, excellent catalytic activity and selectivity were obtained, with an NH₃ yield rate of 2.42 × 10^–10 mol s⁻¹ cm⁻² and a Faradaic efficiency of 7.92% at − 0.6 V vs. RHE in 0.1 M KOH solution. Moreover, the as-synthesized zinc electrode exhibits high stability after five recycling tests and a 24 h potentiostatic test. The comparison with Zn foil, non-doping ZnS/Zn and recent metal sulfide electrocatalysts further demonstrated advanced catalytic performance of N@ZnS/Zn for ENRR. By simple synthesis, S vacancies, and N-doping defects, this promising electrocatalyst would represent a good addition to the arena of transition-metal-based catalysts with superior performance in ENRR.

Graphic abstract

中文翻译：

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安瓿法制备的富硫空位氮掺杂ZnS电极，用于碱性介质中的氨生产

绿色环保和低成本氨的电化学生产要求开发高性能电催化剂。在这项工作中，采用安瓿法通过注入缺陷和低价活性位点来调节锌电极的表面。因此，通过用硫脲硫化而生成N掺杂的ZnS电催化剂，并将其用于电催化氮还原反应（ENRR）。考虑到表面上丰富的硫空位和丰富的Zn-N活性位，获得了出色的催化活性和选择性，NH _3的产率为2.42×10 ^–10  mol s ^-1  cm ^-2在0.1 M KOH溶液中，相对于RHE，在-0.6 V时法拉第效率为7.92％。此外，合成后的锌电极在五次循环测试和24小时恒电位测试后显示出高稳定性。与Zn箔，非掺杂ZnS / Zn和最近的金属硫化物电催化剂的比较进一步证明了N @ ZnS / Zn对ENRR的先进催化性能。通过简单的合成，S空位和N掺杂缺陷，这种有前途的电催化剂将成为过渡金属基催化剂领域的一个很好的补充，在ENRR中具有优异的性能。

图形摘要