Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China.
Small. 2023 Jul;19(27):e2300794. doi: 10.1002/smll.202300794. Epub 2023 Apr 3.
The electrosynthesis of recyclable ammonia (NH ) from nitrate under ambient conditions is of great importance but still full of challenges for practical application. Herein, an efficient catalyst design strategy is developed that can engineer the surface microenvironment of a PdCu hollow (PdCu-H) catalyst to confine the intermediates and thus promote selective NH electrosynthesis from nitrate. The hollow nanoparticles are synthesized by in situ reduction and nucleation of PdCu nanocrystals along a self-assembled micelle of a well-designed surfactant. The PdCu-H catalyst shows a structure-dependent selectivity toward the NH product during the nitrate reduction reaction (NO RR) electrocatalysis, enabling a high NH Faradaic efficiency of 87.3% and a remarkable NH yield rate of 0.551 mmol h mg at -0.30 V (vs reversible hydrogen electrode). Moreover, this PdCu-H catalyst delivers high electrochemical performance in the rechargeable zinc-NO battery. These results provide a promising design strategy to tune catalytic selectivity for efficient electrosynthesis of renewable NH and feedstocks.
在环境条件下从硝酸盐中电化学合成可回收氨（NH ）具有重要意义，但在实际应用中仍充满挑战。本文开发了一种有效的催化剂设计策略，可以对 PdCu 空心（PdCu-H）催化剂的表面微环境进行工程设计，以限制中间体，从而促进从硝酸盐中选择性电合成 NH 。通过在设计良好的表面活性剂的自组装胶束中沿 PdCu 纳米晶原位还原和成核，合成了空心纳米粒子。在硝酸盐还原反应（NO RR）电催化过程中，PdCu-H 催化剂对 NH 产物表现出结构依赖性选择性，在 -0.30 V（相对于可逆氢电极）时可实现 87.3%的高 NH 法拉第效率和 0.551 mmol h mg 的显著 NH 产率。此外，该 PdCu-H 催化剂在可充电锌-NO 电池中表现出高电化学性能。这些结果为高效电合成可再生 NH 和原料的催化选择性提供了一种有前景的设计策略。
