Main‐Group Metal‐Nonmetal Dynamic Proton Bridges Enhance Ammonia Electrosynthesis
Yuntong Sun, Liming Dai, Kai Dong, Nicole L. D. Sui, Yinghao Li, Jingwen Sun, Jianrong Zeng, Wenjun Fan, Wenjun Fan, Meng Tian, Meng Tian, Junwu Zhu, Junwu Zhu, Jong‐Min Lee
Abstract
Abstract The electrochemical nitrogen reduction reaction (eNRR) is a crucial process for the sustainable production of ammonia (NH 3 ) for energy and agriculture applications. However, the reaction's efficiency is highly dependent on the activation of the inert N≡N bond, which is hindered by the electron back‐donation to the π* orbitals of the N≡N bond, resulting in low eNRR capacity. Herein, we report a main‐group metal‐nonmetal (O−In−S) eNRR catalyst featuring a dynamic proton bridge, with In−S serving as the polarization pair and O functioning as the dynamic electron pool. In situ spectroscopic analysis and theoretical calculations reveal that the In−S polarization pair acts as asymmetric dual‐sites, polarizing the N≡N bond by concurrently back‐donating electrons to both the π x * and π y * orbitals of N 2 , thereby overcoming the significant band gap limitations, while inhibiting the competitive hydrogen evolution reaction. Meanwhile, the O dynamic electron pool acts as a “repository” for electron storage and donation to the In−S polarization pair. As a result, the O−In−S dynamic proton bridge exhibits exceptional NH 3 yield rates and Faradaic efficiencies (FEs) across a wide potential window of 0.3 V, with an optimal NH 3 yield rate of 80.07±4.25 μg h −1 mg −1 and an FE of 38.01±2.02 %, outperforming most previously reported catalysts.