Main‐Group Metal‐Nonmetal Dynamic Proton Bridges Enhance Ammonia Electrosynthesis

Abstract

The electrochemical nitrogen reduction reaction is a crucial process for the sustainable production of ammonia 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‐non‐metal (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 πx* and πy* orbitals of N2, 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 NH3 yield rates and Faradaic efficiencies (FEs) across a wide potential window of 0.3 V, with an optimal NH3 yield of 80.07 ± 4.25 μg h‐1 mg‐1 and an FE of 38.01 ± 2.02%, outperforming most previously reported catalysts.