Bo Han, Jie Ding, Man‐Fai Ng, Chengyi Liu, Jianhua Zhang, Cailing Chen, Nan Zhang, Yue Hu, Jing Yan, Beier Jia, Erhai Hu, Mengxin Chen, Zhangliu Tian, Yu Han, Shibo Xi, Chade Lv, Qiang Zhu, Madhavi Srinivasan, Ben Liu, Qingyu Yan
The electrochemical nitrogen reduction reaction (EN 2 RR) provides a sustainable method for synthesizing ammonia at room temperature, but it is hindered by the low ammonia faradic efficiency (FE) and production yield. Herein, we report an effective EN 2 RR electrocatalyst: the ionic liquid-encapsulated aluminum copper bimetallic metal–organic framework (IL-AlCu-MOF). Comparisons across pristine Cu-MOF, AlCu-MOF, IL-Cu-MOF, and IL-AlCu-MOF reveal that the combination of Al doping and IL encapsulation can simultaneously promote dinitrogen activation and accelerate proton generation via water dissociation in a neutral electrolyte, which synergistically enhances the yield and selectivity of ammonia in EN 2 RR. The IL-AlCu-MOF achieves an NH 3 yield of 124.7 μg·h –1 ·mg cat –1 with an FE NH 3 of 20.3% at −0.3 V (vs reversible hydrogen electrode, RHE) in 0.1 M K 2 SO 4 . In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements indicate improved water dissociation kinetics over that of IL-AlCu-MOF, and differential electrochemical mass spectrometry (DEMS) captures the EN 2 RR intermediates. Density functional theory (DFT) calculations show that Al doping modulates the Cu electronic structure for enhanced N 2 activation, while IL encapsulation strengthens water adsorption at the MOF surface and thus accelerates water dissociation, both of which contribute to boosting the EN 2 RR performance.