Modulating Metal-Nitrogen Coupling in Anti-Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia

作者：Gong, Zhiheng; Xiang, Xuepeng; Zhong, Wenye; Jia, Chenghao; Chen, Peiyan; Zhang, Nian; Zhao, Shijun; Liu, Weizhen^*; Chen, Yan^*; Lin, Zhang

来源：Angewandte Chemie - International Edition, 2023, 62(38).

DOI：10.1002/anie.202308775

• Ammonia
• Anti-Perovskite Nitride
• Cation Doping
• Electrochemical Nitrate Reduction
• Hydrogenation
• Metal-Nitrogen Coupling

The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal-nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that the metal-nitrogen coupling in anti-perovskite Co4N can be effective modulated by Cu doping to form Co3CuN, leading to strongly promoted hydrogenation process during electrochemical reduction of nitrate (NO3-RR) to ammonia. The combination of advanced spectroscopic techniques and density functional theory calculations reveal that Cu dopants strengthen the Co-N bond and upshifted the metal d-band towards the Fermi level, promoting the adsorption of NO3- and *H and facilitating the transition from *NO2NO to *NO2HNOH. Consequently, the Co3CuN delivers noticeably better NO3-RR activity than the pristine Co4N, with optimal Faradaic efficiency of 97 % and ammonia yield of 455.3 mmol h(-1) cm(-2) at -0.3 V vs. RHE. This work provides an effective strategy for developing high-performance heterogeneous catalyst for electrochemical synthesis.

• 单位
  y; 中国科学院