Atomically Dispersed Cu Sites on Dual‐Mesoporous N‐Doped Carbon for Efficient Ammonia Electrosynthesis from Nitrate

Abstract

The industrial Haber-Bosch process for ammonia synthesis is extremely important in modern society. However, it is energy intensive and leads to severe pollution, which has motivated eco-friendly NH₃ synthesis research. Electroreduction of contaminant nitrate ions back to NH₃ is an effective complement but is still limited by low NH₃ yields and nitrate-to-NH₃ selectivities. In this study, the electrochemical nitrate reduction reaction (NTRR) is carried out over a single-atom Cu catalyst. Atomically dispersed Cu sites anchored on dual-mesoporous N-doped carbon framework display excellent NTRR performance with NH₃ production rate of 13.8 mol <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mrow></mml:mrow> <mml:mrow><mml:mi>NH</mml:mi> <mml:msub><mml:mrow></mml:mrow> <mml:mn>3</mml:mn></mml:msub> </mml:mrow> </mml:msub> </mml:math> g_cat ^-1 h^-1 and NO₃ ^- -to-NH₃ faradaic efficiency (FE) of 95.5 % at -1.0 V. Cu-N-C catalyst can sustain continuous 120 h NTRR test in the simulated NH₃ synthesis scenarios with large current density (about 200 mA cm^-2 ) and amplified volume of NO₃ ^- solution (9 times). Theoretical calculations reveal that atomically dispersed Cu₁ -N₄ sites reduce the energy barrier of potential-determining step in NTRR and promote the decomposition of primary intermediate in NO₃ ^- -to-N₂ process. These findings provide a guideline for the rational design of highly active, selective and durable electrocatalysts for the NTRR.