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Asymmetric Electronic Distribution at Mn–Cu Dual Atomic Sites Promoting Electrochemical Conversion of N <sub>2</sub> to NH <sub>3</sub>

Sudip Biswas, Jingwen Zhou, Xue‐Lu Chen, Qingying Zhang, Yan‐Ruo Li, Peixin Cui, Chungen Liu, Xing‐Hua Xia

2025Angewandte Chemie International Edition10 citationsDOI

Abstract

Abstract Electrochemical synthesis of ammonia (NH 3 ) is a promising green alternative to the conventional Haber‐Bosch process. Here, we report the synthesis of a heteroatomic metal–metal bonded dual atomic (DA) Mn–Cu catalytic site embedded within nitrogen‐doped carbon (NC) matrix for high‐performance electrochemical reduction of N 2 to NH 3 . The asymmetric electronic distribution localized at the dual atomic sites synergistically enhances the adsorption and activation of N 2 , facilitating the complex proton‐coupled electron transfer process. Compared to single atomic (SA)–Mn/NC, DA–MnCu/NC exhibits a fourfold increase in nitrogen reduction reaction (NRR) performance, achieving a higher Faradaic efficiency of 67.76 ± 0.7% and 88.34 ± 3.6 µg mg cat −1 h −1 at −0.15 V (versus RHE) in 0.5 M NaBF 4 medium. Furthermore, the catalyst demonstrates long‐term stability, retaining its performance over extended operation. This work presents valuable insights into the design of dual atomic catalysts and highlights the critical role of the localized electronic distribution at the catalytic sites in enabling sustainable NH 3 synthesis.

Topics & Concepts

CatalysisElectrochemistryFaraday efficiencyAmmonia productionMaterials scienceAmmoniaElectron transferDual (grammatical number)AdsorptionNitrogenChemistryWork (physics)Matrix (chemical analysis)Selective catalytic reductionReduction (mathematics)Carbon fibersInorganic chemistryChemical physicsLigand (biochemistry)Distribution (mathematics)Chemical engineeringYield (engineering)NanotechnologyAtomic unitsPhysical chemistryElectrochemical cellElectrodeElectronic structureElectrocatalystAmmonia Synthesis and Nitrogen ReductionAdvanced Photocatalysis TechniquesHydrogen Storage and Materials