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Atomic‐Dispersed Cu Catalysts for Electrochemical Nitrate Reduction: Coordination Engineering and Fundamental Insights

Xiaorong Zhu, Xiaolei Yuan, Ming Ge, Yanfeng Tang

2024Small15 citationsDOIOpen Access PDF

Abstract

Abstract The development of Cu‐based atomic dispersed catalysts with tailored coordination environments represents a significant step forward in enhancing the electrocatalytic reduction of nitrate to ammonia. By precisely modulating the electronic structures of Cu active centers, the binding strength of the * NO 3 intermediates is successfully tuned, thereby substantially improving the catalytic activity toward electrochemical nitrate reduction reaction (eNO 3 RR). This study reveals that the N 4 ‐coordinated Cu single‐atom catalyst (Cu‐SAC) exhibits superior performance due to its robust interaction with coordinating atoms. Notably, this optimized catalyst achieves a low limiting potential of −0.38 V, while the dual‐atom system further reduces this value to −0.32 V, demonstrating exceptional activity. Detailed electronic structure analysis, including the examination of d ‐band centers, Bader charges, and projected density of states (PDOS), provides a comprehensive understanding of the origin of this high activity. Specifically, the high and concentrated density of states near the Fermi level plays a crucial role in facilitating the electrocatalytic nitrate reduction process. This work not only offers crucial insights into the underlying mechanisms of eNO 3 RR but also provides valuable guidelines for the rational design of highly efficient electrocatalysts for this important reaction.

Topics & Concepts

CatalysisElectrochemistryAtom (system on chip)Ammonia productionNitrateAmmoniaMaterials scienceFermi levelRedoxSelective catalytic reductionLimitingDensity functional theoryChemical physicsNanotechnologyChemistryCombinatorial chemistryInorganic chemistryComputational chemistryPhysical chemistryElectrodeComputer sciencePhysicsOrganic chemistryQuantum mechanicsEmbedded systemMechanical engineeringEngineeringElectronAmmonia Synthesis and Nitrogen ReductionAdvanced Photocatalysis TechniquesNanomaterials for catalytic reactions