Unveiling Ionized Interfacial Water-Induced Localized H* Enrichment for Electrocatalytic Nitrate Reduction.

Area of Science:

• Electrochemistry
• Catalysis
• Materials Science

Background:

• Electrocatalytic nitrate reduction (NO3RR) is crucial for ammonia synthesis.
• Optimizing ammonia yield and Faradaic efficiency (FE) requires understanding active hydrogen (H*) supply.
• Current strategies need improvement for efficient NO3RR.

Purpose of the Study:

• To synthesize and investigate atomically precise copper-halide clusters for NO3RR.
• To elucidate the role of halogen atoms in enhancing catalytic performance.
• To establish a localized active hydrogen enrichment strategy for improved ammonia synthesis.

Main Methods:

• Synthesis of copper-halide clusters: Cu2X2(BINAP)2 (X=Cl, Br, I).
• Electrocatalytic performance evaluation for NO3RR.
• In situ experiments and theoretical calculations to analyze reaction mechanisms.

Main Results:

• Cu2Cl2(BINAP)2 cluster demonstrated optimal ammonia FE of 94.0% and yield rate of 373.5 μmol h−1 cm−2.
• Halogen atoms, particularly Cl, influence alkali metal-ionized water proximity on the catalyst surface.
• Enhanced water dissociation leads to localized H* enrichment, promoting nitrate hydrogenation.

Conclusions:

• The study highlights the critical role of localized active hydrogen enrichment in NO3RR.
• Atomically precise copper-halide clusters offer a promising pathway for efficient ammonia production.
• Understanding catalyst-water interactions is key to designing advanced electrocatalysts.