Work

Metal-Dependent Intermediate Evolution in Tandem Cu–M Catalysts for Electrocatalytic Ammonia Synthesis from Nitrate

Year: 2026

Type: article

Abstract: Electrocatalytic nitrate reduction to ammonia (NH3) offers a sustainable alternative to the Haber–Bosch process while enabling remediation of nitrate-contaminated water. However, the mechanistic origin of performance differences among bimetallic catalysts remains poorly understood, particularly regarding the metal-dependent evolution of reaction intermediates. Here, we construct a series of phase-pure tandem Cu–M catalysts (M = Co, Ni, Fe, Sn) by physically integrating commercial nanoparticles to examine the role of the secondary metal. In this architecture, Cu governs nitrate adsorption and its initial reduction to nitrite, whereas M dictates downstream hydrogenation toward NH3. Operando ATR–FTIR spectroscopy reveals that NH3 FE is determined by the hydrogenation kinetics of nitrite-derived intermediates rather than nitrate activation itself. Among the examined systems, Cu–Co achieves optimal kinetic matching, enabling rapid nitrite consumption and continuous hydrogenation, delivering an ammonia Faradaic efficiency of 91.2% with minimal nitrite accumulation (~1.0%) and a yield rate of 0.86 mmol h−1 cm−2 at −0.5 V vs. RHE. In contrast, Ni and Fe exhibit sluggish hydrogenation, while Sn induces pronounced intermediate buildup. These findings identify nitrite hydrogenation as the selectivity-determining step in tandem nitrate reduction and establish the chemical nature of the secondary metal as a decisive descriptor for rational catalyst design.

Source: Catalysts

DOI: 10.3390/catal16050402

Authors: Lewa Zhang, Joseph Cao, Bowen Liu, Rongze Li, Bangwei Deng, Chenyuan Zhu

Institutions: University of Electronic Science and Technology of China, Huzhou Normal University, Fudan University, University of Liverpool

Language: English

Topic: Ammonia Synthesis and Nitrogen Reduction

Subfield: Catalysis

Field: Chemical Engineering

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $2,654

Funder: Key Research and Development Program of Zhejiang Province