# Sustainable Ammonia Electrosynthesis Coupled With Glycerol Valorization via an Adaptive Tri‐Component Catalyst

## TL;DR

A new tri-component catalyst boosts ammonia production efficiency and integrates with glycerol conversion, offering a sustainable chemical synthesis strategy.

## Contribution

A tri-component Cu-Ni-W catalyst with high efficiency and synergy for ammonia electrosynthesis and glycerol valorization is introduced.

## Key findings

- The catalyst achieves 97.1% Faradaic efficiency and 43.87 mg h⁻¹ cm⁻² ammonia yield rate.
- Synergistic roles of Cu, Ni, and W components enhance ammonia selectivity and suppress hydrogen evolution.
- Coupling with glycerol valorization demonstrates energy-efficient system design for industrial reactions.

## Abstract

Electrochemical nitrate reduction represents a promising route for sustainable ammonia (NH3) production, yet its practical deployment is constrained by the limited efficiency of state‐of‐the‐art electrocatalysts and immature system architectures. Here, we report a generalist copper–nickel–tungsten tri‐component tandem electrocatalyst via a sequential microwave‐hydrothermal deposition route. Under pulsed electrolysis conditions, the catalyst delivers a remarkable Faradaic efficiency of 97.1% and a record‐high ammonia yield rate of 43.87 mg h−1 cm−2. Online differential electrochemical mass spectrometry (DEMS) identifies key intermediates and associated pathways, while density functional theory (DFT) calculations elucidate the cooperative roles of each component: the copper component facilitates nitrate adsorption and deoxygenation, the nickel component promotes water dissociation for steady *H supply, and the tungsten component serves as a dynamic *H reservoir. This synergy efficiently suppresses hydrogen evolution and enhances ammonia selectivity. Furthermore, coupling with glycerol valorization (to formic acid) as the anodic reaction demonstrates the potential for energy‐efficient ammonia electrosynthesis. Collectively, this work offers both design strategies and mechanistic understanding for next‐generation multi‐component tandem electrocatalysts targeting advanced nitrogen‐based chemical synthesis.

A Cu‐Ni‐W tri‐component catalyst enables efficient nitrate‐to‐ammonia conversion under pulsed electrolysis. Combined experimental and theoretical studies attribute its performance to component synergism and regulated intermediates. Its facile adaptation for glycerol valorization to formic acid underscores a versatile system design concept, advancing electrochemical coupling strategies for a broad spectrum of industrially relevant reactions.