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Nitrogen is an essential element in biological systems, forming a crucial component of proteins, nucleic acids, and other cellular constituents. Many bacteria and archaea acquire nitrogen in the form of nitrate (NO₃⁻) or ammonia (NH₃), which are then assimilated into biomolecules through specific enzymatic pathways.Assimilatory Nitrate ReductionWhen nitrate enters the cell, it undergoes a two-step reduction process known as assimilatory nitrate reduction. Initially, the enzyme nitrate reductase...

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Mechanistic Insight Into Electrocatalytic Nitrogen Reduction to Ammonia Over PdBi Single-Atom Alloys.

Jianglin Tu^1,2, Hang Zhao^1,2, Zhefei Pan^1,2

¹Key Laboratory of Low-grade Energy Utilization Technologies and Systems (Chongqing University), Ministry of Education, Chongqing, China.

Small (Weinheim an Der Bergstrasse, Germany)

|July 10, 2026

Summary

This study developed a palladium-bismuth single-atom alloy for electrocatalytic nitrogen reduction, significantly improving ammonia production efficiency. The catalyst enhances nitrogen activation and lowers energy barriers, offering a promising route for sustainable ammonia synthesis.

Keywords:

ammonia synthesis electrocatalytic N2 reduction reaction electronic structure single‐atom alloys

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Published on: June 24, 2022

Area of Science:

Materials Science
Electrochemistry
Catalysis

Background:

Electrocatalytic nitrogen reduction is key for sustainable ammonia production but faces challenges like high energy barriers and hydrogen evolution competition.
Understanding the mechanism of electrocatalytic nitrogen reduction over single-atom alloys is crucial for catalyst design.

Purpose of the Study:

To investigate the mechanism of electrocatalytic nitrogen reduction reaction (NRR) over palladium-bismuth (PdBi) single-atom alloys.
To engineer an efficient and stable PdBi single-atom alloy catalyst for ammonia synthesis.

Main Methods:

Preparation of PdBi single-atom alloy by anchoring Bi single atoms onto Pd nanosheets.
Electrocatalytic performance evaluation for NRR, including ammonia yield and Faradaic efficiency.
Computational analysis to understand the electronic coupling and energy barriers.

Main Results:

The PdBi single-atom alloy demonstrated enhanced N2 adsorption-activation and a reduced free-energy barrier for the rate-determining step.
Optimized PdBi10 alloy achieved an ammonia yield of 46.9 µg h⁻¹ mg⁻¹ with 13.3% Faradaic efficiency at -0.2 V (vs. RHE).
The catalyst exhibited superior activity and long-term stability for electrocatalytic nitrogen reduction.

Conclusions:

Electronic coupling between Bi and Pd atoms in the single-atom alloy optimizes charge distribution, facilitating NRR.
The study provides mechanistic insights into PdBi single-atom alloys for NRR and offers design principles for future electrocatalyst development.
Engineered single-atom alloys show potential for efficient and durable ammonia production via electrocatalytic nitrogen reduction.