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Asymmetric Pulsed Electrolysis Enhances Nitrate-to-Ammonia Electroreduction via Optimizing the Local Reaction

Yidi Wu1,2, Weiliang Zhou1,2, Zhiyi Chen1,2

  • 1Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China.

ACS Applied Materials & Interfaces
|February 5, 2026
PubMed
Summary

Asymmetric pulsed electrolysis significantly boosts ammonia production from nitrate reduction, optimizing the catalyst

Keywords:
CuMn alloyammoniaasymmetric pulsed electrolysislocal reaction microenvironmentnitrate reduction reaction

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Area of Science:

  • Electrochemistry
  • Catalysis
  • Environmental Chemistry

Background:

  • Electrocatalytic nitrate reduction (NO3-RR) is crucial for ammonia synthesis.
  • Pulsed electrolysis is a promising, yet understudied, method to enhance NO3-RR.
  • The effects of symmetric vs. asymmetric pulsed electrolysis on NO3-RR are not well understood.

Purpose of the Study:

  • To investigate the impact of symmetric and asymmetric pulsed electrolysis on NO3-RR performance.
  • To elucidate the mechanisms by which pulsed electrolysis influences NO3-RR.
  • To optimize pulsed electrolysis parameters for enhanced ammonia (NH3) production.

Main Methods:

  • Utilized a CuMn alloy as a model catalyst for NO3-RR.
  • Employed symmetric and asymmetric pulsed electrolysis techniques.
  • Conducted operando measurements and control experiments to analyze reaction intermediates and local microenvironment.

Main Results:

  • Asymmetric pulsed electrolysis optimized the catalyst's local microenvironment, improving NO3- coverage and N-intermediate generation.
  • Asymmetric pulsed electrolysis suppressed the hydrogen evolution reaction (HER).
  • Optimal asymmetric pulsed electrolysis achieved 94.03% Faradaic efficiency and 9.13 mg h-1 cm-2 NH3 yield, outperforming static electrolysis.

Conclusions:

  • Asymmetric pulsed electrolysis is a superior strategy for enhancing electrocatalytic nitrate reduction to ammonia.
  • The method shows improved performance at lower nitrate concentrations.
  • This approach offers a feasible pathway for efficient ammonia synthesis via NO3-RR.