Publication date: 15th December 2025
Electrocatalytic nitrate reduction (NO₃RR) offers a sustainable pathway for the synthesis of value-added nitrogen-containing chemicals, such as ammonia, and the remediation of nitrogen contaminants in water systems. Investigating NO3RR is also essential for understanding fundamental electrochemical C–N coupling processes, where the activation and hydrogenation of nitrogen–oxygen species govern product selectivity and efficiency [1]. For this reason, exploring the fundamental mechanism of this reaction is crucial for advancing sustainable nitrogen conversion technologies. However, NO3RR is strongly influenced by factors such as electrode material, applied potential, and electrolyte composition [2,3]. Moreover, NO3RR presents significant challenges, arising from the formation of transient nitrogen–oxygen intermediates, which makes its mechanistic understanding challenging [4]. This complexity underscores the need for combined electrochemical and in situ techniques capable of resolving the elementary steps and active species involved.
In this work, we employ silver as a model electrocatalyst to probe the elementary electron transfer steps of NO3RR to nitrite in a neutral electrolyte. A combination of electrochemical characterisation techniques, including cyclic voltammetry and scanning electrochemical microscopy, is used to monitor the dynamic evolution of key reaction intermediates [5]. This correlation provides information on the NO3RR mechanism over silver surfaces and highlights the importance of a rigorous electrochemical characterisation benchmarking. This opens an avenue to accurately compare NO3RR activity across different electrocatalysts, assessing their role in the rate-limiting nitrate-to-nitrite reduction step.
We acknowledge Grant Ref. PID2023-151780OB-I00 funded by the Spanish Ministry of Science, Innovation and Universities MICIU/AEI/10.13039/501100011033 and the European Regional Development Fund (FEDER) from the European Union for funding this work. Jaxiry Barroso Martínez acknowledges the support of the predoctoral program AGAUR-FI ajuts (2023 FI-3 00065) Joan Oró funded by the Secretariat of Universities and Research of the Department of Research and Universities of the Generalitat of Catalonia and the European Social Plus Fund.
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