Ammonia Electrosynthesis from Nitrate Using a Ruthenium–Copper Cocatalyst System: A Full Concentration Range Study

2023/12/28 by Qikun Hu, Ke Yang, Ouwen Peng +9
Chemical Engineering · Computer Science · Energy · #Advanced Photocatalysis Techniques #Ammonia Synthesis and Nitrogen Reduction #Caching and Content Delivery

paper · doi:10.1021/jacs.3c10516

openalex publication_date 2023/12/28 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/31

Abstract

Electrochemical synthesis of ammonia via the nitrate reduction reaction (NO3RR) has been intensively researched as an alternative to the traditional Haber–Bosch process. Most research focuses on the low concentration range representative of the nitrate level in wastewater, leaving the high concentration range, which exists in nuclear and fertilizer wastes, unexplored. The use of a concentrated electrolyte (≥1 M) for higher rate production is hampered by poor hydrogen transfer kinetics. Herein, we demonstrate that a cocatalytic system of Ru/Cu 2 O catalyst enables NO3RR at 10.0 A in 1 M nitrate electrolyte in a 16 cm 2 flow electrolyzer, with 100% faradaic efficiency toward ammonia. Detailed mechanistic studies by deuterium labeling and operando Fourier transform infrared (FTIR) spectroscopy allow us to probe the hydrogen transfer rate and intermediate species on Ru/Cu 2 O. Ab initio molecular dynamics (AIMD) simulations reveal that adsorbed hydroxide on Ru nanoparticles increases the density of the hydrogen-bonded water network near the Cu 2 O surface, which promotes the hydrogen transfer rate. Our work highlights the importance of engineering synergistic interactions in cocatalysts for addressing the kinetic bottleneck in electrosynthesis.

Citations

• Unveiling the Activity Origin of a Copper‐based Electrocatalyst for Selective Nitrate Reduction to Ammonia
• Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters
• Recent advances in non-noble metal electrocatalysts for nitrate reduction
• Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst
• Restoring the Nitrogen Cycle by Electrochemical Reduction of Nitrate: Progress and Prospects
• Recent discoveries in the reaction mechanism of heterogeneous electrocatalytic nitrate reduction
• Electrocatalytic Nitrate Reduction for Sustainable Ammonia Production
• A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate
• Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst
• Nitrate reduction to ammonium: from CuO defect engineering to waste NO _x -to-NH ₃ economic feasibility
• Nitrate electroreduction: mechanism insight, <i>in situ</i> characterization, performance evaluation, and challenges
• Pd doping-weakened intermediate adsorption to promote electrocatalytic nitrate reduction on TiO ₂ nanoarrays for ammonia production and energy supply with zinc–nitrate batteries
• Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion
• Efficient Ammonia Electrosynthesis and Energy Conversion through a Zn‐Nitrate Battery by Iron Doping Engineered Nickel Phosphide Catalyst
• Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst
• Hydrogen bond network connectivity in the electric double layer dominates the kinetic pH effect in hydrogen electrocatalysis on Pt
• Active hydrogen boosts electrochemical nitrate reduction to ammonia
• Sub-nm RuO_<i>x</i> Clusters on Pd Metallene for Synergistically Enhanced Nitrate Electroreduction to Ammonia
• Ultralow overpotential nitrate reduction to ammonia via a three-step relay mechanism

Related

• Sub-nm RuO_<i>x</i> Clusters on Pd Metallene for Synergistically Enhanced Nitrate Electroreduction to Ammonia
• Unveiling the Reaction Mechanism of Electrochemical Nitrate Reduction to Ammonia on a Cu/Cu ₂ O Heterojunction Catalyst
• Electrocatalytic Hydrogenation Boosts Reduction of Nitrate to Ammonia over Single-Atom Cu with Cu(I)-N₃C₁ Sites
• Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters
• Thermally Enhanced Relay Electrocatalysis of Nitrate-to-Ammonia Reduction over Single-Atom-Alloy Oxides