Alloying of Cu with Ru Enabling the Relay Catalysis for Reduction of Nitrate to Ammonia

2023/03/05 by Wensheng Gao, Kefeng Xie, Jin Xie +6 · 3 citations
Chemical Engineering · Chemistry · Computer Science · #Ammonia Synthesis and Nitrogen Reduction #Caching and Content Delivery #Nanomaterials for catalytic reactions

paper · pdf · doi:10.1002/adma.202202952

openalex publication_date 2023/03/05 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

Abstract Involving eight electron transfer process and multiple intermediates of nitrate (NO 3 − ) reduction reaction leads to a sluggish kinetic and low Faradaic efficiency, therefore, it is essential to get an insight into the reaction mechanism to develop highly efficient electrocatalyst. Herein, a series of reduced‐graphene‐oxide‐supported RuCu alloy catalysts (Ru x Cu x /rGO) are fabricated and used for the direct reduction of NO 3 − to NH 3 . It is found that the Ru 1 Cu 10 /rGO shows the ammonia formation rate of 0.38 mmol cm −2 h −1 (loading 1 mg cm −2 ) and the ammonia Faradaic efficiency of 98% under an ultralow potential of −0.05 V versus Reversible Hydrogen Electode (RHE), which is comparable to Ru catalyst. The highly efficient activity of Ru 1 Cu 10 /rGO can be attributed to the synergetic effect between Ru and Cu sites via a relay catalysis, in which the Cu shows the exclusively efficient activity for the reduction of NO 3 − to NO 2 − and Ru exhibits the superior activity for NO 2 − to NH 3 . In addition, the doping of Ru into Cu tunes the d‐band center of alloy and effectively modulates the adsorption energy of the NO 3 − and NO 2 − , which promotes the direct reduction of NO 3 − to NH 3 . This synergetic electrocatalysis strategy opens a new avenue for developing highly efficient multifunctional catalysts.

Citations

• Projector augmented-wave method
• Efficient iterative schemes for<i>ab initio</i>total-energy calculations using a plane-wave basis set
• A consistent and accurate<i>ab initio</i>parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
• Unveiling the Activity Origin of a Copper‐based Electrocatalyst for Selective Nitrate Reduction to Ammonia
• Enhanced Nitrate-to-Ammonia Activity on Copper–Nickel Alloys via Tuning of Intermediate Adsorption
• Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters
• Alternative route for electrochemical ammonia synthesis by reduction of nitrate on copper nanosheets
• Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst
• Theoretical Insights into the Mechanism of Selective Nitrate‐to‐Ammonia Electroreduction on Single‐Atom Catalysts
• Electrocatalytic Nitrate Reduction for Sustainable Ammonia Production
• Electrocatalytic nitrate/nitrite reduction to ammonia synthesis using metal nanocatalysts and bio-inspired metalloenzymes
• Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst
• Nitrate electroreduction: mechanism insight, <i>in situ</i> characterization, performance evaluation, and challenges
• Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion
• Built‐in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra‐Low Concentration and Electroreduction to Ammonia
• Highly reactive Cu-Pt bimetallic 3D-electrocatalyst for selective nitrate reduction to ammonia
• Theoretical Insights into Superior Nitrate Reduction to Ammonia Performance of Copper Catalysts
• Structurally Disordered RuO₂ Nanosheets with Rich Oxygen Vacancies for Enhanced Nitrate Electroreduction to Ammonia
• Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia
• Efficient Electrochemical Nitrate Reduction to Ammonia with Copper‐Supported Rhodium Cluster and Single‐Atom Catalysts

Cited by

• Efficient Neutral Nitrate-to-Ammonia Electrosynthesis Using Synergistic Ru-Based Nanoalloys on Nitrogen-Doped Carbon
• Exposure of Active Metal Sites on Cu ₁₄ Nanoclusters for Highly Selective Electrocatalytic Nitrate Reduction
• Unveiling the Reaction Mechanism of Nitrate Reduction to Ammonia Over Cobalt-Based Electrocatalysts

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