Efficient Neutral Nitrate-to-Ammonia Electrosynthesis Using Synergistic Ru-Based Nanoalloys on Nitrogen-Doped Carbon

Published in Chemistry and Materials

Efficient Neutral Nitrate-to-Ammonia Electrosynthesis Using Synergistic Ru-Based Nanoalloys on Nitrogen-Doped Carbon
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Efficient Neutral Nitrate-to-Ammonia Electrosynthesis Using Synergistic Ru-Based Nanoalloys on Nitrogen-Doped Carbon - Nano-Micro Letters

Electrocatalytic nitrate reduction reaction (NO3RR) represents a sustainable and environmentally benign route for ammonia (NH3) synthesis. However, NO3RR is still limited by the competition from hydrogen evolution reaction (HER) and the high energy barrier in the hydrogenation step of nitrogen-containing intermediates. Here, we report a selective etching strategy to construct RuM nanoalloys (M = Fe, Co, Ni, Cu) uniformly dispersed on porous nitrogen-doped carbon substrates for efficient neutral NH3 electrosynthesis. Density functional theory calculations confirm that the synergic effect between Ru and transition metal M modulates the electronic structure of the alloy, significantly lowering the energy barrier for the conversion of *NO2 to *HNO2. Experimentally, the optimized RuFe-NC catalyst achieves 100% Faraday efficiency with a high yield rate of 0.83 mg h−1 mgcat−1 at a low potential of − 0.1 V vs. RHE, outperforming most reported catalysts. In situ spectroscopic analyses further demonstrate that the RuM-NC effectively promotes the hydrogenation of nitrogen intermediates while inhibiting the formation of hydrogen radicals, thereby reducing HER competition. The RuFe-NC assembled Zn-NO3− battery achieved a high open-circuit voltage and an outstanding power density and capacity, which drive selective NO3− conversion to NH3. This work provides a powerful synergistic design strategy for efficient NH3 electrosynthesis and a general framework for the development of advanced multi-component catalysts for sustainable nitrogen conversion.

As fertilizer demand rises and nitrate pollution spreads, turning waste NO3- into green NH3 has become urgent. Now, researchers from Guizhou University, Hunan Agricultural University and Shanghai University, led by Professor Jili Yuan, Professor Wei Li and Dr Liang Wang, report a selective-etching route to RuM (M = Fe, Co, Ni, Cu) nanoalloys that deliver 100 % Faradaic efficiency for neutral ammonia electro-synthesis at only −0.1 V vs RHE—outperforming most catalysts reported to date.

Why RuM Nanoalloys Matter
   • Energy Efficiency: Alloying shifts the Ru d-band center upward, cutting the *NO2 → *HNO2 barrier to 0.46 eV and suppressing the hydrogen-evolution side-reaction that normally wastes electrons.
   • In-Electrode Conversion: The porous nitrogen-doped carbon host ensures rapid proton/electron delivery, enabling 0.83 mg NH3 h-1 mgcat-1 at room temperature without external heat or pressure.
   • Circular Nitrogen Economy: When assembled into a Zn–NO3- battery the cathode produces 0.688 mg NH3 h-1 mgcat-1 while delivering 10.16 mW cm-2 power—turning nitrate remediation into a self-powered chemical plant.

Innovative Design and Features
   • Nanoalloy Types: RuFe-NC, RuCo-NC, RuNi-NC and RuCu-NC (2–3 nm) are etched in molten urea/NaCl, yielding lattice-contracted (101) planes and uniform metal dispersion verified by HR-TEM, XRD and XPS.
   • Functional Support: Chloride-assisted etching creates mesopores (20–50 nm) that triple the electrochemical surface area, while nitrogen dopants anchor alloys and lower the work function for faster electron injection.
   • Device Architecture: Drop-cast on carbon paper, the catalysts serve as air-breathing cathodes in H-cells and coin-type Zn batteries, demonstrating scalability from 1 cm2 lab cells to 24 h continuous timers.

Applications and Future Outlook
   • Multi-Level Selectivity: RuFe-NC reaches 100 % NH3 FE at −0.1 V, while RuCo-NC maintains 98 % FE after 12 cycles and 96 % in 0.05 M NO3-—a tolerance window critical for real wastewater.
   • Digital Logic Gates: The catalyst layer doubles as a low-potential sensor pixel; changes in NH3 FE are converted to voltage signals, offering a new route for nitrate-aware IoT nodes.
   • Artificial Nitrogen Fixation: In-situ Raman, EPR and ATR-SEIRAS reveal *HNO2 and *NH2 intermediates, confirming a synergy-driven pathway that can be generalized to Co-, Ni- or Cu-based ternary alloys for urea, hydrazine or C–N bond construction.
   • Challenges and Opportunities: The team highlights the need for roll-to-roll etching protocols, membrane-electrode assemblies that separate NH3 from the electrolyte, and life-cycle studies comparing energy input to Haber–Bosch. Future work will explore Ru–Co–Fe trimetallics and AI-guided composition tuning to push onset potentials above 0 V RHE.

 This work provides materials chemists, environmental engineers and energy-storage designers with a universal alloying blueprint for turning nitrate waste into carbon-free ammonia while co-generating electricity. Stay tuned for more advances from Professor Jili Yuan, Professor Wei Li and Dr Liang Wang!

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Nanoscale Design, Synthesis and Processing
Physical Sciences > Materials Science > Nanotechnology > Nanoscale Design, Synthesis and Processing
Metals and Alloys
Physical Sciences > Chemistry > Materials Chemistry > Metals and Alloys
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Porous Materials
Physical Sciences > Chemistry > Materials Chemistry > Porous Materials
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Physical Sciences > Chemistry > Chemical Synthesis > Catalyst Synthesis
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    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.