Ammonia Yield Research Articles

Triggering Heteroatom Ensemble Effect over RuFe Alloy to Promote Nitrogen Chemisorption for Efficient Ammonia Electrosynthesis at Ambient Conditions.

Ammonia (NH3) electrosynthesis from nitrogen (N2) provides a promising strategy for carbon neutrality, circumventing the energy-intensive and carbon-emitting Haber-Bosch process. However, the current system still presents unsatisfactory performance, and the bottleneck lies in the rational synthesis of catalytic centers with efficient N2 chemisorption ability. Herein, a heteroatom ensemble effect is deliberately triggered over RuFe alloy with spatial proximity of metal sites to promote electrocatalytic nitrogen reduction. The heteronuclear RuFe ensemble with increased surface polarization and modulated electronic structure offers the feasibility to optimize the adsorption configuration of electroactive substances and facilitate chemical bond scission. The promotion of N2 chemisorption and the following hydrogenation are demonstrated by the in situ Fourier transform infrared spectroscopy characterizations. The catalyst thus permits significantly enhanced conversion of N2 to NH3 in a 0.1 M HCl environment, with a maximum ammonia yield rate of 75.45 μg h-1 mg-1 and a high Faradaic efficiency of 35.49%.

Unveiling Ionized Interfacial Water-Induced Localized H* Enrichment for Electrocatalytic Nitrate Reduction.

Electrocatalytic nitrate reduction reaction (NO3RR) is a process that requires the participation of eight electrons and nine protons. The regulation of active hydrogen (H*) supply and a deep understanding of related processes are necessary for improving the ammonia yield rate and Faradaic efficiency (FE). Herein, we synthesized a series of atomically precise copper-halide clusters Cu2X2(BINAP)2 (X = Cl, Br, I), among which the Cu2Cl2(BINAP)2 cluster shows the optimal ammonia FE of 94.0% and an ammonia yield rate of 373 μmol h-1 cm-2. In situ experiments and theoretical calculations reveal that halogen atoms, especially Cl in Cu2Cl2(BIANP)2, can significantly affect the distance of alkali metal-ionized water on the catalyst surface, which can promote the water dissociation to enhance the localized H* enrichment for the continues hydrogenation of nitrate to ammonia. This work explains the role of H* in the hydrogenation process of NO3RR and the importance of localized H* enrichment strategy for improving the FEs.

Reversed I1Cu4 single-atom sites for superior neutral ammonia electrosynthesis with nitrate

Electrochemical ammonia (NH3) synthesis from nitrate reduction (NITRR) offers an appealing solution for addressing environmental concerns and the energy crisis. However, most of the developed electrocatalysts reduce NO3- to NH3 via a hydrogen (H*)-mediated reduction mechanism, which suffers from undesired H*-H* dimerization to H2, resulting in unsatisfactory NH3 yields. Herein, we demonstrate that reversed I1Cu4 single-atom sites, prepared by anchoring iodine single atoms on the Cu surface, realized superior NITRR with a superior ammonia yield rate of 4.36 mg h-1 cm-2 and a Faradaic efficiency of 98.5% under neutral conditions via a proton-coupled electron transfer (PCET) mechanism, far beyond those of traditional Cu sites (NH3 yield rate of 0.082 mg h-1 cm-2 and Faradaic efficiency of 36.5%) and most of H*-mediated NITRR electrocatalysts. Theoretical calculations revealed that I single atoms can regulate the local electronic structures of adjacent Cu sites in favor of stronger O-end-bidentate NO3- adsorption with dual electron transfer channels and suppress the H* formation from the H2O dissociation, thus switching the NITRR mechanism from H*-mediated reduction to PCET. By integrating the monolithic I1Cu4 single-atom electrode into a flow-through device for continuous NITRR and in situ ammonia recovery, an industrial-level current density of 1 A cm-2 was achieved along with a NH3 yield rate of 69.4 mg h-1 cm-2. This study offers reversed single-atom sites for electrochemical ammonia synthesis with nitrate wastewater and sheds light on the importance of switching catalytic mechanisms in improving the performance of electrochemical reactions.

Plasmonic‐Promoted Interatomic Hot Carriers Regulation Enhanced Electrocatalytic Nitrogen Reduction Reaction

Utilizing hot carriers for efficient plasmonic‐mediated chemical reactions (PMCRs) to convert solar energy into secondary energy is one of the most feasible solutions to the global environmental and energy crisis. Finding a plasmonic heterogeneous nanostructure with a more efficient and reasonable hot carrier transport path without affecting the intrinsic plasmonic properties is still a major challenge that urgently needs to be solved in this field. Herein, the mechanism by which plasmonic‐promoted interatomic hot electron redistribution on the surface of Au3Cu alloy nanoparticles promotes the electrocatalytic nitrogen reduction reaction (ENRR) is successfully clarified. The localized surface plasmon resonance (LSPR) effect can boost the transfer of plasmonic hot electrons from Au atoms to Cu atoms, trigger the interatomic electron regulation of Au3Cu alloy nanoparticles, enhance the desorption of ammonia molecules, and increase the ammonia yield by approximately 93.9%. This work provides an important reference for rationally designing and utilizing the LSPR effect to efficiently regulate the distribution and mechanism of plasmonic hot carriers on the surface of heterogeneous alloy nanostructures.

Bio-inspired catalysts for enhanced N₂ electroreduction to NH3: Architecting molecular screening interfaces via active sites microenvironment engineering

The electrochemical nitrogen reduction reaction (ENRR) promises a sustainable route for ammonia (NH3) production but faces hurdles from competing hydrogen evolution reaction (HER) and insufficient N2 concentration. Drawing inspiration from Tropical Lizards’ unique mechanism of creating a thin air layer on their hydrophobic skin, we modify the catalyst-water interface using alkyl thiols of different chain lengths on VS2 (Cx-VS2, x = 4,8,12). This novel approach suppresses HER and increases N2 availability. Among the tailored catalysts, C8-VS2 exhibits superior ENRR performance, with an ammonia yield of 58.43 μg h−1 mgcat−1 and a Faradaic efficiency of 34.69 % that surpasses unmodified VS2 (21.05 μg h−1 mgcat−1 and 8.87 %). Supporting measurements and density functional theory (DFT) calculations confirm the pivotal role of the modified interface in optimizing NH3 production. Our findings offer fresh perspectives for designing efficient electrocatalysts via tailoring interface microenvironments, with potential implications for various applications.

Plasmon-Promoted Interatomic Hot Carriers Regulation Enhanced Electrocatalytic Nitrogen Reduction Reaction.

Utilizing hot carriers for efficient plasmon-mediated chemical reactions (PMCRs) to convert solar energy into secondary energy is one of the most feasible solutions to the global environmental and energy crisis. Finding a plasmonic heterogeneous nanostructure with a more efficient and reasonable hot carrier transport path without affecting the intrinsic plasmonic properties is still a major challenge that urgently needs to be solved in this field. Herein, the mechanism by which plasmon-promoted interatomic hot electron redistribution on the surface of Au3Cu alloy nanoparticles promotes the electrocatalytic nitrogen reduction reaction (ENRR) is successfully clarified. The localized surface plasmon resonance (LSPR) effect can boost the transfer of plasmon hot electrons from Au atoms to Cu atoms, trigger the interatomic electron regulation of Au3Cu alloy nanoparticles, enhance the desorption of ammonia molecules, and increase the ammonia yield by approximately 93.9 %. This work provides an important reference for rationally designing and utilizing the LSPR effect to efficiently regulate the distribution and mechanism of plasmon hot carriers on the surface of heterogeneous alloy nanostructures.

Sustainable catalytic hydrogenation of high concentration nitrate to ammonia over Ruthenium-based catalysts

Elevated nitrate levels in natural water bodies significantly disrupt the global nitrogen cycle and pose a substantial environmental and human health risk. This study investigates the selective conversion of nitrate to ammonia via catalytic hydrogenation. This highly efficient and selective process offers a sustainable alternative to traditional ammonia production methods while simultaneously addressing nitrate pollution. Ruthenium (Ru) catalysts supported on ceria (CeO2), titania (TiO2), and tin dioxide (SnO2) were synthesized using a simple impregnation method, incorporating oxygen vacancies and low Palladium (Pd) loadings (0.25–0.5 wt%) to enhance catalytic performance. Ru-Pd/CeO2 exhibited superior activity and selectivity, maintaining near 100 % ammonia selectivity across various nitrate concentrations. At 75 °C, complete conversion of 2000 ppm nitrate to ammonia was achieved within 80 min using Ru-Pd/CeO2, and the yield of ammonia can reach up to 16440 mg•h−1•gRu-1. Subsequent ammonia enrichment through evaporation yielded pure ammonia solutions up to 3.6 wt%. Characterization and theoretical calculations suggest that abundant oxygen vacancies on the CeO2 surface and efficient hydrogen spillover from Pd nanoparticles synergistically contribute to the Ru-Pd/CeO2 catalyst’s superior performance. The catalyst exhibited excellent stability and reusability, maintaining high activity and selectivity over four cycles. This research presents a promising strategy for addressing nitrate pollution in water bodies while offering a sustainable and environmentally friendly route for ammonia synthesis. The findings of this study lay the foundation for further advancing and potentially implementing catalytic hydrogenation technology for nitrate pollution remediation and ammonia synthesis.

Efficient electrochemical nitrate reduction by iron phthalocyanine nanorods decorated on multi-walled carbon nanotubes

Electrochemical nitrate reduction reaction (NO3RR) has the dual effect of relieving nitrate contamination and producing the high value-added NH3, which calls for the creation of sophisticated electrodes in order to attain high yield rate, stability, and Faradaic efficiency (FENH3). In this study, iron-based conjugated molecule electrocatalyst, i.e. iron phthalocyanine (FePc), was fabricated into nanorods with excellent crystallinity by a facile precipitation method and applied in NO3RR electrode. The NO3RR performance is enhanced by decorating FePc nanorods on multi-walled carbon nanotubes (CNT) (denoted as FePc@CNT X:10) due to the improved dispersibility and electrical conductivity. The results disclose that FePc@CNT 6:10 exhibits the highest performance with a FENH3 of 94% at −0.45 V (vs. Reversible Hydrogen Electrode) and an ammonia yield rate of 0.35 mmol h−1 mgcat.−1. Notably, a significant NH3 partial current density of approximately 75 mA cm−2 is attained at −0.50 V, correlating with a marginally deteriorated FENH3 of 92.9% and an ammonia yield rate of 0.46 mmol h−1 mgcat.−1. Besides, this catalyst exhibits a long-term NO3RR stability with the ten consecutive cycles. Operando attenuated total reflection surface-enhanced infrared absorptive spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations reveal that NO3− undergoes deoxygenation and extensive hydrogenation steps and FePc is more likely to convert NO3− to NH3 under the ONH route. This work provides advanced insights into the rational design of metal phthalocyanine catalysts for electrocatalytic reactions.

Enhancement of Lithium-Mediated Nitrogen Reduction by Modifying Center Atom of Tetraalkyl-Type Ionic Liquids.

The lithium-mediated nitrogen reduction reaction (Li-NRR) offers a viable alternative to the Haber-Bosch process for ammonia production. However, ethanol, a common proton carrier in Li-NRR, exhibits electrochemical instability, leading to oxidation at the anode or byproduct formation at the cathode. This study replaces alcoholic proton carriers with ionic liquids (ILs), specifically tetrabutylphosphonium chloride (TBPCl) and tetrabutylammonium chloride (TBACl), to examine how the electronegativity differences between the central atom and adjacent carbon of the cation affect catalytic performance. The results show that switching the central atom in tetraalkyl-type ILs markedly enhances performance, specifically resulting in a 1.45-fold increase in Faradaic efficiency (FE) with the transition from phosphonium to ammonium cation of ILs. Additionally, optimal IL concentrations in the electrolyte are identified to maximize ammonia yield. TBACl, in particular, demonstrates enhanced ammonia production and operational stability, achieving an ammonia yield rate of 13.60 nmol/cm²/s, an FE of 39.5%, and operational stability for over 12 h under conditions of 10 mA/cm² and 10 atm. This research underscores the potential of precise IL modifications for more efficient and sustainable Li-NRR.

Enhancement of Lithium‐Mediated Nitrogen Reduction by Modifying Center Atom of Tetraalkyl‐Type Ionic Liquids

The lithium‐mediated nitrogen reduction reaction (Li‐NRR) offers a viable alternative to the Haber‐Bosch process for ammonia production. However, ethanol, a common proton carrier in Li‐NRR, exhibits electrochemical instability, leading to oxidation at the anode or byproduct formation at the cathode. This study replaces alcoholic proton carriers with ionic liquids (ILs), specifically tetrabutylphosphonium chloride (TBPCl) and tetrabutylammonium chloride (TBACl), to examine how the electronegativity differences between the central atom and adjacent carbon of the cation affect catalytic performance. The results show that switching the central atom in tetraalkyl‐type ILs markedly enhances performance, specifically resulting in a 1.45‐fold increase in Faradaic efficiency (FE) with the transition from phosphonium to ammonium cation of ILs. Additionally, optimal IL concentrations in the electrolyte are identified to maximize ammonia yield. TBACl, in particular, demonstrates enhanced ammonia production and operational stability, achieving an ammonia yield rate of 13.60 nmol/cm²/s, an FE of 39.5%, and operational stability for over 12 h under conditions of 10 mA/cm² and 10 atm. This research underscores the potential of precise IL modifications for more efficient and sustainable Li‐NRR.

CoNi layered double hydroxides grown on Ag nanowires for high-efficient nitrate-to-ammonia conversion

Electrocatalytic reduction of nitrate to ammonia is a promising technology. The sluggish rate of the nitrate-to-nitrite reduction is the core issue. By reducing the energy barrier of this step, the reactivity can be greatly promoted. Here, we have documented Co2Ni1 layered double hydroxide (LDH) on Ag nanowire (NW) that demonstrates efficient catalytic activity in electro-reducing nitrate to ammonia under a diverse set of application conditions. It achieves a high ammonia yield (2.50 mmol h−l cm−2) and Faradaic efficiency (99.6 %) at −0.7 V versus a reversible hydrogen electrode (VRHE). Through comparative experiments, it has been proven that the selective reduction of nitrate to nitrite on Ag NW is the key. This series of Ag NW heterostructure electrodes provides new insights into the design principles of high-performance and high-durability nitrate reduction electrodes under environmentally relevant wastewater conditions.

Nanoarchitectonics of S-Scheme Heterojunction Photocatalysts: A Nanohouse Design Improves Photocatalytic Nitrate Reduction to Ammonia Performance.

Photocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse-like S-scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano-house has a floor of plate-like metal organic framework-based photocatalyst (NH2-MIL-125), on which another photocatalyst Co(OH)2 nanosheet is grown while ZIF-8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF-8 wall can modulate the environment in the nanohouse by (i) NO3 - enrichment/NH4 + discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron-hole separation and strong redox capability in the NH2-MIL-125@Co(OH)2 S-scheme heterjunction confined in the nano-house, the designed photocatalyst delivers an ammonia yield of 2454.9 μmol g-1 h-1 and an apparent quantum yield of 8.02 % at 400 nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst.

Nanoarchitectonics of S‐Scheme Heterojunction Photocatalysts: A Nanohouse Design Improves Photocatalytic Nitrate Reduction to Ammonia Performance

AbstractPhotocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse‐like S‐scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano‐house has a floor of plate‐like metal organic framework‐based photocatalyst (NH2‐MIL‐125), on which another photocatalyst Co(OH)2 nanosheet is grown while ZIF‐8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF‐8 wall can modulate the environment in the nanohouse by (i) NO3− enrichment/NH4+ discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron‐hole separation and strong redox capability in the NH2‐MIL‐125@Co(OH)2 S‐scheme heterjunction confined in the nano‐house, the designed photocatalyst delivers an ammonia yield of 2454.9 μmol g−1 h−1 and an apparent quantum yield of 8.02 % at 400 nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst.

Mitigating Side Reactions in Electrocatalytic Ammonia Synthesis by Nitrate Reduction

Electrocatalytic nitrate reduction holds significant promise for generating green ammonia and mitigating pollution, reducing energy input, and exhibiting zero-carbon emissions. However, the intricate multiple electron and proton transfer processes complicate the pathways from nitrate to ammonia, hindering the development of electrocatalysts with high activity and selectivity for practical use. The primary side reactions, such as the conversion of nitrate to gaseous nitrogen species and the hydrogen reduction reaction, limit the Faradaic efficiency of nitrate-to-ammonia conversion. In this work, we have developed a controllable methodology for preparing highly active Cu-based nanocatalysts. These nanocatalysts exhibit remarkable activity and selectivity in the electrochemical nitrate reduction reaction within a flow-cell device, with a high ammonia yield and high Faradaic efficiency.

In Situ Fe/Co/B Codoped MoS2 Ultrathin Nanosheets Enable Efficient Electrocatalytic Nitrogen Reduction.

The development of sustainable and effective electrochemical nitrogen fixation catalysts is crucial for the mitigation of the terrible energy consumption resulting from the Haber-Bosch process. Molybdenum disulfide (MoS2) exhibits promise toward nitrogen reduction reaction (NRR) on account of its similar structure to natural nitrogenases MoFe-co but still undergoes serious challenges with unsatisfactory catalytic performance resulted from limited active sites, conductivity, and selectivity. In this work, Fe/Co/B codoped MoS2 ultrathin nanosheets are synthesized and verified as excellent NRR catalysts with high activity, selectivity, and durability. The FeCoB-MoS2 demonstrates a high ammonia yield of 36.99 μg h-1 mgcat-1 at -0.15 V vs RHE and Faraday efficiency (FE) of 30.65% at -0.10 V vs RHE in 0.1 M HCl. The experimental results and the density functional theory (DFT) calculations emphasize that codoping of Fe, Co, and B into MoS2 synergistically enhances its conductivity and optimizes the electronic structure of the catalyst, which significantly improves the electrocatalytic ammonia synthesis performance. This work broadens the potential and enlightens the strategy for designing efficient electrocatalysts in the NRR field.

FeTiO3/TiO2 heterojunction for the electrocatalytic and photo-assisted electrocatalytic reduction of nitric oxide into ammonia

FeTiO3/TiO2 (FTTO) was successfully synthesized and applied for both electrocatalytic NO reduction reaction (eNORR) and photo-assisted eNORR. By introducing Fe into TiO2, a heterojunction of FeTiO3/TiO2 was constructed to enhance the electron transfer capability. The large specific surface area of FTTO can provide more active sites. In the eNORR, the FTTO achieved an NH3 yield of 2845.82 μg h−1 mg−1 at a voltage of −0.70 V (vs. RHE) in K2SO4 solution, which is 2.04 times that of unmodified TiO2. In the photo-assisted eNORR, the FTTO photoelectrode showed superior ammonia yield of 4259.97 μg h−1 mg−1, which is 11.74 times of that under exclusive illumination and 1.50 times for eNORR. The Zn–NO battery system, using FTTO as the positive electrode and Zn as the negative electrode, demonstrated an open-circuit voltage (OCV) of 2.15 V vs. Zn and an NH3 yield of 388.72 μg h−1 mg−1 at a current density of 5 mA cm−2.

Unraveling the Active Sites on Mesoporous CuFe2O4@N-Carbon Catalysts with Abundant Oxygen Vacancies and M-N-C Content for Boosted Nitrogen Reduction Toward Electrosynthesis of Ammonia.

Transition metal centers dispersed over nitrogen-doped carbon (M-NC) supports have been widely explored for electrocatalytic reactions; however, sparsely reported for electrochemical nitrogen reduction reaction (ENRR). Particularly, the single-atom catalysts (SACs) have shown reasonable ammonia yield rate and faradaic efficiency (FE), but their complex synthesis and low durability for long-term electrocatalysis runs restrict their use on a larger scale. Importantly, the catalytic active sites in metal nanostructured-based M-NC catalysts toward enhanced N2 adsorption and activation are still not clear as they are highly challenging to reveal. A few studies have predicted that the surface oxygen vacancies (Ovac) favor an enhanced ENRR performance. Herein, a strategy using tailored M-NC content and Ovac in a single catalyst for enhanced ammonia electrosynthesis is devised. A mesoporous bimetallic spinel oxide (CuFe2O4) supported over N-doped carbon (CuFe2O4@NC) derived from Prussian blue analog (PBA) via controlled pyrolysis possess is found to show boosted ENRR activity. Moreover, operando NH3 formation over the catalyst is observed using four electrode set up. This approach enables rapid evaluation ofelectrocatalytic efficacy and avoids false positive results. The rotating disc electrode results reveal that mass transport in acidic media and surface absorption in alkline media primarily regulate ENRR over CuFe2O4@NC electrocatalyst.

Incorporating Zinc Metal Sites in Aluminum-Coordinated Porphyrin Metal-Organic Frameworks for Enhanced Photocatalytic Nitrogen Reduction to Ammonia.

Rationally designing photocatalysts is crucial for the solar-driven nitrogen reduction reaction (NRR) due to the stable N≡N triple bond. Metal-organic frameworks (MOFs) are considered promising candidates but suffer from insufficient active sites and inferior charge transport. Herein, it is demonstrated that incorporating 3d metal ions, such as zinc (Zn) or iron (Fe) ions, into Al-coordinated porphyrin MOFs (Al-PMOFs) enables the enhanced ammonia yield of 88.7 and 65.0µggcat -1h-1, 2.5- and 1.8-fold increase compared to the pristine Al-PMOF (35.4µggcat -1h-1), respectively. The origin of ammonia (NH3) is verified via isotopic labeling experiments. Incorporating Zn or Fe into Al-PMOF generates active sites in Al-PMOF, that is, Zn-N4 or Fe-N4 sites, which not only facilitates the adsorption and activation of N2 molecules but suppresses the charge recombination. Photophysical and theoretical studies further reveal the upshift of the lowest unoccupied molecular orbital (LUMO) level to a more energetic position upon inserting 3d metal ions (with a more significant shift in Zn than Fe). The promoted nitrogen activation, suppressed charge recombination, and more negative LUMO levels in Al-PMOF(3d metal) contribute to a higher photocatalytic activity than pristine Al-PMOF. This work provides a promising strategy for designing photocatalysts for efficient solar-to-chemical conversion.

Engineered wettability-gradient porous structure enabling efficient water manipulation in regenerative fuel cells

Regenerative fuel cells can operate alternately as an electrolyzer and as a fuel cell, frequently involving water as a reactant or product. Modifying the electrode surface to manipulate water can prevent electrode flooding and enhance the electrode's mass transfer efficiency by facilitating better contact with gaseous reactants. However, conventional electrodes face difficulties in allowing water droplets to penetrate in a single direction leaving electrodes. In this work to address this issue, a wettability gradient electrode is designed and fabricated for efficient water manipulation in regenerative fuel cells. The findings demonstrate that the water removal strategy in the electrolyzer mode yields the highest ammonia yield and Faradaic efficiency of 3.39 × 10-10 mol s-1 cm-2 and 0.49 %, respectively. Furthermore, in the fuel cell mode, the discharging process sustains for approximately 20.5 h, which is six times longer than the conventional strategy. The ability to sustain the discharging process for extended periods is particularly advantageous in regenerative fuel cells, as it enables the cells to operate for longer periods without the need for regeneration.

A Bio‐Inspired Dendritic MoOx Electrocatalyst for Efficient Electrochemical Nitrate Reduction to Ammonia

AbstractDrawing inspiration from the nitrate reductase enzymes, which catalyze nitrate to nitrite in nature, here a bio‐inspired, reduced molybdenum oxide (MoOx) shell is introduced that is grown on top of a dendritic nickel foam core (NiNF). The resulting MoOx/NiNF material is prepared via a facile, two‐step electrodeposition strategy using commercially available, low‐cost precursors. This catalytic material displays a remarkable faradaic efficiency (FE) of 99% at −0.5 V versus RHE and a high ammonia (NH3) yield rate of up to 4.29 mmol h−1 cm−2 at −1.0 V versus RHE in neutral media. Most importantly, MoOx/NiNF exhibits exceptional stability for the nitrate reduction reaction (NO3RR), maintaining operation for over 3100 h at a high current density of −650 mA cm−2, with a yield rate of 2.6 mmol h−1 cm−2 and a stable average NH3 FE of ≈83%. Through combined XPS and in situ Raman spectroscopy it is shown that the pronounced affinity of MoOx/NiNF for nitrate is associated with a substantial presence of oxygen vacancies within the material.