Efficient N2 Research Articles

Modulating Nitrogen Adsorption Mode and Microenvironment of Active Sites for Boosting Electrochemical Nitrogen Reduction.

Electrochemical reduction of N2(NRR) offers a sustainable approach for ammonia (NH3) synthesis, serving as a complementary to the traditional emission- and energy-intensive Haber-Bosch process. However, it faces challenges in N2 activation and competing with pronounced hydrogen evolution reaction (HER). Herein an efficient electrocatalyst comprised of ultrafine Ru nanoclusters (NCs) confined by a hydrophobic molecular layer is developed on the surface of 2D Ti3C2Tx for NRR. These experimental and theoretical calculation results demonstrate that 1) ultrafine Ru NCs dispersed on the Ti3C2Tx surface form paired active sites for N2 chemisorption in a unique tilted configuration with low-energy activation 2) the hydrophobic molecular layer modulates the local microenvironment surrounding catalytically active sites, enabling efficient N2 accumulation while repelling H2O diffusion to the active sites on the Ti3C2Tx surface, thereby leading to an increased N2 concentration and suppressed HER. As a result, an exceptionally high NH3 yield rate of 33.5µg h-1mg-1cat and Faradaic efficiency of 65.3% are obtained at -0.25V versus reversible hydrogen electrode (RHE) in 0.1m Na2SO4, outperforming those previously reported Ti3C2Tx-derived electrocatalysts. This work provides a valuable strategy for the rational design of advanced electrocatalysts by manipulating active sites and local microenvironments for efficient electrocatalysis.

Boosting electrochemical ammonia synthesis via dynamic nitrogen carriers coupled with electron-rich Lewis acidic sites on TiO2−x nanofiber

In light of the high energy consumption and substantial carbon emissions associated with traditional NH3 production based on the Haber–Bosch process, the aqueous electrochemical nitrogen reduction reaction (NRR) offers a clean and sustainable alternative production route. Nevertheless, activating the NN bonds at room temperature is challenging due to the high bond energy, severely hindering the development and commercialization of the electrochemical NRR. Herein, we report a synergistic strategy for achieving efficient N2 activation at ambient conditions that combines electrolyte engineering with catalytic site-modulated TiO2−x nanofiber electrocatalysts. The synthesized TiO2−x nanofiber electrocatalysts contained abundant intrinsic oxygen vacancies and were further modified with hydroxyl groups to create electron-rich Lewis acidic Ti sites. Additionally, BF3 was engineered into the electrolyte microenvironment, and it could form adducts with N2, serving as a dynamic carrier for N2 transport. The electron-rich Lewis acidic sites and the dynamic carriers exerted a ‘pull–pull’ effect on N2, thereby weakening the NN bonds. Through electrochemical performance evaluation, the designed electrocatalytic scheme achieved an NH3 yield of ∼57.15 μg h−1 mg−1 and a Faradaic efficiency of ∼15.14 %. We anticipate that this methodology will provide new insights into the development of electrochemical ammonia synthesis, particularly in relation to multifaceted design.

Toward High-Performance Electrochemical Ammonia Synthesis by Circumventing the Surface H-Mediated N2 Reduction.

The rapid performance decay with potentials is a significant obstacle to achieving an efficient electrocatalytic N2 reduction reaction (eNRR), which is typically attributed to competition from hydrogen evolution. However, the potential-dependent competitive behavior and reaction mechanism are still under debate. Herein, we theoretically defined N2 adsorption, H mediation, and H2 evolution as three crucial regions along the potentials by revisiting the potential-dependent competitive adsorption between N2 and H on FeN4 and RuN4 catalysts. We revealed that the surface H-mediated mechanism makes eNRR feasible at low potentials but introduces sluggish reaction kinetics, showing a double-edged sword nature. In view of this, we proposed a new possibility to achieve high-performance NH3 synthesis by circumventing the H-mediated mechanism, where the ideal catalyst should have a wide potential interval with N2-dominated adsorption to trigger direct eNRR. Using this mechanistic insight as a new criterion, we proposed a theoretical protocol for eNRR catalyst screening, but almost none of the theoretically reported electrocatalysts passed the assessment. This work not only illustrates the intrinsic mechanism behind the low-performance dilemma of eNRR but also points out a possible direction toward designing promising catalysts with high selectivity and high current density.

One Iron for Two Iron Sites in a Metal–Organic Framework Toward Simultaneous N2−H2 Activation under Mild Conditions

AbstractIron‐based catalysts play an important role in the ammonia industry. As one of the most abundant iron minerals, Fe3O4 containing FeII and FeIII sites is widely distributed in the earth's crust and even on exoplanets, theoretically giving it both economic and catalytic potentials in ammonia synthesis. However, in the absence of specific active co‐catalyst and harsh conditions, Fe3O4 is impossible to achieve ammonia synthesis alone. Here, we designed to activate the relatively inert FeII and FeIII sites in Fe3O4 with a third FeIII site inlayed in a coordination framework (MIL‐101(Fe)) to achieve the unpresented multi‐site collaborative catalysis. In‐depth mechanism study confirmed the roles of three different Fe sites in N2 activation, H2 activation, and product transfer, respectively. Efficient N2−H2 activation to NH3 on the Fe3O4‐based catalytic system has been achieved at extremely mild conditions. Our research provides a theoretical basis and a new strategy for designing efficient non‐noble metal‐based ammonia synthesis catalyst with minimized energy consumption.

New Lewis acidic ionic liquid coupled carbon shell coated defective WO3 for efficient photocatalytic N2 reduction

Herein, a new strategy to enhance the nitrogen concentration around the photocatalyst for photocatalytic nitrogen reduction was proposed. And new type of acidic ionic liquid (IL) coupled defective tungsten oxide coated with carbon shell (W@C) was designed and synthesized. The results show that the interaction force between IL and nitrogen is stronger than that between water and nitrogen, which increases the concentration of nitrogen around the tungsten oxide catalyst. In addition, the carbon shell with a hollow structure has a molecular enrichment effect, which can effectively achieve nitrogen enrichment and reduce IL escape. Finally, the ammonia synthesis performance of acidic IL coupled W@C is 52.6 μmol g−1 h−1, which is about 9 times and 2 times of tungsten oxide and W@C sample, respectively. This work fully reveals the importance of designing the catalyst structure reasonably and increasing the nitrogen concentration around the catalyst to improve the photocatalytic nitrogen reduction performance.

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%.

Promoting photothermal catalytic N2 reduction through dynamic mass transfer and accelerated charge transfer dynamics

The effective adsorption and mass transfer of N2 at the catalytic active site, along with efficient photogenerated charge transfer at the interface are the prerequisites for the photothermal catalysis N2 reduction. Here, the hydrophobic-hydrophilic biphasic heterojunction Bi2WO6/ Bi2Sn2O7 (BWSO-20) was prepared by solvothermal method, and a strong interfacial internal electric field (IEF) was formed. The effects of N2 dynamic mass transfer and interface charge transfer kinetics on the performance of photothermal catalytic N2 reduction (PTC-NRR) was investigated. The results from in-suit DRIFTS, DFT, and molecular dynamics simulations (MD) indicated that a biphasic structure enhanced the dynamic mass transfer of N2 in the hydrophobic phase (BSO) and H2O in the hydrophilic phase (BWO) simultaneously. Additionally, the IEF that accelerates the transfer kinetics of photo-generated charges. Therefore, more photo-generated electrons and holes could transfer to the surface of the hydrophobic/hydrophilic phase catalyst and undergo redox semi-reactions with N2 and H2O. The PTC-NRR reached 366.1 μmoL·g−1 when using BWSO-20 without adding sacrificial agent. This work provides a new way to achieve efficient photothermal N2 reduction based on the interfacial charge transfer kinetics accelerated by the interfacial internal electric field and the dynamic mass transfer enhanced by hydrophobic – hydrophilic two-phase heterojunction.

Fe-Single-Atom Catalysts on Nitrogen-Doped Carbon Nanosheets for Electrochemical Conversion of Nitrogen to Ammonia

Electrochemical nitrogen reduction reaction (NRR) has been established as a promising and sustainable alternative to the Haber–Bosch process, which requires intensive energy to produce ammonia. Unfortunately, NRR is constrained by the high adsorption/activation of the N2 energy barrier and the competing hydrogen evolution reaction, resulting in low faradic efficiency. Herein, a well-dispersed iron single-atom catalyst was successfully immobilized on nitrogen-doped carbon nanosheets (FeSAC-N-C) synthesized from pre-hydrothermally derived Fe-doped carbon quantum dots with an average particle size of 2.36 nm and used for efficient electrochemical N2 fixation at ambient conditions. The as-synthesized FeSAC-N-C catalyst records an onset potential of 0.12 VRHE, exhibiting a considerable faradic efficiency of 23.7% and an NH3 yield rate of 3.47 μg h–1 cm–2 in aqueous 0.1 M KOH electrolyte at a potential of −0.1 VRHE under continuous N2 feeding conditions. The control experiments assert that the produced NH3 molecules only emerge from the dissolved N2-gas, reflecting the remarkable stability of the nitrogen–carbon framework during electrolysis. The DFT calculations showed the FeSAC-N-C catalyst to demonstrate a lower energy barrier during the rate-limiting step of the NRR process, consistent with the observed high activity of the catalyst. This study highlights the exceptional potential of single-atom catalysts for electrochemical NRR and offers a comprehensive understanding of the catalytic mechanisms involved. Ultimately, this work provides a facile synthesis strategy of FeSAC-N-C nano-sheets with high atomic-dispersion, creating a novel design avenue of FeSAC-N-C that can vividly have a potential applicability in the large spectrum of electrocatalytic applications.

Heteropoly blue-modified ultrathin bismuth oxychloride nanosheets with oxygen vacancies for efficient photocatalytic nitrogen fixation in pure water

Photocatalytic nitrogen reduction is a promising green technology for ammonia synthesis under mild conditions. However, the poor charge transfer efficiency and weak N2 adsorption/activation capability severely hamper the ammonia production efficiency. In this work, heteropoly blue (r-PW12) nanoparticles are loaded on the surface of ultrathin bismuth oxychloride nanosheets with oxygen vacancies (BiOCl-OVs) by electrostatic self-assembly method, and a series of xr-PW12/BiOCl-OVs heterojunction composites have been prepared. Acting as a robust support, ultrathin two-dimensional (2D) structure of BiOCl-OVs inhibits the aggregation of r-PW12 nanoparticles, enhancing the interfacial contact between r-PW12 and BiOCl. More importantly, the existence of oxygen vacancies (OVs) provides abundant active sites for efficient N2 adsorption and activation. In combination of the enhanced light absorption and promoted photogenerated carriers separation of xr-PW12/BiOCl-OVs heterojunction, under simulated solar light, the optimal 7r-PW12/BiOCl-OVs exhibits an excellent photocatalytic N2 fixation rate of 33.53 µmol g-1h−1 in pure water, without the need of sacrificial agents and co-catalysts. The reaction dynamics is also monitored by in situ FT-IR spectroscopy, and an associative distal pathway is identified. Our study demonstrates that construction of heteropoly blues-based heterojunction is a promising strategy for developing high-performance N2 reduction photocatalysts. It is anticipated that combining of different defects with heteropoly blues of different structures might provide more possibilities for designing highly efficient photocatalysis systems.

Z-scheme metal organic framework/Ag@AgCl heterojunction photocatalysts with elevated photocatalytic N2 fixation activity

As one of the most consumed chemical reagents, ammonia (NH3) has a wide range of applications in many fields. The demand for ammonia may continue to increase with the advancement of technology and the acceleration of industrialization. The traditional high energy consumption and high pollution ammonia synthesis methods (Haber-Bosch) need to be optimized and improved to reduce environmental pollution and energy dependence. In this work, a series of Z-scheme NM/Ag@AgCl heterojunctions were prepared as catalysts for the research of photocatalytic nitrogen fixation. By in-situ photodeposition, Ag@AgCl was uniformly distributed on the NM surface, and the interfaces of different substances were tightly bonded. The SPR effect that generated by Ag nanoparticles significantly enhanced the light energy absorption performance of heterojunction materials. In the ESR spectra, the signal peak intensity of NM/Ag@AgCl was higher than that of NM under light condition. Constructing of heterojunction was beneficial to the formation of Ti3+. The strong built-in electric field among NM and AgCl promoted the generation of Z-scheme heterojunction. NM/Ag@AgCl had sufficient redox potential to overcome thermodynamic barriers and drive the catalytic reaction. Without adding any sacrificial reagent, the ammonia production of NM/Ag@AgCl-3 reached 76.7 µmol g−1 h−1 under full spectrum radiation. The rate of ammonia formation of NM/Ag@AgCl was almost seven times than that of NM. The synergistic effect between NM and Ag@AgCl optimized the photogenerated carrier separation path. This work provided a new vision for the practical application of efficient photocatalytic N2 reduction.

Exploring dynamics in single atom catalyst research: A comprehensive DFT-kMC study of nitrogen reduction reaction with focus on TM aggregation

Transition metal (TM)-based single atom catalysts (SACs) have emerged as a promising solution for the electrochemical nitrogen reduction reaction (NRR) due to their unique d-orbitals and low coordination, which facilitate efficient N2 bond weakening and increased reactivity. However, conventional theoretical approaches fail to incorporate the kinetics of TM aggregation, a crucial factor in SAC systems that affects catalyst stability and activity over time. Addressing this, we combined kinetic evaluations with thermodynamic and electronic analyses on 216 SAC candidates, using boron carbon nitride (BCN) as a substrate. Our findings revealed that Cr anchored to BCN exhibits a high turnover frequency (3.1 × 10−6 s−1) under mild conditions (300 K, 1 bar), attributed to its minimal TM aggregation over time. This research not only fills the gap in kinetic research within the SAC field but also proposes a SAC candidate distinguished by its superior kinetics, thermodynamic, and electronic properties.

Construction of Fe(III) Active Sites on Phenanthroline-Grafted g-C3N4: Reduced Work Function and Enhanced Intramolecular Charge Transfer for Efficient N2 Photofixation.

Photocatalytic nitrogen fixation is one of the important pathways for green and sustainable ammonia synthesis, but the extremely high bonding energy of the N≡N triple bond makes it difficult for conventional nitrogen fixation photocatalysts to directly activate and hydrogenate. Given this, we covalently grafted the phenanthroline unit onto graphitic carbon nitride nanosheets (CN) by the simple thermal oxidation method and complexed it with transition metal Fe3+ ions to obtain stable dispersed Fe active sites, which can significantly improve the photocatalytic activity. The Fe(III)-4-P-CN photocatalyst morphology consists of porous lamellar structures internally connected by nanowires. The special morphology of the catalysts gives them excellent nitrogen fixation performance, with an average NH3 yield of 492.9 μmol g-1 h-1, which is 6.5 times higher than that of the pristine CN, as well as better photocatalytic cycling stability. Comprehensive experiments and density-functional theory results show that Fe(III)-4-P-CN is more favorable than pristine CN for *N2 activation, effectively lowering the reaction energy barrier. Moreover, other byproducts (such as nitrate and H2O2) are also produced during the photocatalytic nitrogen fixation process, which also provides a new way for nitrogen-fixing photocatalysts to achieve multifunctional applications.

Tandem photocatalysis of nitrate to nitrogen on Cu@CN/TiOx S-scheme heterojunction

The persistent challenge of nitrate (NO3–) pollution in water systems, profoundly impacting ecosystems and human health, demands effective remediation strategies. Here, we present an innovative S-scheme Cu@CN/TiOx heterojunction for high-efficiency photocatalytic denitrification (PCDN). Evaluation of its performance demonstrates exceptional NO3– removal efficiency (99.5%) and remarkable N2 selectivity (95.5%), with 13.7 and 4.1 times higher rate constants of NO3– removal than the individual Cu@CN and TiOx components. Notably, this catalyst exhibits impressive stability across multiple cycles, maintaining consistent high conversion rates and selectivity. Mechanistic insights unveiled a tandem reaction pathway where Cu@CN selectively reduced NO3– to NO2–, followed by the TiOx-mediated CO2•– generation, enabling highly selective NO2– to N2 conversion. This unique catalytic system, featuring spatially separated redox-active sites, presents a promising avenue for efficient, selective, and stable denitrification processes, offering significant potential in addressing water pollution challenges and advancing tandem catalytic systems.

Highly efficient N2 electroreduction to NH3 on Cu7·2S4/C with sulfur vacancies synthesized using a continuous microchannel reactor

The electrochemical nitrogen reduction reaction (NRR) has emerged as a sustainable and environmental–friendly alternative for ammonia synthesis compared with conventional Haber–Bosch process. However, considerable challenges persist in developing cost-effective catalysts for NRR. Herein, Cu7·2S4/C was synthesized using a continuous microchannel reactor followed by carbonization sulfurization at 600 °C. The as-prepared Cu7·2S4/C catalyst, featuring abundant sulfur vacancies, exhibited outstanding electrochemical performance for NRR, achieving an ammonia yield of 52 μg h−1mgcat.−1 and Faraday efficiency of 32.2%. In addition, density functional theory calculations suggest that sulfur vacancies contribute to a decrease in Gibbs free energy during N2-activated hydrogenation, thereby facilitating adsorption of N2 and formation of Cu–N bonds at catalytic active centers. This study introduces a novel strategy for synthesizing economical and efficient NRR electrocatalysts based on transition metal-based metal–organic frameworks.

Tuning oxygen vacancies on Bi2MoO6 surface for efficient electrocatalytic N2 reduction reaction

Electrocatalytic nitrogen reduction reaction (NRR) is a green and environmentally friendly ammonia production method, which is expected to replace the conventional Haber-Bosch process. In this paper, a Bi2MoO6 electrocatalyst with abundant oxygen vacancies was obtained by solvothermal method and sodium hydroxide etching treatment. The introduction of oxygen vacancies increased the active site of the catalyst and promoted the charge transfer and N2 adsorption, which finally significantly increased the activity of the catalyst. In 0.1 M Na2SO4 solution at a potential of -0.2 V (vs. RHE), the Bi2MoO6 with oxygen vacancies obtained an excellent Faradaic efficiency of 16.51% and an NH3 yield of 13.18 μg h−1 mg−1, which is about 4 times that of bare Bi2MoO6. This study provides a new idea to improve the activity of the catalyst for NRR.

Engineering of local electron properties optimization in single-atom catalysts enabling sustainable photocatalytic conversion of N2 into NH3

Photocatalytic synthesis of ammonia (NH3) from nitrogen (N2) offers a promising strategy for carbon neutrality, as it avoids the energy-intensive and carbon-emitting industrial processes. The exploration of high-efficiency N2 photofixation systems for photocatalytic N2 reduction reaction (pNRR) is critical but it remains a challenge since the lack of rational structural design and atomic-level insights into molecular N2 activation mechanism. Herein, an atomically dispersed single-atom palladium (Pd) active sites decorated oxygen-deficient molybdenum oxide (Pd/MoO3-x) was creatively designed for assessing pNRR performance. Interestingly, the integration of single-atom Pd active sites in MoO3-x can significantly weaken the N≡N bond of adsorbed N2 and effectively lower the activation energy barrier during the pNRR process. This is attributed to the fact that the modified Pd single-atom sites of Pd/MoO3-x play a dominant role in the N2 spontaneous adsorption process as well as possess a remarkable photogenerated electron trapping ability, which could be assisted to inject electrons into N2 antibonding orbital, thus significantly accelerates the reaction kinetics. Consequently, the Pd/MoO3-x photocatalyst reaches an impressive NH3 yield rate of 103.2 μggcat.−1h−1, which is superior to that of pristine MoO3-x (21.2 μggcat.−1h−1) and commercial MoO3 (6.5 μggcat.−1h−1), respectively. The present study not only creates a reliable approach to expand efficient N2 photofixation system under mild conditions through the fabrication of atomically dispersed monometallic active sites, but also offers atomic-level insights into the underlying mechanism of pNRR catalytic process.

Highly efficient nitrogen fixation over S-scheme heterojunction photocatalysts with enhanced active hydrogen supply.

Photocatalytic N2 fixation is a promising strategy for ammonia (NH3) synthesis; however, it suffers from relatively low ammonia yield due to the difficulty in the design of photocatalysts with both high charge transfer efficiency and desirable N2 adsorption/activation capability. Herein, an S-scheme CoSx/ZnS heterojunction with dual active sites is designed as an efficient N2 fixation photocatalyst. The CoSx/ZnS heterojunction exhibits a unique pocket-like nanostructure with small ZnS nanocrystals adhered on a single-hole CoSx hollow dodecahedron. Within the heterojunction, the electronic interaction between ZnS and CoSx creates electron-deficient Zn sites with enhanced N2 chemisorption and electron-sufficient Co sites with active hydrogen supply for N2 hydrogenation, cooperatively reducing the energy barrier for N2 activation. In combination with the promoted photogenerated electron-hole separation of the S-scheme heterojunction and facilitated mass transfer by the pocket-like nanostructure, an excellent N2 fixation performance with a high NH3 yield of 1175.37 μmol g-1 h-1 is achieved. This study provides new insights into the design of heterojunction photocatalysts for N2 fixation.

Efficient catalyst-free N2 fixation by water radical cations under ambient conditions

The growth and sustainable development of humanity is heavily dependent upon molecular nitrogen (N2) fixation. Herein we discover ambient catalyst-free disproportionation of N2 by water plasma which occurs via the distinctive HONH-HNOH+• intermediate to yield economically valuable nitroxyl (HNO) and hydroxylamine (NH2OH) products. Calculations suggest that the reaction is prompted by the coordination of electronically excited N2 with water dimer radical cation, (H2O)2+•, in its two-center-three-electron configuration. The reaction products are collected in a 76-needle array discharge reactor with product yields of 1.14 μg cm–2 h–1 for NH2OH and 0.37 μg cm–2 h–1 for HNO. Potential applications of these compounds are demonstrated to make ammonia (for NH2OH), as well as to chemically react and convert cysteine, and serve as a neuroprotective agent (for HNO). The conversion of N2 into HNO and NH2OH by water plasma could offer great profitability and reduction of polluting emissions, thus giving an entirely look and perspectives to the problem of green N2 fixation.

Fast Joule heating for transformation of Fe-MIL-125(Ti) to Fe/TiO2 with enhanced photocatalytic activity in N2 fixation

It is critical to develop a highly efficient catalyst for the photocatalytic fixation of nitrogen to produce ammonia under ambient conditions. Herein, we reported on a fast Joule heating (FJH) method to synthesize 1.0 wt% Fe-doped TiO2 (JH Fe/TiO2) derived from MIL-125(Ti). For comparison, Fe/TiO2 calcined in a tube furnace was also prepared (TF Fe/TiO2). The photocatalytic production rate of ammonia on JH Fe/TiO2 was increased to 56.87 μmol g−1 h−1, which was 1.5 times higher than that of TF Fe/TiO2. As detected, FJH might lead to the formation of lattice defects with oxygen vacancies (OVs) formation. These OVs and defects had the potential to act as adsorption and reactive sites for N2. Furthermore, in-situ infrared (FT-IR) along with Density Functional Theory (DFT) simulation were applied to study the possible reaction pathways of photocatalytic reduction of N2. As calculated, the substitution of Feδ+ for Ti4+ with the formation of Fe-Ti dual active sites synergistically interacted with the OVs to facilitate the photocatalytic reduction process. Moreover, an alternative pathway was more favorable for the production of NH3. The reasonable design of Fe-doped transition metal oxides and the proposed Fe-Ti dual active sites opened a new approach for highly efficient photocatalytic N2 fixation.

Unraveling the mechanism of modulating external electric fields for regulating nitrogen fixation and activation on three-atom metal clusters

Efficient N2 fixation and activation under mild conditions are critical for green ammonia synthesis. Coupling external electric fields with three-atom transition metal clusters is a promising approach to realizing this vision. Herein, we report an effective strategy by modulating external electric fields to regulate the adsorption and activation of N2 on Sc3. The mechanism is further elucidated through DFT calculations. The most favorable adsorption site for N2 is the hollow site of Sc3. Although external electric fields inhibit the adsorption process of N2 on Sc3, the adsorbing performance of Sc3 is still very superior. Positive fields promote the activation and polarization of the adsorbed dinitrogen on the three-atom cluster, and negative fields have the opposite effect. The synergistic effect of positive/negative electric fields and Sc3 regulates the charge distribution of NN* in different ways. Furthermore, the d-band center (relative to the Fermi level), which determines the adsorption strength of N2, is affected by both positive and negative fields, resulting from the electron donation and back-donation mechanism between the NN* and the Sc3. This work provides guidelines for designing surface-anchored three-atom clusters with superior ammonia synthesis performance under electric fields in the future.