N2 Activation Research Articles

Modulating the electronic structure of MoS3 catalyst via heteroatom doping for Electrocatalytic nitrogen reduction reaction: A theoretical study

Heteroatom doping is an effective strategy to enhance the catalytic activity of catalysts. In this study, we propose a series of heteroatom doping (P, O) MoS3 catalysts to investigate the effect of heteroatoms on the catalytic activity of these catalysts for electrocatalytic nitrogen reduction reaction (eNRR). In P doping catalysts, the electron-donating ability of the Mo1 active site is improved by raising the P atom content, and N2 is activated by the π*-acceptation effect. In O doping catalysts, the electron-accepting ability of the Mo1 active site is improved by raising the O atom content, meanwhile, the N2 activation process transforms from the π*-acceptation effect to the σ-donation effect. The reaction mechanism of the catalysts can be accurately depicted under the constant-potential method, the calculated results elucidate that the MoS8/3O1/3 catalyst with a tiny amount of O atom exhibits good catalytic activity for eNRR with the limiting potential of -0.43 V vs. RHE. Additionally, the Eads(*N2) and Eads(*NNH) can be served as the descriptors to understand the origins of catalytic activity for the catalysts.

Highly Selective N2 Electroreduction to NH3 Using a Boron-Vacancy-Rich Diatomic NbB Catalyst.

The ambient electrochemical N2 reduction reaction (NRR) is a future approach for the artificial NH3 synthesis to overcome the problems of high-energy consumption and environmental pollution by Haber-Bosch technology. However, the challenge of N2 activation on a catalyst surface and the competitive hydrogen evolution reaction make the current NRR unsatisfied. Herein, this work demonstrates that NbB2 nanoflakes (NFs) exhibit excellent selectivity and durability in NRR, which produces NH3 with a production rate of 30.5µg h-1 mgcat -1 and a super-high Faraday efficiency (FE) of 40.2%. The high-selective NH3 production is attributed to the large amount of active B vacancies on the surface of NbB2 NFs. Density functional theory calculations suggest that the multiple atomic adsorption of N2 on both unsaturated Nb and B atoms results in a significantly stretched N2 molecule. The weakened NN triple bonds are easier to be broken for a biased NH3 production. The diatomic catalysis is a future approach for NRR as it shows a special N2 adsorption mode that can be well engineered.

Fluorine‐Stabilized Defective Black Phosphorene as a Lithium‐Like Catalyst for Boosting Nitrogen Electroreduction to Ammonia

AbstractElectrocatalytic N2 reduction reaction (NRR) is recognized as a zero‐carbon emission method for NH3 synthesis. However, to date, this technology still suffers from low yield and low selectivity associated with the catalyst. Herein, inspired by the activation of N2 by lithium metal, a highly reactive defective black phosphorene (D−BPene) is proposed as a lithium‐like catalyst for boosting electrochemical N2 activation. Correspondingly, we also report a strategy for producing environmentally stable D−BPene by simultaneously constructing defects and fluorination protection based on topochemical reactions. Reliable performance evaluations show that the fluorine‐stabilized D−BPene can induce a high NH3 yield rate of ≈70 μg h−1 mgcat.−1 and a high Faradaic efficiency of ≈26 % at −0.5 V vs. RHE in an aqueous electrolyte. This work not only exemplifies the first stable preparation and practical application of D−BPene, but also brings a new design idea for NRR catalysts.

Fluorine-Stabilized Defective Black Phosphorene as a Lithium-Like Catalyst for Boosting Nitrogen Electroreduction to Ammonia.

Electrocatalytic N2 reduction reaction (NRR) is recognized as a zero-carbon emission method for NH3 synthesis. However, to date, this technology still suffers from low yield and low selectivity associated with the catalyst. Herein, inspired by the activation of N2 by lithium metal, a highly reactive defective black phosphorene (D-BPene ) is proposed as a lithium-like catalyst for boosting electrochemical N2 activation. Correspondingly, we also report a strategy for producing environmentally stable D-BPene by simultaneously constructing defects and fluorination protection based on topochemical reactions. Reliable performance evaluations show that the fluorine-stabilized D-BPene can induce a high NH3 yield rate of ≈70 μg h-1 mgcat. -1 and a high Faradaic efficiency of ≈26 % at -0.5 V vs. RHE in an aqueous electrolyte. This work not only exemplifies the first stable preparation and practical application of D-BPene , but also brings a new design idea for NRR catalysts.

Revealing electrocatalytic C[sbnd]N coupling for urea synthesis with metal–free electrocatalyst

Urea is ubiquitous in agriculture and industry, but its production consumes a lot of energy. The conversion of nitrogen (N2) and carbon dioxide (CO2) into urea via an electrocatalytic CN coupling reaction under ambient conditions would be a major boon to sustainable development. However, designing a metal − free catalyst with high activity and selectivity for urea remains a major challenge. Herein, by means of density functional theory (DFT) and ab − initio molecular dynamics (AIMD) computations, the B12 cluster doped on nitrogenated graphene (C2N) substrate catalyst (B12@C2N) with superior stability was designed for electrocatalytic urea synthesis starting from the CO2 and N2 through four reaction mechanisms. The nature of the co-adsorption activation of CO2 and N2 on the B12@C2N catalyst was investigated, the electrochemical proton − electron transfer steps and the CN thermochemical coupling led to the synthesis of urea. The study showed that the B12@C2N catalyst exhibited high catalytic activity for urea synthesis with the lowest limiting potential of − 1.01 V following the *HNNH mechanism compared with other mechanisms. The potential − determining step (PDS) is the formation of the *CO+*NH2NH2 species. However, the two − step CN coupling barriers of *NCON species are 0.13 eV and 0.60 eV using AIMD and a “slow − growth” sampling approach in an explicit water molecules model. Calculations also showed that the byproducts of carbon monoxide (CO), methane (CH4), methanol (CH3OH), ammonia (NH3), and hydrogen (H2) can be inhibited on the B12@C2N catalyst. Therefore, the metal − free catalyst not only has a good performance for the hydrogenation of CO2 and N2 promoting the electrochemical reaction, but also facilitates CN thermochemical coupling for urea synthesis. This work provides new insights into the synthesis of urea via the CN coupling reaction on a metal − free electrocatalyst, a process that could contribute to greenhouse gas mitigation to help meet carbon neutrality targets.

Development of CuFe2O4/Palygorskite nanocomposite for photocatalytic cellulose reformation coupled with nitrogen fixation

Using natural minerals to simultaneously convert nitrogen into ammonia and biomass into value-added chemicals under renewable solar energy is promising for a sustainable world. Herein, Fe reconstructed palygorskite (Fe-Pal) was loaded by CuFe2O4 using microwave-hydrothermal method, which was applied for photocatalytic cellulose reformation coupled with nitrogen fixation. When the mass ratio of CuFe2O4 content was 8 wt%, the cellulose to 2,5-Diformylfuran (DFF) yield reached as high as 80% while nitrogen fixation to ammonia reached the highest of 390 μmol·gcat−1·h−1. The Fe-Pal enabled the adsorption and activation of N2 due to its porous microstructure and the high affinity of FeN bonds. The numerous Lewis acid sites and localized surface plasmon resonance (LSPR) of the in-situ grown CuFe2O4 nanorods increased the absorbance range to near-infrared (NIR) light and provided a substrate for local thermal activation favoring the cellulose transformation. The photoexcited electron and hole pairs of CuFe2O4/Fe-Pal heterostructure followed the type-II mechanism, which effectively separated electrons and hole pairs, thereby improving the utilization of sunlight and enhancing photocatalytic redox reaction efficiency.

Advances in Semiconductor-Based Nanocomposite Photo(electro)catalysts for Nitrogen Reduction to Ammonia.

Photo(electro)catalytic nitrogen fixation technology is a promising ammonia synthesis technology using clean solar and electric energy as the driving energy. Abundant nitrogen and water as raw materials uphold the principle of green and sustainable development. However, the generally low efficiency of the nitrogen reduction reaction has seriously restricted the application and development of this technology. The paper introduces the nitrogen reduction process and discusses the main challenges and differences in the current photo(electro)catalytic nitrogen fixation systems. It focuses on promoting the adsorption and activation of N2 and the resolution and diffusion of NH3 generated. In recent years, reviews of the modification strategies of semiconductor materials in light of the typical cases of nitrogen fixation have been reported in the literature. Finally, the future development trend of this field is analyzed and prospected.

Mo2P Monolayer as a Superior Electrocatalyst for Urea Synthesis from Nitrogen and Carbon Dioxide Fixation: A Computational Study

Urea synthesis through the simultaneous electrocatalytic reduction of N2 and CO2 molecules under ambient conditions holds great promises as a sustainable alternative to its industrial production, in which the development of stable, highly efficient, and highly selective catalysts to boost the chemisorption, activation, and coupling of inert N2 and CO2 molecules remains rather challenging. Herein, by means of density functional theory computations, we proposed a new class of two‐dimensional nanomaterials, namely, transition‐metal phosphide monolayers (TM2P, TM = Ti, Fe, Zr, Mo, and W), as the potential electrocatalysts for urea production. Our results showed that these TM2P materials exhibit outstanding stability and excellent metallic properties. Interestingly, the Mo2P monolayer was screened out as the best catalyst for urea synthesis due to its small kinetic energy barrier (0.35 eV) for C–N coupling, low limiting potential (−0.39 V), and significant suppressing effects on the competing side reactions. The outstanding catalytic activity of the Mo2P monolayer can be ascribed to its optimal adsorption strength with the key *NCON species due to its moderate positive charges on the Mo active sites. Our findings not only propose a novel catalyst with high‐efficiency and high‐selectivity for urea production but also further widen the potential applications of metal phosphides in electrocatalysis.

Enhanced Nitrogen Reduction to Ammonia by Surface- and Defect-Engineered Co-catalyst-Modified Perovskite Catalysts under Ambient Conditions and Their Charge Carrier Dynamics.

An electrocatalytic nitrogen reduction reaction is considered a potential approach for green ammonia production─a zero-carbon fertilizer, fuel, and energy storage for renewable energy. To harness the synergistic properties of perovskites, the inherent dipole moment due to their non-centrosymmetric structure (that facilitates better charge separation), oxygen vacancies, and the presence of Ni metal sites that permit activation and reduction of N2 efficiently, the NiTiO3-based nanoelectrocatalysts have been synthesized. Further, these catalysts have been modified with ultra-small metal nanocrystal co-catalysts to form heterointerfaces that not only aid to improve the charge separation but also activate N2 and lower overpotential requirements. The appearance of peaks corresponding to (012), (104), (110), (11-3), (024), (11-6), (018), (027), and (300) confirms the formation of rhombohedral NiTiO3. The shift in the XRD peak corresponding to the (104) plane to a smaller 2θ value and peak shifting and widening of Raman spectra imply the lattice distortion that signifies the formation of Pd-NiTiO3 and Pt-NiTiO3 heterojunction electrocatalysts with the loadings of 0.4 and 0.3 wt % of Pd and Pt, respectively, as confirmed by ICP-OES analysis. The detailed XPS analysis reveals the presence of Pd (0), Pd (II), and Pt (0), Pt (II) in respective electrocatalysts. The appearance of XPS peaks at 528.7 and 531.1 eV suggests the presence of oxidative oxygen species (O2-/O-) and the presence of oxygen defects due to oxygen vacancy. The detailed nitrogen reduction (NRR) investigation exhibits a 5-fold enhancement in ammonia yield rate (∼14.28 μg h-1 mg-1 at -0.003 V vs RHE), a faradic efficiency of 27% (at 0.097 V vs RHE) for Pd-NiTiO3 electrocatalysts than that for bare NiTiO3 (3.08 μg h-1 mg-1), and 9-folds higher than that of the activity shown by the commercial TiO2 (P25) (1.52 μg h-1mg-1). The formation of ammonia was further confirmed by using isotopic nitrogen as the feeding gas. Furthermore, the highest NRR is observed at lower cathodic potential (-0.003 V vs RHE) in the case of the Pd-NiTiO3 electrocatalyst than that of the Pt-NiTiO3 electrocatalyst (-0.203 V vs RHE), implying significantly reduced overpotential requirement. Such enhanced NRR activity with lower overpotential requirement in the case of the Pd-NiTiO3 electrocatalyst is due to efficient charge separation as shown by the semicircle Nyquist plot, decreased photoluminescence emission intensity, shorter average lifetime (∼29 ns) of excitons, appropriate band bending, and improved activation of N2 by the oxygen vacancies and heterointerface formed between Pd nanocrystals and NiTiO3. Furthermore, no change is observed in the current density, after stabilization in the initial few seconds, even up to 2 h, which signifies that these electrocatalysts are stable. The structural and morphological integrity of the optimized catalyst remained even after the nitrogen reduction reactions, as revealed by no significant change observed in FESEM, elemental mapping, and EDS analysis.

Boosting solar-driven N2 to NH3 conversion using defect-engineered TiO2/CuO heterojunction photocatalyst

Ammonia (NH3) is one of the important energy sources for sustainable chemical products and carbon-free energy carriers. Artificial N2 photofixation is one of the promising approaches for the clean production of NH3 using photocatalysts in N2-dissolved water as a hydrogen source. We prepared defect-engineered TiO2/CuO heterojunction photocatalysts by the simple evaporation-induced self-assembly (EISA) method followed by post-thermal annealing under inert gas flow. The formation of a type-Ⅱ using TiO2 and CuO facilitated light absorption in near IR to UV light and the separation of photoexcited electron-hole pairs. In addition, the further post-thermal annealing under N2 gas flow resulted not only in an increase in crystallinity for the photoactive Anatase TiO2 and Tenorite CuO in the bulk but also in the in-situ formation of Ti3+ defect sites on the TiO2 surface. The increased crystallinity enhanced the photoexcited charge transport, while the defect sites improved N2 adsorption and activation, promoting the photocatalytic conversion of N2 to NH3. The defect-engineered TiO2/CuO photocatalysts exhibited a high NH3 production rate (1.575 μ mol g−1h−1) under visible light irradiation (λ≥ 420 nm) without any sacrificial agent, this value is 9.4 times and 2.5 times higher than those obtained with pristine TiO2 and TiO2/CuO photocatalysts, respectively. This work clearly demonstrates the synergistic effect of heterojunction and defect-engineering and provides insights into how each strategy can affect solar-driven NH3 production.

Theoretical design toward highly efficient single-atom catalysts for nitrogen reduction by regulating the “acceptance-donation” mechanism

Single-atom catalysts (SACs) show great potential for driving electrochemical nitrogen reduction reaction (NRR). However, the lack of physico-chemical understanding of the ambiguous activation mechanism impedes the development of electrocatalysts. In this work, using first principles calculations, we tuned NRR activity and elucidated regulation mechanism of N2 activation by constructing SACs based on defective Ti2CO2 and Ti2NO2 MXenes. Interestingly, Mo@Ti2CO2-v and W@Ti2CO2-v show excellent NRR activity and selectivity with low limiting potentials of –0.27 and –0.27 V at the first hydrogenation (*N2→*NNH) and the last hydrogenation (*NH2→*NH3) steps via distal pathway, respectively. The intrinsic activity tendency can be related to adsorption energy of intermediate *NNH (ΔE(*NNH)). Furthermore, electronic structure analysis demonstrates that number of unpaired electrons in d orbitals (Nun-d) determines occupation of d orbitals, thus regulating the “acceptance-donation” mechanism. Particularly, transition metals with Nun-d of 5 and 4 show moderate “acceptance-donation” interaction, thus achieving encouraging NRR performance. Moreover, ΔE(*NNH) and Nun-d can be considered as promising descriptors for screening and designing effective SACs. Finally, our investigation not only contributes to discovery of novel SACs toward NRR, but also provides insightful guidance for other electrochemical reactions with high bond-order molecules and multi-electron steps, such as ORR and CO2RR.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance.

Atomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X-ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3 ) of 28.3 μg h-1 mgcat -1 (7447 μg h-1 mgSn -1 ) at -0.3 V. Furthermore, the enhanced N2 Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance

AbstractAtomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X‐ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3) of 28.3 μg h−1 mgcat−1 (7447 μg h−1 mgSn−1) at −0.3 V. Furthermore, the enhanced N2Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

Dinitrogen Activation and Addition to Unsaturated C-E (E=C, N, O, S) Bonds Mediated by Transition Metal Complexes.

Dinitrogen (N2 ) activation and functionalization is of fundamental interest and practical importance. This review focuses on N2 activation and addition to unsaturated substrates, including carbon monoxide, carbon dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, and allenes, mediated by transition metal complexes, which afforded a variety of N-C bond formation products. Emphases are placed on the reaction modes and mechanisms. We hope that this work would stimulate further explorations in this challenging field.

Dinitrogen Activation and Addition to Unsaturated C−E (E=C, N, O, S) Bonds Mediated by Transition Metal Complexes

AbstractDinitrogen (N2) activation and functionalization is of fundamental interest and practical importance. This review focuses on N2 activation and addition to unsaturated substrates, including carbon monoxide, carbon dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, and allenes, mediated by transition metal complexes, which afforded a variety of N−C bond formation products. Emphases are placed on the reaction modes and mechanisms. We hope that this work would stimulate further explorations in this challenging field.

Pulsed Electrocatalysis Enabling High Overall Nitrogen Fixation Performance for Atomically Dispersed Fe on TiO2

AbstractAtomically dispersed Fe was designed on TiO2and explored as a Janus electrocatalyst for both nitrogen oxidation reaction (NOR) and nitrogen reduction reaction (NRR) in a two‐electrode system. Pulsed electrochemical catalysis (PE) was firstly involved to inhibit the competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Excitingly, an unanticipated yield of 7055.81 μmol h−1 g−1cat.and 12 868.33 μmol h−1 g−1cat.were obtained for NOR and NRR at 3.5 V, respectively, 44.94 times and 7.8 times increase in FE than the conventional constant voltage electrocatalytic method. Experiments and density functional theory (DFT) calculations revealed that the single‐atom Fe could stabilize the oxygen vacancy, lower the energy barrier for the vital rupture of N≡N, and result in enhanced N2fixation performance. More importantly, PE could effectively enhance the N2supply by reducing competitive O2and H2agglomeration, inhibit the electrocatalytic by‐product formation for longstanding *OOH and *H intermediates, and promote the non‐electrocatalytic process of N2activation.

Boosting photocatalytic ammonia synthesis performance over OVs-Rich Ru/W18O49: Insights into the roles of oxygen vacancies in enhanced hydrogen spillover effect

Synergistic water activation and nitrogen reduction process is significant to the photocatalytic ammonia synthesis reaction, in which the obtainment of active hydrogen (H*) from H2O dissociation and then transfer to N2 activation site is essential. Herein, the oxygen vacancies (OVs) enhanced hydrogen spillover is used to increase the H* transfer between the H2O activation site (Ru) and the N2 activation site (OVs-rich W18O49). Results shown that the OVs-rich Ru/W18O49 achieves high activity for NH3 production with a yield of 222.75 µmol‧g−1‧h−1, which is 5.60 folds of the OVs-deficient Ru/W18O49. Control experiments, characterization, and theoretical calculation made it clear that OVs played crucial roles in enhancing the hydrogen spillover by modifying the support's Gibbs free energy for hydrogen adsorption and lowering the barrier of H* migration. Finally, the detail mechanism was explained from a new perspective. This strategy may provide new insights for other hydrogenation reactions under mild conditions.

Pulsed Electrocatalysis Enabling High Overall Nitrogen Fixation Performance for Atomically Dispersed Fe on TiO2.

Atomically dispersed Fe was designed on TiO2 and explored as a Janus electrocatalyst for both nitrogen oxidation reaction (NOR) and nitrogen reduction reaction (NRR) in a two-electrode system. Pulsed electrochemical catalysis (PE) was firstly involved to inhibit the competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Excitingly, an unanticipated yield of 7055.81 μmol h-1 g-1 cat. and 12 868.33 μmol h-1 g-1 cat. were obtained for NOR and NRR at 3.5 V, respectively, 44.94 times and 7.8 times increase in FE than the conventional constant voltage electrocatalytic method. Experiments and density functional theory (DFT) calculations revealed that the single-atom Fe could stabilize the oxygen vacancy, lower the energy barrier for the vital rupture of N≡N, and result in enhanced N2 fixation performance. More importantly, PE could effectively enhance the N2 supply by reducing competitive O2 and H2 agglomeration, inhibit the electrocatalytic by-product formation for longstanding *OOH and *H intermediates, and promote the non-electrocatalytic process of N2 activation.

Hole scavenger-free nitrogen photofixation in pure water with non-metal B-doped carbon nitride: Implicative importance of B species for N2 activation

Being the energy glutton and top ranker of greenhouse gas emission, Haber-Bosch is undoubtedly a grand challenge to reaching sustainability and carbon neutrality. Solar-driven nitrogen (N2) fixation under mild conditions is highly attractive and promising for sustainable ammonia (NH3) production. However, low conversion efficiency remains as a serious problem yet to be solved due to the difficult activation of strongly non-polar NN bond. In this study, defective and atomically thin g-C3N4 with boron sites was synthesized via a facile decomposition-thermal polymerization technique. The optimum photocatalyst displayed an NH3 yield of 213.59 μmol gcat−1 h−1 under visible light irradiation (λ > 400 nm) without any hole scavenger, bestowing high suitability for N2 fixation in pure water. The impressive performance is largely ascribed to the introduction of B species, which could act as the active sites for N2 adsorption, activation and reduction. Additionally, the atomically thin layer (∼3.25 nm) shortens charge carrier transport pathway while the B atoms and defects suppress quantum size effect as well as extends photo-response through bandgap reduction. These attributes synergistically lead to suppressed electron-hole recombination, efficacious charge transport, enhanced light utilization and enriched catalytic sites for N2 fixation. As a whole, this work presents an easy strategy to realize efficient N2 photofixation over a metal-free, low-cost and non-toxic photocatalyst in pure water as a continuous effort in advancing the burgeoning field of photocatalytic N2 fixation.

Dinitrogen Complexes of Cobalt(-I) Supported by Rare-Earth Metal-Based Metalloligands.

Sequential reactions of heptadentate phosphinoamine LH3 with rare-earth metal tris-alkyl precursor (Me3SiCH2)3Ln(THF)2 (Ln = Sc, Lu, Yb, Y, Gd) and a low-valent cobalt complex (Ph3P)3CoI afforded rare-earth metal-supported cobalt iodide complexes. Reduction of these iodide complexes under N2 allowed the isolation of the first series of dinitrogen complexes of Co(-I) featuring dative Co(-I) → Ln (Ln = Sc, Lu, Yb, Y, Gd) bonding interactions. These compounds were characterized by multinuclear NMR spectroscopy, X-ray diffraction analysis, electrochemistry, and computational studies. The correlation of N-N vibrational frequencies with the pKa of [Ln(H2O)6]3+ showed that strongest activation of N2 was achieved with the least Lewis acidic Gd(III) ion. Interestingly, these Ln-Co-N2 complexes catalyzed silylation of N2 in the presence of KC8 and Me3SiCl with turnover numbers (TONs) up to 16, where the lutetium-supported Co(-I) complex showed the highest activity within the series. The role of the Lewis acidic Ln(III) was crucial to achieve catalytic turnovers and tunable reactivity toward N2 functionalization.