Nitrogen Reduction Reaction Selectivity Research Articles

Catalysts with Trimetallic Sites on Graphene-like C2N for Electrocatalytic Nitrogen Reduction Reaction: A Theoretical Investigation.

Electrocatalytic nitrogen reduction reaction (NRR) is a green and highly efficient way to replace the industrial Haber-Bosch process. Herein, clusters consisting of three transition metal atoms loaded on C2N as NRR electrocatalysts are investigated using density functional theory (DFT). Meanwhile, Ca was introduced as a promoter and the role of Ca in NRR was investigated. It was found that Ca anchored to the catalyst can act as an electron donor and effectively promote the activation of N2 on M3. In both M3@C2N and M3Ca@C2N (M=Fe, Co, Ni), the limiting potential (UL) is less negative than that of the Ru(0001) surface and has the ability to suppress the competitive hydrogen evolution reaction (HER). Among them, Fe3@C2N is suggested to be the most promising candidate for NRR with high thermal stability, strong N2 adsorption ability, low limiting potential, and good NRR selectivity. The concepts of trimetallic sites and alkaline earth metal promoters in this work provide theoretical guidance for the rational design of atomically active sites in electrocatalytic NRR.

Enhanced Activity and Selectivity for Nitrogen Reduction Reaction in Electrode-based Heterostructures: A DFT Computational Study.

Developing sustainable and efficient catalysts for ammonia synthesis from atmospheric molecular N2 under ambient conditions presents a significant 21st-century challenge. Two-dimensional heterostructures, particularly single-atom catalysts (SACs) supported on two-dimensional materials, have emerged as a promising avenue due to their remarkable catalytic activity and selectivity. Electrides, characterized by an abundance of free electrons and high surface activity, have attracted substantial attention in this context. Through density functional theory (DFT) calculations, this study proposes electride-graphene heterostructures (EGHS) as catalysts to effectively regulate charge distribution at the catalytic center, facilitating the optimization of catalytic performance. The EGHS model addresses challenges related to excessive adsorbate binding, mitigating electron transfer compared to electride monolayer adsorption. This novel approach utilizes heterogeneous heterostructures to finely tune the catalytic site, optimizing electron input for enhanced catalysis.Based on the optimized charge transfer for N2 activation, the Cr-doped EGHS (Cr@EGHS) exhibits a promising performance in the nitrogen reduction reaction, leading to, a relatively low limiting potential of -0.85 V and high selectivity. The hypothesis charge transfer depend on N2 activation is further supported by modulating the distance between component layers of heterostructure. These findings contribute to design principles for 2D heterostructure catalysts and offer a reference for experimental synthesis.

Electrochemical nitrogen reduction reaction catalyzed by a cucurbit[6]uril-phosphomolybdic-copper cation hybrid

The electrocatalytic nitrogen reduction reaction (NRR) provides an energy-saving and environmentally friendly method to synthesize ammonia. Herein, a molybdenum-containing hybrid material (Q[6]-PMA-Cu) was prepared form the assembly of Keggin-type phosphomolybdic acid (PMA) with cucurbit[6]uril (Q[6]) and Cu2+ cations. Q[6]-PMA-Cu with multiple active sites and stable properties not only enables a high selectivity for NRR, but also shows a distinct advantage to suppress HER process, affording a high ammonia yield of 135.04±4.25 µg h−1 mgcat−1 with a Faradaic efficiency (FE) of 85.48±3.33%. 15N2 isotope labeling and control experiments were conducted to verified the nitrogen resource of ammonia formation. The results of experiments and DFT calculations demonstrates the reaction mechanism along the alternate association pathway, of which the metal active sites (Mo & Cu) play crucial role in electron transfer and the presence of hydrophobic Q[6] is responsible to inhibit side reaction of HER.

Screening of borophene-supported highly active and selective single-atom catalysts for electrocatalytic nitrogen reduction reactions

Ammonia (NH3) is an ideal zero-carbon clean energy source because of its substantial hydrogen capacity, high-energy density and facile transportability. Compared to disadvantages of Haber–Bosch processes, such as demanding reaction conditions, high energy consumption and inefficiency, the electrocatalysis nitrogen reduction reaction (NRR) can achieve green synthesis of NH3 due to mild reactive conditions. Utilizing density functional theory (DFT), explored the potential of borophene-supported transition metals as single atom catalysts (SACs) for NRR. The NRR pathways and Gibbs free-energy (ΔG) of the selected V@Bβ12, Cr@Bβ12, Zr@Bβ12 and Mo@Bβ12 were studied in detail after rigorous screening processes. The limiting potentials of NRR in optimal path are -0.10, -0.27, -0.18 and -0.07 V, respectively, which are excellent catalysts for NRR. Under operating voltage conditions, TM@Bβ12 has excellent ability to resist surface oxidation and inhibit hydrogen evolution reaction (HER). In addition, V@Bβ12, Cr@Bβ12, Zr@Bβ12 and Mo@Bβ12 have good selectivity for NRR. Cr@Bβ12 and Mo@Bβ12 are also potential catalysts for HER. The source of TM@Bβ12 catalytic activity in NRR fully confirms the good conductive properties, and the transmission of the charge contribute to improve catalytical activity of NRR. This paper provides theoretical guidance on the synthesis of a new type of NRR catalyst.

Achieving 78.2 % Faraday Efficiency for Electrochemical Ammonia Production Via Covalent Modification of CNTs with B4C

AbstractElectrochemical reduction of N2 to NH3 provides an alternative to the Haber‐Bosch process for sustainable NH3 production driven by renewable electricity. Here, we reported carbon nanotubes (CNTs) covalently modified with boron carbide (B4C) as a nonmetallic catalyst for efficient electrochemical nitrogen reduction reaction (NRR) under ambient conditions. The structure of the catalyst was characterized by transmission electron microscopy (TEM), X‐ray diffraction (XRD), elemental mapping, X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The catalyst held a superior selectivity for NRR with high Faraday efficiency of 78.2 % accompanying with NH3 yield rate of 14.0 μg mg−1cat. h−1 under the condition of 0.1 M Na2SO4 and −0.6 V vs. RHE. Electrochemical experiments including cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization curves were performed to explain the best electrochemical properties of B4C/CNTs among the samples. This work demonstrates that the strategy of covalent modification plays an important role to improve the selectivity of electrochemical NRR catalyst, thus allowing the reactions to proceed more efficiently.

A Coherent Pd–Pd16B3 Core–Shell Electrocatalyst for Controlled Hydrogenation in Nitrogen Reduction Reaction

AbstractThe manipulation of surface catalytic sites has rarely been explored for metal borides, and the subsurface effects on the electrocatalytic activity of the nitrogen reduction reaction (NRR) remain unknown. Herein, this work develops a core–shell nanoparticle catalyst with a Pd core that ensures high electron transfer rates and an Pd16B3 atomical shell that possess tunable active sites for regulating the NRR. The atomic structural evolution from Pd to Pd16B3 is investigated by precisely controlling the B atom diffusion, molecular rearrangement, and d–sp orbital hybridization. Pd/Pd16B3 core–shell nanocrystals exhibit an exceptional NRR performance with a high NH3 Faradaic efficiency of 30.8%, which is superior to those of pristine Pd (1.2%) and B‐doped Pd (4.8%) under identical conditions, and a yield rate of 0.81 µmol h−1 cm−2. This work discovers that the Pd16B3 shell could promote the NRR selectivity by separating the separating the hydrogen evolution reaction proceeded on hole sites and NRR proceeded on bridge sites, and the Pd core could provide the excellent conductivity to Pd16B3 shell through regulated electron interactions. Consequently, the controlled chemical ordering of palladium boride on palladium surfaces provides insight into the synthesis of advanced NRR electrocatalysts.

Screening Efficient C-N Coupling Catalysts for Electrosynthesis of Acetamide and Output Ammonia through a Cascade Strategy of Electrochemical CO2 and N2 Reduction Using Cu-Based Nitrogen-Carbon Nanosheets.

Due to the limitation of the high-value-added products obtained from electrocatalytic CO2 reduction within an acid environment, introducing additional elements can expand the diversity of the products obtained during the CO2 reduction reaction (CO2RR) and nitrogen reduction reaction (NRR). Thus, coelectroreduction of CO2 and N2 is a new strategy for producing acetamide (CH3CONH2) via both C-C and C-N bond coupling using Cu-based nitrogen-carbon nanosheets. CO2 can reduce to CO, and a key ketene (*C═C═O) can be generated from *CO*CO dimerization; this ketene is postulated as an intermediate in the formation of acetamide. However, most studies focus on promoting the C-C bond formation. Here, we propose that C-N bond coupling can form acetamide through the interaction of *C═C═O with NH3. The acetamide is formed via a nucleophilic attack between *NH3 and the *C═C═O intermediate. The C-N coupling mechanism was successfully applied to expand the variety of nitrogen-containing products obtained from CO2 and N2 coreduction. Thus, we successfully screened Cu2-based graphite and Cu-based C3N4 as catalysts that can produce C2+ compounds by integrating CO dimerization with acetamide synthesis. In addition, we observed that Cu2-based C2N and Cu-based C3N4 catalysts are suitable for the NRR. Cu-based C3N4 showed high CO2RR and NRR activities with small negative limiting potential (UL) values of -0.83 and -0.58 V compared to those of other candidates, respectively. The formation of *COHCOH from *COHCO was considered the rate-determining step (RDS) during acetamide electrosynthesis. The limiting potential value of Cu2-based C2N was only -0.46 V for NH3 synthesis, and the formation of *NNH was via the RDS via an alternating path. The adsorption energy difference analysis both CO2 and N2 compare with the hydrogen evolution reaction (HER), suggesting that Cu2-based C2N exhibited the highest CO2RR and NRR selectivity among the 13 analyzed catalysts. The results of this study provide innovative insights into the design principle of Cu-based nitrogen-carbon electrocatalysts for generating highly efficient C-N coupling products.

Surface Electronic Properties-Driven Electrocatalytic Nitrogen Reduction on Metal-Conjugated Porphyrin 2D-MOFs.

Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between ΔGmax and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.

Design of high performance nitrogen reduction electrocatalysts by doping defective polyoxometalate with a single atom promoter.

Single-atom catalysts (SACs) are emerging as promising candidates for electrochemical nitrogen reduction reaction (NRR). Previous studies have shown that the single-atom centers of SACs can not only serve as active sites, but also act as promoters to affect the catalytic properties. However, the use of single metal atoms as promoters in electrocatalysis has rarely been studied. In this work, the defective Keggin-type phosphomolybdic acid (PMA) is used as a substrate to support the single metal atoms. We aim to tune the electronic structures of the exposed molybdenum active sites on defective PMA by using these supported single atoms as promoters for efficient NRR. Firstly, the stability and N2 adsorption capacity were studied to screen for an effective catalyst capable of activating N2. Most of the SACs were found to have good stability and N2 adsorption capacity. Then, we compared the selectivity and NRR activity of the catalysts and found that catalysts with metal atom promoters have improved NRR selectivity and activity. Finally, electronic structure analysis was carried out to understand the promoting effect of the promoter on N2 activation and the activity of the NRR process. This work provides a new strategy for designing efficient catalysts for electrocatalytic reactions by introducing promoters.

Unveiling the synergistic effect between the metallic phase and bridging S species over MoS2 for highly efficient nitrogen fixation

Electrocatalytic nitrogen reduction reaction (NRR) is considered an appealing approach towards sustainable NH3 production but still undergoes serious challenges with unsatisfactory catalytic performance, which hinders its large-scale application. In this work, the S-rich 1T‐MoS2 with an ultrahigh 1T phase content and S-enrichment has been successfully synthesized and firstly verified as an exceptional NRR catalyst with high activity and selectivity. The optimized MoS2.30 catalyst exhibits a high NH3 yield rate (98.30±1.63 μg h–1 mg–1cat.) and FE (23.10±0.38%), surpassing nearly all the reported MoS2-based NRR catalysts and the overwhelming majority of advanced NRR catalysts, demonstrating the encouraging role-playing of the synergistic effect between 1T phase and bridging S22– species on NRR performances. DFT calculations reveal that the high properties empowered by MoS2.30 are on account of the synergistic effect that induces the enhanced NRR activity via the strengthened N2 adsorption and reduced energy barrier (Eb) as well as the improved NRR selectivity through the optimized competitive adsorption and reduced energy barrier against the hydrogen evolution reaction (HER). This work fabricates a MoS2-based electrocatalyst for highly efficient NRR and proves an effective strategy to improve the catalytic performance, which is worth being extended to other catalytic reactions.

Modulating the coordination environment of active site structure for enhanced electrochemical nitrogen reduction: The mechanistic insight and an effective descriptor

The effect of coordination environment of active site structure can never be underestimated in the rational design of a high-performance catalyst especially in electrochemical application. We designed a B-modified C2N-based double-atom catalyst (M2@B2-C2N) with the hybrid coordination of B2N4, on which electrochemical nitrogen reduction reaction (NRR) was computationally studied. Our DFT calculations revealed that the NRR could proceed highly efficiently for M2 = Mo2 and W2 with the onset potential of UL = -0.25 V and UL = -0.27 V, respectively. Remarkably, the NRR complied with a special quasi-dissociative mechanism instead of the conventional associative mechanism on M2@B2-C2N (M2 = Mo2 and W2). Using the optimal metal-based catalyst as a reference, these two model catalysts could yield superior NRR selectivity with respect to HER. The AIMD simulation demonstrated that the NRR could proceed with the applied potential of cathode as URHE = -0.20 V (Mo2) and −0.39 V (W2). The underlying chemical and structural origin of coordination environment was formulated as an effective descriptor Ω, which enables to bridge the NRR activity and active site structure. Our study could further the understanding of metal active site structure that catalyzes an electrochemical reaction involving small molecules.

High efficiency carbon nanotubes-based single-atom catalysts for nitrogen reduction

Carbon-based single-atom catalysts (SACs) for electrochemical nitrogen reduction reaction (NRR) have received increasing attention due to their sustainable, efficient, and green advantages. However, at present, the research on carbon nanotubes (CNTs)-based NRR catalysts is very limited. In this paper, using FeN3@(n, 0) CNTs (n = 3 ~ 10) as the representative catalysts, we demonstrate that the CNT curvatures will affect the spin polarization of the catalytic active centers, the activation of the adsorbed N2 molecules and the Gibbs free energy barriers for the formation of the critical intermediates in the NRR processes, thus changing the catalytic performance of CNT-based catalysts. Zigzag (8, 0) CNT was taken as the optimal substrate, and twenty transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, W, Re, Ir, and Pt) were embedded into (8, 0) CNT via N3 group to construct the NRR catalysts. Their electrocatalytic performance for NRR were examined using DFT calculations, and TcN3@(8, 0) CNT was screened out as the best candidate with a low onset potential of − 0.53 V via the distal mechanism, which is superior to the molecules- or graphene-support Tc catalysts. Further electronic properties analysis shows that the high NRR performance of TcN3@(8, 0) CNT originates from the strong d-2π* interaction between the N2 molecule and Tc atom. TcN3@(8, 0) CNT also exhibits higher selectivity for NRR than the competing hydrogen evolution reaction (HER) process. The present work not only provides a promising catalyst for NRR, but also open up opportunities for further exploring of low-dimensional carbon-based high efficiency electrochemical NRR catalysts.

Role of Peripheral Coordination Boron in Electrocatalytic Nitrogen Reduction over N-Doped Graphene-Supported Single-Atom Catalysts.

In this work, we investigate the effect of peripheral B doping on the electrocatalytic nitrogen reduction reaction (NRR) performance of N-doped graphene-supported single-metal atoms using density functional theory (DFT) calculations. Our results showed that the peripheral coordination of B atoms could improve the stability of the single-atom catalysts (SACs) and weaken the binding of nitrogen to the central atom. Interestingly, it was found that there was a linear correlation between the change in the magnetic moment (μ) of single-metal atoms and the change in the limiting potential (UL) of the optimum NRR pathway before and after B doping. It was also found that the introduction of the B atom suppressed the hydrogen evolution reaction, thereby enhancing the NRR selectivity of the SACs. This work provides useful insights into the design of efficient SACs for electrocatalytic NRR.

The transition metal doped B cluster (TM4B18) as catalysis for nitrogen fixation

Renewable electrically/light-driven nitrogen reduction from earth's abundant nitrogen is considered one of the most attractive strategies for clean energy transport and storage through nitrogen cycle. To this end, developing inexpensive, rich and excellent performance catalysts for nitrogen reduction reaction (NRR) is essential but challenging. Here, we systematically studied 18 kind of transition metal boron clusters TM4B18 (TM = 3d, 4d and 5d) as promising photocatalytic catalysis for NRR. Our first-principles calculations demonstrate that these TM4B18 clusters possess outstanding water environment stability and high selectivity for NRR under hydrogen evolution reaction (HER) side reaction. In particular, three candidate catalysts (Zr4B18, V4B18 and Mn4B18) for ammonia synthesis with excellent performance are selected by high-throughput screening of TM4B18 materials using a "Four-Step" method. Most notably, Zr4B18 cluster performs best with onset potential lower -0.50 eV through the enzymatic mechanism, such result is owing to the part of occupied d orbitals of the active metal atoms. Furthermore, these TM4B18 clusters with appropriate energy gap that is able to absorb light from the visible to ultraviolet to driven NRR. These theoretical researches offer vital physical views for using the superior transition metal doped B cluster materials for driving by solar energy and ammonia production.

Newly designed photocatalyst of Fe4 single clusters on g-C6N6 for nitrogen reduction reaction

The current industrial synthesis of ammonia proceeds through Haber–Bosch process, in which the adsorbed N2 are directly dissociated, and the reaction is limited by Brønsted–Evans–Polanyi (BEP) relation. In this work, the catalytic properties of Fe4 clusters fixed on g-C6N6 for nitrogen reduction reaction (NRR) are explored by first-principle calculations. The studies on the structural stability, adsorption capacity for N2 and the change of Gibbs free energy proves that Fe4 cluster catalyst exhibits excellent catalytic activity and high selectivity for NRR. The “acceptance-donation” interaction between Fe4@g-C6N6 and N atoms presented by PDOS and Bader charge analysis will facilitate the breaking of NN bonds. The 100 % Faraday efficiency further proves the high NRR selectivity. The results provide an effective strategy for designing high-performance electrochemical NRR catalysts.

P-Block Metal-Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview.

Electrochemical nitrogen reduction reaction (NRR) to ammonia (NH3 ) using renewable electricity provides a promising approach towards carbon neutral. What's more, it has been regarded as the most promising alternative to the traditional Haber-Bosch route in current context of developing sustainable technologies. The development of a class of highly efficient electrocatalysts with high selectivity and stability is the key to electrochemical NRR. Among them, P-block metal-based electrocatalysts have significant application potential in NRR for which possessing a strong interaction with the N 2p orbitals. Thus, it offers a good selectivity for NRR to NH3 . The density of state (DOS) near the Fermi level is concentrated for the P-block metal-based catalysts, indicating the ability of P-block metal as active sites for N2 adsorption and activation by donating p electrons. In this work,wesystematically review the recent progress of P-block metal-based electrocatalysts for electrochemical NRR. The effect of P-block metal-based electrocatalysts on the NRR activity, selectivity and stability are discussed. Specifically, the catalyst design, the nature of the active sites of electrocatalysts and some strategies for boosting NRR performance, the reaction mechanism, and the impact of operating conditions are unveiled. Finally, some challenges and outlooks using P-block metal-based electrocatalysts are proposed.

Theoretical screening of a graphyne-supported transition metal single-atom catalyst for the N2 reduction reaction.

The electrocatalytic nitrogen reduction reaction (NRR) is a promising technology for the synthesis of NH3 in an ambient environment. However, developing low-cost and high-efficiency electrocatalysts still remains a long-standing challenge. In this work, density function theory (DFT) calculations are done to systematically investigate the NRR catalytic activity of transition metals (TM = Sc-Cu, Y-Ag, and Hf-Au) supported on monolayer graphyne (GY). TM@GY (TM = Sc, V, Mn, Y, Tc, and Os) with excellent NRR performance are demonstrated. The mixed pathway is the most favorable for Sc, V, Y, and Os@GY with the potentials of -0.37, -0.27, -0.40, and -0.36 V, respectively, while the distal reaction pathway is most favorable for Mn and Tc@GY with the potentials of -0.37 and -0.42 V. Most strikingly, Mn, Tc, and Os@GY exhibit high NRR selectivity. This work provides a screening scheme for exploring highly efficient electrocatalysts for the electrochemical NRR under ambient conditions.

Unveiling the Protonation Kinetics‐Dependent Selectivity in Nitrogen Electroreduction: Achieving 75.05 % Selectivity

AbstractWhile higher selectivity of nitrogen reduction reaction (NRR) to ammonia (NH3) is always achieved in alkali, the selectivity dependence on nitrogen (N2) protonation and mechanisms therein are unrevealed. Herein, we profile how the NRR selectivity theoretically relies upon the first protonation that is collectively regulated by proton (H) abundance and adsorption‐desorption, along with intermediate‐*NNH formation. By incorporating electronic metal modulators (M=Co, Ni, Cu, Zn) in nitrogenase‐imitated model‐iron polysulfide (FeSx), a series of FeMSx catalysts with tailorable protonation kinetics are obtained. The key intermediates behaviors traced by in situ FT‐IR and Raman spectroscopy and operando electrochemical impedance spectroscopy demonstrate the strong protonation kinetics‐dependent selectivity that mathematically follows a log‐linear Bradley curve. Strikingly, FeCuSx exhibits a record‐high selectivity of 75.05 % at −0.1 V (vs. RHE) for NH3 production in 0.1 M KOH electrolyte.

Unveiling the Protonation Kinetics-Dependent Selectivity in Nitrogen Electroreduction: Achieving 75.05 % Selectivity.

While higher selectivity of nitrogen reduction reaction (NRR) to ammonia (NH3 ) is always achieved in alkali, the selectivity dependence on nitrogen (N2 ) protonation and mechanisms therein are unrevealed. Herein, we profile how the NRR selectivity theoretically relies upon the first protonation that is collectively regulated by proton (H) abundance and adsorption-desorption, along with intermediate-*NNH formation. By incorporating electronic metal modulators (M=Co, Ni, Cu, Zn) in nitrogenase-imitated model-iron polysulfide (FeSx), a series of FeMSx catalysts with tailorable protonation kinetics are obtained. The key intermediates behaviors traced by in situ FT-IR and Raman spectroscopy and operando electrochemical impedance spectroscopy demonstrate the strong protonation kinetics-dependent selectivity that mathematically follows a log-linear Bradley curve. Strikingly, FeCuSx exhibits a record-high selectivity of 75.05 % at -0.1 V (vs. RHE) for NH3 production in 0.1 M KOH electrolyte.

Computational Insight into Defective Boron Nitride Supported Double-Atom Catalysts for Electrochemical Nitrogen Reduction

Designing highly selective and efficient double-atom electrocatalysts (DACs) is essential for achieving a superior nitrogen-reduction reaction (NRR) performance. Herein, we explored the defective boron nitride–supported cage-like double-atom catalysts to rummage the qualified NRR catalysts. Based on a systematic evaluation of the stability, N2 adsorption, NRR selectivity and activity of 10 DACs of TM1-TM2@VB-BN, we predicted Ru-Ti@VB-BN to be the NRR candidate with a limiting potential of −0.40 V. Compared to the corresponding single-atom catalysts, the introduction of Ti/Mo modulates the d-band center of the active metal atom, which improves the NRR performance. Moreover, the magnetic Ru-Ti dimer can facilitate the transfer of charge to molecular N2, ensuring a significant activation of the inert N≡N bond. This research not only opens up new avenues for designing boron nitride–supported DACs for NRR, but also deepens the understanding of DACs in N2 activation.