Nitrogen Reduction Reaction Catalytic Activity Research Articles

Theoretical exploration of the nitrogen fixation mechanism of two-dimensional dual-metal FeTM@GY (TM = Fe, Mo, Co, and V) electrocatalysts.

In contrast to the energy-consuming Haber-Bosch process, ammonia synthesis by electrocatalysis under ambient conditions is an efficient and environmentally friendly method. In this work, through first principles calculations, the potential of four dual-atom FeTM (TM = Fe, Mo, Co, and V) anchored graphyne (FeTM@GY) as efficient nitrogen reduction reaction (NRR) catalysts is systematically investigated. Among them, FeMo@GY is the most promising, with excellent NRR catalytic activity, high ability to suppress the competing hydrogen evolution reaction (HER), and good stability. Moreover, NRR prefers the maximum pathway with the calculated onset potentials of -0.27 V for FeMo@GY. This work not only suggests that FeMo@GY holds great promise as an efficient, low-cost, and stable dual-atom catalyst for NRR but also further provides a guiding idea for the design of efficient NRR catalysts.

Metal dimers anchored on boron nitride monolayers with boron divacancy as an effective nitrogen fixation electrocatalyst: A computational study

As a fascinating approach for sustainable NH3 production, the electrocatalytic nitrogen reduction reaction (NRR) is still hampered by low Faraday efficiency due to high energy required for inert N N triple bond activation and competitive hydrogen evolution reaction (HER). In this paper, we propose a method to increase the NRR catalytic activity by constructing bimetallic sites on boron nitride (BN) monolayer. In order to approach the efficient NRR region, the metal-based linear-scaling relationship between adsorbed intermediates is broken by synergistic effects between the bimetallic active sites. TiRu-BN was identified as an effective NRR electrocatalyst with low limiting potential (−0.28 V) and superior selectivity after systematic evaluation of the thermal stability, electrochemical stability, activity, and selectivity of 36 homo- and heteronuclear diatomic catalyst candidates. Analysis on the origin of high performance shows the screened high-performance diatomic catalyst is located in the region of moderate linear-scaling relationship breaking of intermediates. Breaking the linear scale relationship to the most significant extend does not imply the most improved catalytic activity. This work not only provides experimentally synthesizable exceptional NRR electrocatalyst candidates, but also provides theoretical guidance for practical application of efficient NRR electrocatalyst.

Rational design single-atom modified Zr2CO2 MXene as a promising catalyst for nitrogen reduction reaction

Renewable production of ammonia via the electrocatalytic nitrogen reduction reaction (NRR) is highly desirable. However, rational design of electrocatalysts with high promising activity under ambient conditions is a challenging subject. In this work, the stability, NRR activity and selectivity of single transition metal (TM, TM = Ti, V, Fe, Ni, Nb, Mo, Ru, and W), nonmetal B and N, and TM and N3 co-modification Zr2CO2 (named TM/Zr2CO2, B(N)/Zr2CO2, and TMN3/Zr2CO2, respectively) are investigated by density functional theory (DFT) calculations. The results revealed that single atom (both transition metal and nonmetal atoms) modification can greatly enhance the NRR catalytic activity and selectivity of original Zr2CO2, and different nonmetal doping concentration can deliver different NRR activity by adjust the interaction strength between doping atom and Zr atom. Among the studied materials, W/Zr2CO2 possesses the highest NRR performance via the distal pathway with the NRR overpotential (ηNRR) of 0.14 V, B/Zr2CO2 possesses the highest NRR performance (ηNRR = 0.26 V) and selectivity via the enzymatic pathway, and for the co-doped systems, RuN3/Zr2CO2 delivers the highest NRR activity with the corresponding ηNRR of 0.54 V. The crystal orbital Hamilton population (COHP), density of states, charge transfers, and work function (Φ) results indicated that the TM and nonmetal atoms can adjust the electronic properties of the Zr2CO2 surface to break the inertness of N2 and form the key intermediate *NNH or *N-*NH, and therefore enhance their NRR activity. The ab initio molecular dynamics (AIMD) simulation results suggested that the structures of the modified Zr2CO2 are dynamically stable at reaction temperature. These results indicated that the proposed surface modifications by W and nonmetal B are the effective approaches for achieving promising NRR electrocatalysts for N2 fixation.

Single-atom W anchored Janus transition metal dichalcogenides as a promising catalyst for the ammonia synthesis

Electrochemical nitrogen reduction reaction (NRR) has emerged as an eco-friendly and economical tactic for ammonia synthesis recently. However, for most NRR catalysts, high overpotential and low Faraday efficiency are the main bottlenecks for their practical applications. Herein, a sequence of transition metals anchored on a novel category of transition metal dichalcogenides monolayers, Janus TMDs (TM@MoSSe, TM = Sc-Zn, Mo, W, Ru-Ag, and Os-Au), as NRR catalysts were investigated through a three-step detailed screening based on the density function theory (DFT) calculations. According to the estimated stability, high catalytic activity, and unexceptionable selectivity of TMDs, W@MoSSe and Os@MoSSe were identified as effective candidate catalysts for NRR, of which W@MoSSe was screened as the optimal NRR catalyst, and the limiting potential is −0.15 V. Importantly, W@MoSSe exhibits remarkable inhibition on the hydrogen evolution reaction (HER), due to the ultra-high Faraday efficiency (100%). Notably, more density of states in W@MoSSe, apparent charge transfer, and strong orbital hybridization between W@MoSSe and NRR intermediates may contribute to its observed high NRR catalytic activity. These findings showed the feasible applications of Janus TMDs in the single-atom catalysis of the NH3 synthesis, which could open a new bright prospect for exploring efficient NRR catalysts experimentally.

Theoretical screening of single-atom electrocatalysts of MXene-supported 3d-metals for efficient nitrogen reduction

Single-atom catalysts (SACs) with metal atoms embedded in MXenes are potentially low-cost, highly efficient, and environment-friendly electrocatalysts for ammonia production due to their high stability, unique electronic structure, and the highest atom utilization. Here, density functional theory calculations are carried out to systematically investigate the geometries, stability, electronic properties of SACs with the 3d-transition metal M (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) atoms embedded in the Ti defect sites of Ti2CO2 (denoted as M1@Ti2CO2). A highly stable V1@Ti2CO2 catalyst has been found to show excellent catalytic performance for N2 reduction reaction to produce NH3 after screening the 3d transition metals. The results show that V1@Ti2CO2 can not only strongly adsorb N2, but also exhibits an excellent Nitrogen reduction reaction (NRR) catalytic activity with a limiting potential of only −0.20 V and a high ability to suppress the competing hydrogen evolution reaction. The excellent NRR catalytic activity of V1@Ti2CO2 is attributed to the strong covalent metal-support interaction that leads to superb N2 adsorption ability of V atom. Furthermore, the embedded V single atoms facilitate electron transfer, thus improving the catalytic performance for NRR. These results demonstrate that V1@Ti2CO2 is a potentially promising 2D material for building robust electrocatalyst for NRR.

First principles study on the structural properties of 13 transition metal doped CdS and the reaction mechanism of ammonia synthesis

Single-atom catalysts with ultra-high atomic utilization and selectivity show great potential in the production of NH3 through electrocatalytic nitrogen reduction reaction (NRR). In this paper, 13 single-atom cadmium sulfide (TM − CdS) doped with different transition metals (TM) (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Ag) were constructed separately using a density functional theory approach to calculate the structural stability and the reaction mechanism of catalytic ammonia synthesis. hree systems, Fe − CdS, Mo − CdS, and Ru − CdS, were screened out from the 13 doped metal 0structures on the basis of the computational results. The above three systems have more stable structures, can transfer more charge to activate N2 molecules, and exhibit better NRR catalytic activity. The limiting potential NRR on the Mo − CdS structure is only − 0.261 V, which is lower than that of Fe − CdS (−0.353 V), Ru − CdS (−0.461 V) and CdS (−2.124 V). This work will be of great value of designing and employing the doped single-atom catalysts for efficient electrolytic nitrogen reduction reaction.

Mo-based catalysts based on B-modified two-dimensional carbon-rich conjugate frameworks for efficient nitrogen reduction reaction

Under environmental conditions, electrochemical nitrogen reduction reaction (NRR), which has the advantages of low energy consumption, zero CO2 emissions, green and sustainability, is considered to be an alternative to the Haber-Bosch method for ammonia synthesis. However, the practical application of NRR is hindered by the poor N2 adsorption capacity, low NH3 synthesis efficiency, and poor selectivity of the catalyst. In this paper, from a theoretical point of view, we design a Mo-based catalyst with multiple active sites based on B-modified 2D CCFs. The B atom has a similar N2 activation mechanism to transition metal atoms in that their empty orbitals (sp3, d orbitals) can accept lone pairs of electrons of nitrogen and feedback electrons to the anti-bond orbitals of the NˆN bond. Moreover, the addition of the B atom leads to new orbital hybridization and charge distribution, which strengthens the N2 adsorption capacity and reduces the energy change, thereby improving the NRR catalytic activity. After a series of analyses, it is concluded that MoZr-BPc CCF catalyst has the best NRR activity with the minimum limiting potential of −0.36 V, the overpotential of 0.20 V, and FENRR of 100%, and it can well inhibit the HER extremely. The synergistic effect of non-metallic and metal atoms provides a new idea for the rational design of NRR electrocatalysts and lays a theoretical foundation for the widespread use of NRR in practical applications.

Single-Atom Metal Anchored Penta-Graphene for Highly Efficient and Selective Electroreduction of Nitrogen into Ammonia

The Haber-Bosch (H–B) process might take place by electrochemical nitrogen reduction reaction (NRR) to generate ammonia if appropriate electrocatalysts can be matured. We methodically investigate the reaction mechanisms of the electrochemical NRR on a single-atom metal anchored penta-graphene (TM-PG, TM = Sc–Hg) by density functional theory computations. Particularly, 14 TM-PGs including Ti-, V-, Cr-, Co-, Cu-, Nb-, Mo-, Tc-, Ru-, Rh-, W-, Re-, Os-, and Ir-PG are selected benefiting from their high activity for the NRR (limiting potential ≤ −0.98). We also studied the competitive hydrogen evolution reaction (HER) on the TM-PGs. Among them, 12 TM-PG (Ti-, V-, Cr-, Co-, Mo-, Tc-, Ru-, Rh-, W-, Re-, Os-, and Ir-PG) catalysts suppressing the competitive HER with high selectivity (Faradaic efficiency of ∼100%) are obtained. The Cr-, Mo-, Tc-, Re-, Os-, and Ir-PG will have superior performance for the NRR with a low limiting potential less than 0.6 V. Partial density of states (PDOS) and Bader charge analysis shed light on the origin of NRR catalytic activity of TM-PG. This study extends the penta-carbon family as promising electrocatalysts for the NRR as well as provides a modus for the practical design of NRR catalysts under ambient conditions.

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.

Engineering oxygen vacancies and low-valent bismuth at the surface of Bi2MoO6 nanosheets for boosting electrocatalytic N2 reduction

Electrochemical nitrogen reduction reaction (NRR) is considered as an alternative to industrial Haber-Bosch N2 fixation process. Herein, an iodide ion assisted one-step hydrothermal method was developed to prepare Bi2MoO6 nanosheets with oxygen vacancies (OVs) and low-valent bismuth at the surface. The introduction of OVs makes Bi2MoO6 nanosheets possess rich unsaturated coordination surface atoms, and enhances the conductivity and N2 adsorption. Low-valent bismuth with 6p orbits reinforces the interaction with N2 via π back-donation. The high-efficiency adsorption and protonation of N2 over OVs-Bi2MoO6 catalyst was confirmed by N2 in-situ DRFTIR spectra and temperature-programmed-desorption. The obtained OVs-Bi2MoO6 nanosheets accomplished a favorable ammonia yield of ∼24.38 μg·mg−1h − 1 and a high Faradaic efficiency of 14.1% at −0.3 V in 0.1 M HCl solution. A feasible OVs assisted π back-donation mechanism was proposed for the enhanced NRR catalytic activity on OVs-Bi2MoO6 catalyst.

1+1>2: Learning from the interfacial modulation on single-atom electrocatalysts to design dual-atom electrocatalysts for dinitrogen reduction

Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene (hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction (NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dual-atom catalysts for NRR.

Computational Insight into Metallated Graphynes as Single Atom Electrocatalysts for Nitrogen Fixation.

The electrochemical nitrogen reduction reaction (NRR) is expected to achieve sustainable ammonia synthesis via direct nitrogen fixation; however, the high-quality catalysts that play a crucial role in the NRR are still lacking. The emerging transition metal-1,3,5-triethynylbenzene (TM-TEB) frameworks offer attractive possibilities in the electrochemical catalysis due to the featured atomic and electronic structures. This work presents a comprehensive first-principles study of the TM-TEB systems for TMs from the first three d-block series and systematically explores their potential applications as NRR electrocatalysts. By designing a hierarchical screening strategy, the TM-TEB systems are evaluated based on the NRR catalytic activity as well as the competition from the hydrogen evolution reaction. In addition, in order to have a deeper understanding of the catalytic activities of the TM-TEB systems, diverse possible NRR paths on the TM-TEB surfaces are completely analyzed as well. Our analysis reveals that the TM-TEB systems with TM = V, Mo, Tc, W, and Os are electrocatalysts with a high NRR catalytic activity, while among them, only Mo- and V-TEB show promising NRR selectively. This work demonstrates the great potential of the TM-TEB systems as electrocatalysts in the NRR process, which improves the understanding of the TM-TEB systems and can motivate further exploration of their application in catalysis.

Ni-Doped Mo2C Anchored on Graphitized Porous Carbon for Boosting Electrocatalytic N2 Reduction.

Facilitating the efficient activation of N2 molecules and inhibiting the competing hydrogen evolution reaction remain a challenge in the nitrogen reduction reaction (NRR). A heteroatom doping strategy is an effective way to optimize the energy barrier during the NRR process to improve the catalytic efficiency. Herein, we report Ni-doped Mo2C anchored on graphitized porous conductive carbon for regulating the electronic structure and catalytic properties of electrocatalysts toward NRR. Benefiting from the porous structure and graphitization features of the carbon matrix, more active sites and high electronic conductivity were achieved. Meanwhile, with the doping of Ni atoms, the electronic configuration near the Ni-Mo active sites was optimized and the adsorption of N2 on them was also promoted due to the increased electron transfer. Moreover, the lowered energy barrier of the NRR process and the suppressed hydrogen adsorption on the active site all resulted in the high catalytic activity and selectivity of the catalyst. Therefore, a high NH3 yield rate of 46.49 μg h-1 mg-1 and a faradic efficiency of 29.05% were achieved. This work not only validates the important role of heteroatom doping on the regulation of NRR catalytic activity but also provides a promising avenue for the green synthesis of NH3.

Phase Transfer of Mo2C Induced by Boron Doping to Boost Nitrogen Reduction Reaction Catalytic Activity

AbstractFacilitating the cleavage of a NN bond and suppressing the competition hydrogen evolution reaction is essential, and but still remains a challenge in nitrogen reduction reaction (NRR). Crystal phase tailoring is an effective approach to optimize the energy barrier during the NRR process to improve the catalytic efficiency. Herein, a boron‐doping strategy to induce phase transfer from hexagonal Mo2C to cubic Mo2C for regulating the electronic structure and catalytic properties of electrocatalysts toward NRR is reported. The B doped cubic Mo2C is found to increase the exposure of active sites, regulate the d band center of Mo for enhancing the adsorption and activation of nitrogen, and reduce the energy barrier of NRR pathway, giving rise to a high ammonia yield of 52.1 μg h−1 mg−1 at −0.6 V versus reversible hydrogen electrode under ambient conditions. More importantly, the hydrogen adsorption on the surface of electrocatalyst is significantly inhibited due to the B‐doping, further improving the faradic efficiency to 36.9%, which is 4 times that of hexagonal Mo2C (9%). This work not only sheds light on the atomic‐scale design of efficient NRR electrocatalysts, but also provides a promising avenue for synchronizing the catalytic activity and selectivity for catalytic reactions.

Single transition metal atom anchored on VSe2 as electrocatalyst for nitrogen reduction reaction

There has been an increasing interest in converting nitrogen (N2) to ammonia (NH3) via electrochemical nitrogen reduction reaction (NRR). In this study, the NRR catalytic performance of a series of single transition metal (TM) atoms anchored on two dimensional VSe2 (TM-VSe2) was studied via performing the first-principles calculations. Among the investigated single-atom catalyst of TM-VSe2, W-VSe2 demonstrates the best NRR catalytic performance with a limiting potential of −0.36 V and effective inhibition of the competitive hydrogen evolution reaction. Meanwhile, our calculations demonstrate that W-VSe2 is highly stable as single-atom anchored on the surface of VSe2 monolayer, whose improved electrical conductivity ensures the electron transform during NRR process. Moreover, we found that the limiting potential of NRR on TM-VSe2 was negatively correlated with the adsorption energy of reaction intermediate *N-NH, and related with the total magnetic moment of TM-VSe2. Importantly, we identified the origin of the NRR catalytic activity from electronic aspect. Our results provide a new way for measuring the NRR catalytic activity of single-atom catalysts.

A theoretical study on molybdenum and sulfur co-doped graphene for electrocatalytic nitrogen reduction

The electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy to generate NH3 in mild condition. Herein, we designed four NRR single-atom catalysts to mimic the structures of FeMo-cofactor in nitrogenase, in which a Mo or Fe atom is anchored to sulfur doped graphene carbon nanosheets (Mo/Fe@S-gCNS). Density functional theory calculations were performed to investigate the stability of Mo/Fe@S-gCNS, as well as their NRR activity. The results suggest that Mo@S-gCNS coordinated with three S (Mo-S3) displays the best NRR catalytic activity among the four catalysts, and the NRR prefers to proceed through the enzymatic pathway with an overpotential as low as 0.24 V. The outstanding performance is mainly attribute to the appropriate coordination environment together with the intrinsic electronic structure of the embedded Mo atom. These findings contribute to designing the NRR single-atom catalysts and understanding the potential active sites of the FeMo-cofactor.

First-principles study of two-dimensional material Cr2B2 as catalyst for electrochemical nitrogen reduction reaction

• The catalytic performance of Cr 2 B 2 for NRRby using DFT method. • There is an excellent NRR catalytic activity when N 2 adsorbed Cr-B bond. • The limiting potential can be reduced by N N breaking to acquire better NRR performance. Electrochemical nitrogen reduction reaction (NRR) is becoming increasingly promising alternatively to the traditional Haber-Bosch process but developing efficient electrocatalysts is still a challenge. In this job, we searched that the catalytic performance of Cr 2 B 2 for NRR by way of density functional theory (DFT) calculations. We mainly screened out four favorable N 2 adsorbed structures, including N 2 adsorption on the B-B bonds, Cr-B bonds, top site of B and Cr atom. It was found that the largest adsorption energy was −1.235 eV when N 2 was adsorbed on the Cr-B bond in a side-on structure, and has a better excellent NRR catalytic activity with the limiting potential is 0.29 V. The catalytic activity of all structures was better in the alternating mechanism of nitrogen reduction reaction. As the antibonding orbitals approach the Fermi level, the number of electrons in the antibonding orbitals increases. The limiting potential of T Cr _end can also be reduced from 0.88 V to 0.35 V by N N bond breaking after the second hydrogen, which contribute to the greater NRR performance. We hope that this research will offer a viable strategy for the design of NRR catalysts, and offer a new way of thinking for MBene as a catalyst for NRR.

Anchoring an Fe Dimer on Nitrogen-Doped Graphene toward Highly Efficient Electrocatalytic Ammonia Synthesis.

Electrochemical reduction of N2 to NH3 based on sustainable energy is a green technique to produce decentralized and on-demand ammonia. In this work, taking graphene as a design platform, we explore the dual-atom catalysts (DACs) via embedding two homonuclear transition metal (TM) atoms into graphene decorated with four neighboring pyrrolic nitrogen atoms (TM2N4@graphene) to computationally screen the qualified nitrogen reduction reaction (NRR) catalysts. On the basis of the activity, selectivity, and stability of 15 homonuclear DACs of TM2N4@graphene, Fe2N4@graphene is identified as the most efficient NRR catalyst with a limiting potential of only -0.32 V. Electronic structure analysis demonstrates that the low oxidation state of Fe (+1) remarkably activates the molecular N2, which contributes to its excellent NRR catalytic activity. Moreover, the kinetic studies reveal all of the NRR elementary steps exhibiting barriers smaller than that of the hydrogen evolution reaction (HER), showing that HER is effectively suppressed. In addition, we find that the integral crystal orbital Hamilton population (ICOHP) can be used as a descriptor to describe the Gibbs free energy of each step for its NRR performance. This work not only provides theoretical guidance for designing DACs for NRR but also promotes the understanding of DACs for N2 fixation.

Modulation effect in adjacent dual metal single atom catalysts for electrochemical nitrogen reduction reaction

Nitrogen reduction reaction (NRR) is a clean mode of energy conversion and the development of highly efficient NRR electrocatalysts under ambient conditions for industrial application is still a big challenge. Metal-nitrogen-carbon (M-N-C) has emerged as a class of single atom catalyst due to the unique geometric structure, high catalytic activity, and clear selectivity. Herein, we designed a series of dual metal single atom catalysts containing adjacent M-N-C dual active centers (MN4/M'N4-C) as NRR electrocatalysts to uncover the structure-activity relationship. By evaluating structural stability, catalytic activity, and selectivity using density functional theory (DFT) calculations, 5 catalysts, such as CrN4/M'N4-C (M’ = Cr, Mn, Fe, Cu and Zn), were determined to exhibit the best NRR catalytic performance with the limiting potential ranging from −0.64 V to −0.62 V. The CrN4 center acted as the main catalytic site and the adjacent M'N4 center could enhance the NRR catalytic activity by modulation effect based on the analysis of the electronic properties including the charge density difference, partial density of states (PDOS), and Bader charge variation. This study offers useful insights on understanding the structure-activity relationship of dual metal single atom catalysts for electrochemical NRR.

Single transition metal atom modified MoSe2 as a promising electrocatalyst for nitrogen Fixation: A first-principles study

Single atom electrocatalysts show great potential to nitrogen reduction reaction (NRR). Here, we studied transition metals (V, Cr, Nb, Mo, Ta, W) doped on MoSe2 as single atom electrocatalysts by first-principles theory. We investigated different NRR pathways and its corresponding Gibbs free energy. It is found that W/MoSe2 has a better NRR catalytic activity than others due to the larger charge composition with N2 molecule. Furthermore, the limiting potential has a quasi-linear relationship with the N2 adsorption energy, which is also related to the changes of charge composition. The result highlights a new family of efficient TM/MoSe2 catalysts for NRR.