First-principles study of the conversion of N 2 to NH 3 bygraphene- supported transition metal catalyst

First-principles study of the conversion of N 2 to NH 3 bygraphene- supported transition metal catalyst | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article First-principles study of the conversion of N 2 to NH 3 bygraphene- supported transition metal catalyst Jiale Liu, Jinqiang Li, Xiao Liu, Wei Song This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7179356/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 29 Oct, 2025 Read the published version in Structural Chemistry → Version 1 posted 11 You are reading this latest preprint version Abstract NH 3 is the most basic raw material in industrial and agricultural production, and it is also an excellent hydrogen carrier, which plays a vital role in the global economy. NH 3 synthesis usually adopts the traditional Haber-Bosch method, which not only consumes a lot of energy but also causes damage to the ecological environment. Electrocatalytic nitrogen reduction reaction (NRR) can produce NH 3 at normal temperature and pressure, so it has attracted a lot of attention. In this study, density functional theory was used to calculate the NRR catalytic mechanism and electrocatalytic performance of graphene-supported triatomic metal clusters. The results showed that VMn 2 @Gra has potential as an NRR catalyst, and the lowest energy barrier simulated was 0.56 eV. Through the analysis of electronic properties, it was found that there was charge transfer between metal and N atom, which further promoted the catalytic process. This study promotes the application of triatomic cluster catalysts in the field of NRR, and these findings provide a new understanding of the theory and experiment of new cluster catalytic systems. Nitrogen reduction reaction Metal clusters Graphene DFT calculations Electrocatalyst Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction NH 3 is not only an important raw material for fertilizer production and chemical industry, but also a good carbon-free energy storage carrier. At present, the widely used industrial synthesis of NH 3 is Haber-Bosch process, which needs to be carried out under high temperature and high pressure. As a result, the process requires a large amount of energy consumption, while producing a large amount of CO 2 , leading to the greenhouse effect and aggravating global warming. Therefore, it is urgent to find a new type in order to break through the limitations of traditional NH 3 synthesis. The emerging electrocatalytic nitrogen reduction reaction (NRR) can synthesize NH 3 using renewable energy under mild conditions, showing great development potential and application value [ 1 – 10 ]. Compared with the traditional Haber-Bosch process, electrocatalytic NRR has many advantages, such as it can be carried out under mild conditions and the process is simple and easy to operate, but also does not produce greenhouse gases such as CO 2 . The electrocatalyst is the core of the catalytic system, and the efficient electrocatalytic reaction cannot be carried out without the careful design of the catalyst. N 2 is difficult to activate due to its inherent chemical inertness, and the hydrogen evolution reaction (HER) with low overpotential will compete with the NRR and reduce the selectivity of the reaction products, so higher requirements are put forward for the design of electrocatalysts [ 11 , 12 ]. Nanocluster catalysts are also popular research objects in the field of electrocatalysis. Such as noble metal containing electrocatalysts (Pd, Au, Ru), non-noble metal electrocatalysts (Mo, Fe, Ti, Co, Ni) and metal-free electrocatalysts (B, N, P). Noble metal catalyst has always been the focus of research in the field of catalysts. The unfilled d orbital of noble metal has a strong ability of electron binding, showing high activity, and the chemical inertia makes it have the advantages of oxidation resistance and corrosion resistance. However, the high cost and small content in nature are not conducive to its universal use. Metal-free catalysts avoid the problems of high cost and environmental pollution of traditional metal catalysts, but the problems of low catalytic activity, poor stability and poor selectivity are difficult to solve. Although non-noble metal materials have low catalytic activity compared with noble metals, they can be combined with each other to enhance the catalytic performance. At the same time, they have been widely concerned by researchers because of their advantages of low cost, good catalytic activity, good selectivity, and easy synthesis. Due to the low stability and induction efficiency of metal cluster catalysts at room temperature, two-dimensional nanomaterials have high specific surface area, a large number of exposed active sites and rich electronic properties [ 11 , 13 – 17 ]. Therefore, the development of new non-noble metal atom supported on two-dimensional catalysts with high activity and selectivity for NRR process has become a hot spot in this field. Due to the relatively large surface area of the cluster, the ideal catalyst can be obtained by changing the composition of some atoms in the cluster. For example, in theory, Su et al. [ 18 ] screened out catalysts with excellent performance anchored in nitro-doped graphene transition metal dimers through the performance of diatomic catalysts superior to single-atomic catalysts. Sixteen catalysts stood out, among which ScMo@N 6 -GN had the limiting potential of − 0.09 V and Faraday efficiency of 100%. This provided promising candidates and reasonable high-throughput screening strategies for NRR catalysts. Wang et al .[ 19 ] screened the catalytic performance of 36 homonuclear and heteronuclear diatomic catalysts by building bimetallic active sites on a single layer of boron nitride, and finally found that TiRu@BN was an effective NRR electrocatalyst with low limiting potential (–0.28 V) and excellent selectivity. This not only provided excellent NRR electrocatalyst candidates that can be synthesized experimentally, but also provided theoretical guidance for the practical application of efficient electrocatalysts. In terms of experiments, Tu et al .[ 20 ] synthesized Bi nanosheets grown on three-dimensional copper foam substrate through a simple substitution reaction and used them as efficient NRR catalysts. The results showed that Bi nanosheets showed the best activity after 24h replacement reaction. A new method to increase the performance of NRR by developing electrodes through couple substitution was introduced. Feng et al .[ 21 ] constructed a stable non-bonded structure of W-Se atom pairs on C 3 N 4 carrier by photoassisted low temperature reduction (WSe@C 3 N 4 ). The experimental results showed high yield and selectivity, which surpassed all current non-noble metal single atom catalysts (SACs). This experiment provided an advanced strategy for the rational design of new SACs. Among the many two-dimensional material substrates, carbon nanomaterials have the characteristics of high specific surface area, pore structure, good adsorption, good electrical conductivity and low cost, which can be used as excellent substrates. Among many carbon nanomaterials, graphene (Gra) is an allotrope of carbon. Carbon atoms are bonded by sp² hybridization to form a single-layer hexagonal honeycomb lattice structure. It has excellent optical, electrical and mechanical properties, and has important application prospects in nanofabration, materials science, energy, biomedicine and drug delivery. It is considered to be a future revolutionary material [ 22 ] and is widely used in catalysis [ 23 , 24 ]. For example, Chen et al. [ 25 ] and Wu et al. [ 26 ] used density functional theory (DFT) to study a series of atomic catalysts based on the surface of graphene for the NRR process, and found that N ≡ N can be effectively activated, providing new insights for the production of efficient catalysts. The new cluster catalyst composed of carbon nanomaterials combined with metal atoms not only has the advantages of non-metal catalysts, such as high efficiency, low energy consumption, corrosion resistance, etc, but also inherits the advantages of metal-based catalysts, such as high catalytic activity, reusable, selective and wide application. Among them, the metal atoms such as V and Ge have good N 2 fixation properties, and the clusters can effectively adsorb N 2 when the metal elements are paired with each other. The product of the reaction can be effectively desorbed from the surface of the catalyst, making the catalyst use rate higher. For example, Hu et al .[ 27 ] evaluated three graphite-acetylene limited SACs (Mo-TEB, Mo@GY and Mo@GDY) by combining the actual electrochemical conditions with the DFT method, and found that they played a key role in electrode potential and PH. The excellent NRR performance of Mo-TEB is attributed to the proximity of the d-band center to the Fermi level and the enhancement of the magnetic moment at the atomic center, which provided insights into the mechanism of NRR. Zhang et al .[ 28 ] systematically studied a single transition metal anchored on pyrazine-based graphene (py-GY) by using first-principles, and found that WI@py-GY and Moi@py-Gy SACs have good catalytic properties and thermodynamic stability, providing guidance for reasonable design of SACs. In experimental research, Xu et al. [ 29 ] and He et al. [ 30 ] used chemical vapor deposition to prepare ultrathin sandwich structure catalysts (Fe atoms sandwiched between ultrathin BN (catalytic layer) and graphene film (conductive layer)) and F-Fe-NC active sites for electrocatalysis of NRR, respectively. The catalytic results showed excellent NH 3 yield and Faraday efficiency. It provides a new idea for the construction of new NRR electrocatalytic structures and a new strategy for the construction of microenvironments. Therefore, using DFT method, the transition metals atom (TM = V, Cr and Mn) was used to form three atomic clusters loaded on graphene as the research model, and we systematically explores the influence of the X m Y n @Gra (m + n = 3) on the electrocatalytic NRR. 2. Calculation method All calculations in this study were performed using the VASP software package for the first principles of DFT. The generalized gradient approximation (GGA) of the Perdew-Burke-Ernzerhof (PBE) functional is used to describe the exchange correlation energy. The projection plus plane-wave (PAW) method is used for pseudopotential [ 30 – 33 ]. The Graphene model is constructed in 4×4×1 supercell with a 20 Å vacuum layer along the z axis to ensure no interaction between the two periodic units. The plane wave error truncation energy is set to 450 eV, the convergence standard of geometric relaxation energy is 10 − 5 eV, and the convergence standard of force is 0.02 eV/Å. The DFT-D3 method is used to correct the van der Waals interaction. The 3×3×1 grid is used to sample K-points in Brillouin region for structural optimization and static self-consistent calculation. Bader charge analysis is used to study charge transfer between adjacent atoms. The VESTA program is used for visual analysis of differential charge density. Adsorption energy ( E ads ) is determined as follows: E ads = E total – E sur – E mol Where E total is the total energy of the adsorption state, E sur is the energy of the pure surface, and E mol is the energy of the adsorbed molecule. According to the computational hydrogen electrode (CHE) model proposed by Nørskov et al. [ 34 – 36 ], the Gibbs free energy change Δ G is used to evaluate the catalytic performance of NRR. The formula is as follows: Δ G = Δ E + Δ E ZPE – TΔ S Where Δ E is the reaction energy difference of each hydrogenation step in the NRR path; Δ E ZPE and Δ S are the zero-point energy change of each hydrogenation step and the entropy difference at room temperature (T = 298.15 K), respectively. e and U are the number of electrons transferred and the limiting potential applied, respectively. The electrode potential of the key steps to be discussed in this paper is derived from the formula U = − Δ G/e , U L corresponds to the limiting potential, which describes the maximum energy barrier to be overcome in the NRR. 3. Results and discussion 3.1 Adsorption stability of N 2 on X m Y n @Gra, N 2 adsorption on catalyst surface is a prerequisite for NRR process. In the adsorption process, it is necessary to find a suitable adsorption site to ensure the stability of the adsorption process and the smooth progress of the subsequent nitrogen removal process. For the adsorption of N 2 on X m Y n @Gra all possible configurations are considered comprehensively, it is found that N 2 can be adsorbed on metal atoms in two forms, namely end-on and side-on, with a total of 12 configurations. By comparison, it is found that the adsorption energy of N 2 on all X m Y n @Gra configurations is negative (Fig. 1 ), which is an exothermic reaction, reflecting that the adsorption process can be spontaneous. However, we found that the adsorption energy ( E ads ) of four configurations, including MnV 2 @Gra-side, MnV 2 @Gra-end, VCr 2 @Gra-end and CrV 2 @Gra-side, is lower than − 2 .0 eV, and E ads value is too negative, which lead to the difficult removal of N 2 adsorption. Therefore, the possibility of these four configurations as efficient catalysts is excluded. Among all configurations, the E ads difference between the side-on and end-on configurations adsorbed by N 2 at MnV 2 @Gra, MnCr 2 @Gra, VMn 2 @Gra and CrMn 2 @Gra is less than 0.01 eV, and the final simulated configurations are all end-on configurations, so they are combined for further calculation and simulation. 3.2 Screening of electrocatalyst X m Y n @Gra The most important steps in the NRR process are the synthesis of first N 2 H and the dissociation of last NH 3 . This is because N 2 has an inert triple bond and it takes a lot of energy to generate *N 2 H. In addition, the production of the last NH 3 is generally an endothermic process, which is very unfavorable to the dissociation of NH 3 . These two steps are the potential-determining step (PDS) of the NRR process. In order to find efficient catalysts, the adsorption free energies of *N 2 →*N 2 H and *NH 2 →*NH 3 processes were studied to quickly screen out the most suitable catalysts. We need to ensure that the energy barrier of PDS under the action of the catalyst is the lowest, and such catalyst has the highest activity, which can catalyze the NRR process more efficiently. From Fig. 2 , the lowest adsorption free energy of PDS is VMn 2 @Gra-end, which has the best performance. That is, the values of Δ G (*N 2 →*N 2 H) and Δ G (*NH 2 →*NH 3 ) are 0.28 eV and 0.56 eV. However, the surface PDS of other catalysts were all greater than 0.6 eV, indicating that their catalytic activity was relatively poor and no further study was needed. In addition, in order to further determine the catalytic activity of the catalyst, we compared the relationship between the N – N bond length and the charge transfer amount (Table 1). According to the tabular analysis, the length of N – N bond becomes shorter when the amount of charge transfer increases. When N atom is doped on the catalyst surface, the amount of charge transfer increase, so that N 2 can be firmly adsorbed on X m Y n @Gra and the N – N bond can be shortened, which is consistent with the results shown in the simulation. 3.3 Reaction mechanism of VMn 2 @Gra After determining the potential of VMn 2 @Gra as a catalyst, we investigated distal and alternative pathways. The calculated free energy and optimized geometric structures are shown in Fig. 3 and Fig. 4 . For N 2 adsorption, the Δ G value is − 0.95 eV for both distal and alternative pathways. For the distal pathway, the first and second hydrogenation step is *N 2 →*N−*NH and *N−*NH→*NH−*NH with the free energy barrier of 0.24 and 0.17 eV. In the next three to five hydrogenation steps, *N, *NH, *NH 2 intermediates are formed, and the Δ G values are reduced by 0.93, 0.35, 0.53 eV, respectively. At the last hydrogenation step (*NH 2 →*NH 3 ), the free energy is the highest (Δ G = 0.54 eV), indicating that this step is the PDS of the distal pathway. Following the alternative pathway, the hydrogenation step of *N 2 →*N−*NH, *N−*NH→*NH−*NH, and *NH − NH→*NH − NH 2 requires 0.24, 0.13, 0.10 eV input, respectively. These hydrogenation steps are non-spontaneous. On the contrary, this process of *NH − NH 2 →*NH 2 − NH 2 is exothermic (Δ G = − 1.91 eV). The subsequent hydrogenation reaction produces *NH 2 and *NH 3 , with corresponding Δ G values increase of 0.04 and 0.54 eV. Therefore, the PDS in the alternative pathway is also the last hydrogenation step of *NH 2 →*NH 3 with the limiting potential of − 0.54 V. 3.4 VMn 2 @Gra Performance Research In order to more accurately analyze the charge distribution of N-containing intermediates during the catalyst surface adsorption process, we used VESTA software to calculate and draw the charge density difference (CDD) diagram. The CDD allows a more realistic display of changes in the charge distribution in space. The yellow region represents the accumulation of charge, and the cyan region represents the dissipation of charge. As shown in Fig. 5 , charge is transferred from VMn 2 @Gra to *NH 2 and *NH 3 , and there is both accumulation and dissipation of charge on N atom, which shows that during the process of charge transfer, the electrons are transferred bidirectional between the N-containing intermediate and VMn 2 @Gra, which promotes the NRR process. The 3d orbitals in V and Mn atom have occupied orbitals and unoclocked orbitals, which have a crucial influence on the activation of N 2 . To facilitate the analysis of the interaction between 3d orbitals of V and Mn atomr and 2p orbitals of N and C atom, we plotted the partial density of states (PDOS). In Fig. 6 , the vertical and horizontal coordinates represent the density number of electronic states, and the Fermi energy level, respectively. Comparing PDOS, it can be found that in the range near and below the Fermi level, many hybrid peaks are formed between Mn-3d, V-3d and C-2p, and there is an obvious polarization phenomenon. This indicates that VMn 2 @Gra is has a strong catalytic activity. In addition, we find that between − 5 eV and − 1 0 eV, there is a tiny hybrid peak, which is due to the non-occupied 3d orbitals of Mn combining the electrons of the 2π and 3σ orbitals of the N atom to form a bond. At the same time, the strong coupling of the d-2π orbital also causes N 2 to occupy part of the 2π* orbital near the Fermi level, which is also consistent with the previous CDD description. 4. Conclusion NH 3 is an important component of many industrial materials and agricultural supplies. At present, most NH 3 synthesis still relies on Haber-Bosch method, which has low efficiency, high energy consumption and high pollution, so it is urgent to develop a green and efficient method to prepare NH 3 . Electrocatalytic NRR is an ideal alternative method. In this study, we adopted the DFT calculation method, using X m Y n @Gra as the support carrier to find the catalyst with the best activity. During the screening, VMn 2 @Gra-end was refined to be an excellent NRR catalytic system with the highest energy barrier of 0.54 eV. In our further study, we found that there is an effective charge transfer between VMn 2 @Gra and N 2 , which promotes the activation of N 2 and the occurrence of NRR process. This study promotes more applications of triatomic cluster catalysts in the field of NRR, and these findings provide new insights into the theory and experiment of new cluster catalytic systems. Declarations Ethical Approval This study mainly obtained data through computational simulation and did not conduct experiments on humans or animals.Therefore,this statement is not applicable. Funding This work was supported by the [Natural Science Foundation of Henan Department of Education], [Grant No.25A150037]; the [Natural Science Foundation of Henan Province, China ], [Grant No. 252300420021 and 252300420317]. Availability of data and materials The data sources of this study were mainly calculated through Vasp software, and then the data were organized. The data were integrated and summarized through the plotting software Orgin and VESTA.Data can be accessed upon reasonable request from the corresponding author at [ [email protected] ]. Acknowledgments The authors thank Natural Science Foundation of Henan Department of Education (No. 25A150037), Natural Science Foundation of Henan Province, China (Grant No. 252300420021 and 252300420317). Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. 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Supplementary Files Table1.docx Cite Share Download PDF Status: Published Journal Publication published 29 Oct, 2025 Read the published version in Structural Chemistry → Version 1 posted Editorial decision: Revision requested 09 Aug, 2025 Reviews received at journal 08 Aug, 2025 Reviews received at journal 08 Aug, 2025 Reviews received at journal 04 Aug, 2025 Reviewers agreed at journal 29 Jul, 2025 Reviewers agreed at journal 29 Jul, 2025 Reviewers agreed at journal 27 Jul, 2025 Reviewers invited by journal 27 Jul, 2025 Editor assigned by journal 26 Jul, 2025 Submission checks completed at journal 25 Jul, 2025 First submitted to journal 21 Jul, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7179356","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":491862983,"identity":"9899f9b6-6733-4761-83cf-180936337de5","order_by":0,"name":"Jiale Liu","email":"","orcid":"","institution":"Henan Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Jiale","middleName":"","lastName":"Liu","suffix":""},{"id":491862985,"identity":"79adba07-da17-4fd0-841f-037af7c0f44a","order_by":1,"name":"Jinqiang Li","email":"","orcid":"","institution":"Henan Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Jinqiang","middleName":"","lastName":"Li","suffix":""},{"id":491862991,"identity":"0e7a3f11-1f7a-4b03-b41f-64bd698fda05","order_by":2,"name":"Xiao Liu","email":"","orcid":"","institution":"Henan Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Xiao","middleName":"","lastName":"Liu","suffix":""},{"id":491862994,"identity":"7f71054e-07f0-4ee1-b294-16f809caab6c","order_by":3,"name":"Wei Song","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAqElEQVRIiWNgGAWjYDACCTBpw8PP30CaljQZyRkHSNNy2MagIYFIHfyzm49u/Nl2nseA4QDjh485xFhy51jabd622zzmzA3MkjO3EaHFQCLH7Dbjtts8lg0H2Jh5idOS/+3mz23neAwOJBCtJYftBu+2AyRokbiRZnab918yj+SMg83E+YV/RvKzmz/O2Nnz8zcf/PCRGC1IgLGBNPWjYBSMglEwCnADAKFyNtgKYAJhAAAAAElFTkSuQmCC","orcid":"","institution":"Henan Institute of Technology","correspondingAuthor":true,"prefix":"","firstName":"Wei","middleName":"","lastName":"Song","suffix":""}],"badges":[],"createdAt":"2025-07-21 16:10:25","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7179356/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7179356/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11224-025-02655-8","type":"published","date":"2025-10-29T15:57:50+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":87816648,"identity":"dc8d015b-fe1d-4426-ba91-6388b1bb16c8","added_by":"auto","created_at":"2025-07-29 10:13:22","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":80305,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorption energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e) of N\u003csub\u003e2\u003c/sub\u003e on X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra in the end-on and side-on configuration.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/0355ef68b211565bfa3f808b.png"},{"id":87816650,"identity":"6708d233-9599-40d5-ad6d-b57885bab1ec","added_by":"auto","created_at":"2025-07-29 10:13:22","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":78220,"visible":true,"origin":"","legend":"\u003cp\u003eGibbs free energy screening results of NRR process catalyzed by X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra, of *N\u003csub\u003e2\u003c/sub\u003e­→*N\u003csub\u003e2\u003c/sub\u003eH and *NH\u003csub\u003e2\u003c/sub\u003e→*NH\u003csub\u003e3\u003c/sub\u003e processes.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/b37c6c5976423a2ca989b2a5.png"},{"id":87816649,"identity":"55ec3104-475f-42bb-9e7a-9655d8ca2027","added_by":"auto","created_at":"2025-07-29 10:13:22","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":164594,"visible":true,"origin":"","legend":"\u003cp\u003eFree energy diagrams of the NRR process at zero (blue lines) and applied potential (red lines) of various reaction intermediates adsorbed on VMn\u003csub\u003e2\u003c/sub\u003e@Gra via (a) distal and (b) alternative pathway.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/a0b30bddb2fa36eed78bcffb.png"},{"id":87816652,"identity":"3d11c999-830e-42a0-90ba-9adc6f87f61b","added_by":"auto","created_at":"2025-07-29 10:13:22","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":356403,"visible":true,"origin":"","legend":"\u003cp\u003eOptimized geometric structures of various intermediates adsorbed on VMn\u003csub\u003e2\u003c/sub\u003e@Gra via distal and alternative pathway.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/04111cffd29e922b89a8af59.png"},{"id":87816659,"identity":"01dee7a9-7b07-4a63-82f8-22c5b10e1502","added_by":"auto","created_at":"2025-07-29 10:13:22","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":242759,"visible":true,"origin":"","legend":"\u003cp\u003eCharge density difference maps for NH\u003csub\u003e2\u003c/sub\u003e and NH\u003csub\u003e3\u003c/sub\u003e adsorbed on VMn\u003csub\u003e2\u003c/sub\u003e@Gra, where the isosurface value is set to be 0.005 \u003cem\u003ee\u003c/em\u003e/Å\u003csup\u003e3\u003c/sup\u003e and the yellow and cyan color represent the charge accumulation and depletion, respectively.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/a8dad37c94ff709f4672a7b8.png"},{"id":87816654,"identity":"2d4e5da6-bda8-4461-b861-3b4303d98bb5","added_by":"auto","created_at":"2025-07-29 10:13:22","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":185190,"visible":true,"origin":"","legend":"\u003cp\u003eThe calculated partial density of states (PDOS) of (a) NH\u003csub\u003e2\u003c/sub\u003e and (b) NH\u003csub\u003e3\u003c/sub\u003e adsorbed on VMn\u003csub\u003e2\u003c/sub\u003e@Gra; The Fermi level is set to zero in the dotted line.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/ca38c32ab429a2abad133480.png"},{"id":95040450,"identity":"fac614e5-ef58-444e-bb17-ffc4f1364b11","added_by":"auto","created_at":"2025-11-03 16:08:56","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1615019,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/f4a204b5-cb40-47c6-9019-f4a748eaf72c.pdf"},{"id":87818713,"identity":"5c04b058-ee60-426e-a29e-a17d8b53ac49","added_by":"auto","created_at":"2025-07-29 10:37:22","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":91437,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-7179356/v1/c05b6833b0ac655301a1ce8c.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"First-principles study of the conversion of N 2 to NH 3 bygraphene- supported transition metal catalyst","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eNH\u003csub\u003e3\u003c/sub\u003e is not only an important raw material for fertilizer production and chemical industry, but also a good carbon-free energy storage carrier. At present, the widely used industrial synthesis of NH\u003csub\u003e3\u003c/sub\u003e is Haber-Bosch process, which needs to be carried out under high temperature and high pressure. As a result, the process requires a large amount of energy consumption, while producing a large amount of CO\u003csub\u003e2\u003c/sub\u003e, leading to the greenhouse effect and aggravating global warming. Therefore, it is urgent to find a new type in order to break through the limitations of traditional NH\u003csub\u003e3\u003c/sub\u003e synthesis.\u003c/p\u003e\u003cp\u003eThe emerging electrocatalytic nitrogen reduction reaction (NRR) can synthesize NH\u003csub\u003e3\u003c/sub\u003e using renewable energy under mild conditions, showing great development potential and application value [\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8 CR9\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. Compared with the traditional Haber-Bosch process, electrocatalytic NRR has many advantages, such as it can be carried out under mild conditions and the process is simple and easy to operate, but also does not produce greenhouse gases such as CO\u003csub\u003e2\u003c/sub\u003e. The electrocatalyst is the core of the catalytic system, and the efficient electrocatalytic reaction cannot be carried out without the careful design of the catalyst. N\u003csub\u003e2\u003c/sub\u003e is difficult to activate due to its inherent chemical inertness, and the hydrogen evolution reaction (HER) with low overpotential will compete with the NRR and reduce the selectivity of the reaction products, so higher requirements are put forward for the design of electrocatalysts [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eNanocluster catalysts are also popular research objects in the field of electrocatalysis. Such as noble metal containing electrocatalysts (Pd, Au, Ru), non-noble metal electrocatalysts (Mo, Fe, Ti, Co, Ni) and metal-free electrocatalysts (B, N, P). Noble metal catalyst has always been the focus of research in the field of catalysts. The unfilled d orbital of noble metal has a strong ability of electron binding, showing high activity, and the chemical inertia makes it have the advantages of oxidation resistance and corrosion resistance. However, the high cost and small content in nature are not conducive to its universal use. Metal-free catalysts avoid the problems of high cost and environmental pollution of traditional metal catalysts, but the problems of low catalytic activity, poor stability and poor selectivity are difficult to solve. Although non-noble metal materials have low catalytic activity compared with noble metals, they can be combined with each other to enhance the catalytic performance. At the same time, they have been widely concerned by researchers because of their advantages of low cost, good catalytic activity, good selectivity, and easy synthesis. Due to the low stability and induction efficiency of metal cluster catalysts at room temperature, two-dimensional nanomaterials have high specific surface area, a large number of exposed active sites and rich electronic properties [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan additionalcitationids=\"CR14 CR15 CR16\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Therefore, the development of new non-noble metal atom supported on two-dimensional catalysts with high activity and selectivity for NRR process has become a hot spot in this field.\u003c/p\u003e\u003cp\u003eDue to the relatively large surface area of the cluster, the ideal catalyst can be obtained by changing the composition of some atoms in the cluster. For example, in theory, Su \u003cem\u003eet al.\u003c/em\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e] screened out catalysts with excellent performance anchored in nitro-doped graphene transition metal dimers through the performance of diatomic catalysts superior to single-atomic catalysts. Sixteen catalysts stood out, among which ScMo@N\u003csub\u003e6\u003c/sub\u003e-GN had the limiting potential of \u0026minus;\u0026thinsp;0.09 V and Faraday efficiency of 100%. This provided promising candidates and reasonable high-throughput screening strategies for NRR catalysts. Wang \u003cem\u003eet al\u003c/em\u003e.[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] screened the catalytic performance of 36 homonuclear and heteronuclear diatomic catalysts by building bimetallic active sites on a single layer of boron nitride, and finally found that TiRu@BN was an effective NRR electrocatalyst with low limiting potential (\u0026ndash;0.28 V) and excellent selectivity. This not only provided excellent NRR electrocatalyst candidates that can be synthesized experimentally, but also provided theoretical guidance for the practical application of efficient electrocatalysts. In terms of experiments, Tu \u003cem\u003eet al\u003c/em\u003e.[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e] synthesized Bi nanosheets grown on three-dimensional copper foam substrate through a simple substitution reaction and used them as efficient NRR catalysts. The results showed that Bi nanosheets showed the best activity after 24h replacement reaction. A new method to increase the performance of NRR by developing electrodes through couple substitution was introduced. Feng \u003cem\u003eet al\u003c/em\u003e.[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e] constructed a stable non-bonded structure of W-Se atom pairs on C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e carrier by photoassisted low temperature reduction (WSe@C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e). The experimental results showed high yield and selectivity, which surpassed all current non-noble metal single atom catalysts (SACs). This experiment provided an advanced strategy for the rational design of new SACs.\u003c/p\u003e\u003cp\u003eAmong the many two-dimensional material substrates, carbon nanomaterials have the characteristics of high specific surface area, pore structure, good adsorption, good electrical conductivity and low cost, which can be used as excellent substrates. Among many carbon nanomaterials, graphene (Gra) is an allotrope of carbon. Carbon atoms are bonded by sp\u0026sup2; hybridization to form a single-layer hexagonal honeycomb lattice structure. It has excellent optical, electrical and mechanical properties, and has important application prospects in nanofabration, materials science, energy, biomedicine and drug delivery. It is considered to be a future revolutionary material [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e] and is widely used in catalysis [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. For example, Chen \u003cem\u003eet al.\u003c/em\u003e [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e] and Wu \u003cem\u003eet al.\u003c/em\u003e [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e] used density functional theory (DFT) to study a series of atomic catalysts based on the surface of graphene for the NRR process, and found that N\u0026thinsp;\u0026equiv;\u0026thinsp;N can be effectively activated, providing new insights for the production of efficient catalysts.\u003c/p\u003e\u003cp\u003eThe new cluster catalyst composed of carbon nanomaterials combined with metal atoms not only has the advantages of non-metal catalysts, such as high efficiency, low energy consumption, corrosion resistance, etc, but also inherits the advantages of metal-based catalysts, such as high catalytic activity, reusable, selective and wide application. Among them, the metal atoms such as V and Ge have good N\u003csub\u003e2\u003c/sub\u003e fixation properties, and the clusters can effectively adsorb N\u003csub\u003e2\u003c/sub\u003e when the metal elements are paired with each other. The product of the reaction can be effectively desorbed from the surface of the catalyst, making the catalyst use rate higher. For example, Hu \u003cem\u003eet al\u003c/em\u003e.[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e] evaluated three graphite-acetylene limited SACs (Mo-TEB, Mo@GY and Mo@GDY) by combining the actual electrochemical conditions with the DFT method, and found that they played a key role in electrode potential and PH. The excellent NRR performance of Mo-TEB is attributed to the proximity of the d-band center to the Fermi level and the enhancement of the magnetic moment at the atomic center, which provided insights into the mechanism of NRR. Zhang \u003cem\u003eet al\u003c/em\u003e.[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e] systematically studied a single transition metal anchored on pyrazine-based graphene (py-GY) by using first-principles, and found that WI@py-GY and Moi@py-Gy SACs have good catalytic properties and thermodynamic stability, providing guidance for reasonable design of SACs. In experimental research, Xu \u003cem\u003eet al.\u003c/em\u003e [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e] and He \u003cem\u003eet al.\u003c/em\u003e [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e] used chemical vapor deposition to prepare ultrathin sandwich structure catalysts (Fe atoms sandwiched between ultrathin BN (catalytic layer) and graphene film (conductive layer)) and F-Fe-NC active sites for electrocatalysis of NRR, respectively. The catalytic results showed excellent NH\u003csub\u003e3\u003c/sub\u003e yield and Faraday efficiency. It provides a new idea for the construction of new NRR electrocatalytic structures and a new strategy for the construction of microenvironments.\u003c/p\u003e\u003cp\u003eTherefore, using DFT method, the transition metals atom (TM\u0026thinsp;=\u0026thinsp;V, Cr and Mn) was used to form three atomic clusters loaded on graphene as the research model, and we systematically explores the influence of the X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra (m\u0026thinsp;+\u0026thinsp;n =\u0026thinsp;3) on the electrocatalytic NRR.\u003c/p\u003e"},{"header":"2. Calculation method","content":"\u003cp\u003eAll calculations in this study were performed using the VASP software package for the first principles of DFT. The generalized gradient approximation (GGA) of the Perdew-Burke-Ernzerhof (PBE) functional is used to describe the exchange correlation energy. The projection plus plane-wave (PAW) method is used for pseudopotential [\u003cspan additionalcitationids=\"CR31 CR32\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. The Graphene model is constructed in 4\u0026times;4\u0026times;1 supercell with a 20 \u0026Aring; vacuum layer along the z axis to ensure no interaction between the two periodic units. The plane wave error truncation energy is set to 450 eV, the convergence standard of geometric relaxation energy is 10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e eV, and the convergence standard of force is 0.02 eV/\u0026Aring;. The DFT-D3 method is used to correct the van der Waals interaction. The 3\u0026times;3\u0026times;1 grid is used to sample K-points in Brillouin region for structural optimization and static self-consistent calculation. Bader charge analysis is used to study charge transfer between adjacent atoms. The VESTA program is used for visual analysis of differential charge density.\u003c/p\u003e\u003cp\u003eAdsorption energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e) is determined as follows:\u003c/p\u003e\u003cp\u003e\u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e\u003cem\u003e= E\u003c/em\u003e\u003csub\u003etotal\u003c/sub\u003e \u003cem\u003e\u0026ndash; E\u003c/em\u003e\u003csub\u003esur\u003c/sub\u003e \u003cem\u003e\u0026ndash; E\u003c/em\u003e\u003csub\u003emol\u003c/sub\u003e\u003c/p\u003e\u003cp\u003eWhere \u003cem\u003eE\u003c/em\u003e\u003csub\u003etotal\u003c/sub\u003e is the total energy of the adsorption state, \u003cem\u003eE\u003c/em\u003e\u003csub\u003esur\u003c/sub\u003e is the energy of the pure surface, and \u003cem\u003eE\u003c/em\u003e\u003csub\u003emol\u003c/sub\u003e is the energy of the adsorbed molecule.\u003c/p\u003e\u003cp\u003eAccording to the computational hydrogen electrode (CHE) model proposed by N\u0026oslash;rskov \u003cem\u003eet al.\u003c/em\u003e[\u003cspan additionalcitationids=\"CR35\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e], the Gibbs free energy change Δ\u003cem\u003eG\u003c/em\u003e is used to evaluate the catalytic performance of NRR. The formula is as follows:\u003c/p\u003e\u003cp\u003eΔ\u003cem\u003eG\u0026thinsp;=\u003c/em\u003e\u0026thinsp;Δ\u003cem\u003eE\u0026thinsp;+\u003c/em\u003e\u0026thinsp;Δ\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eZPE\u003c/em\u003e\u003c/sub\u003e \u003cem\u003e\u0026ndash;\u003c/em\u003e TΔ\u003cem\u003eS\u003c/em\u003e\u003c/p\u003e\u003cp\u003eWhere Δ\u003cem\u003eE\u003c/em\u003e is the reaction energy difference of each hydrogenation step in the NRR path; Δ\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eZPE\u003c/em\u003e\u003c/sub\u003e and Δ\u003cem\u003eS\u003c/em\u003e are the zero-point energy change of each hydrogenation step and the entropy difference at room temperature (T\u0026thinsp;\u003cem\u003e=\u003c/em\u003e\u0026thinsp;298.15 K), respectively. \u003cem\u003ee\u003c/em\u003e and U are the number of electrons transferred and the limiting potential applied, respectively. The electrode potential of the key steps to be discussed in this paper is derived from the formula U = \u003cem\u003e\u0026minus;\u003c/em\u003eΔ\u003cem\u003eG/e\u003c/em\u003e, \u003cem\u003eU\u003c/em\u003e\u003csub\u003eL\u003c/sub\u003e corresponds to the limiting potential, which describes the maximum energy barrier to be overcome in the NRR.\u003c/p\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e\u003cb\u003e3.1 Adsorption stability of N\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e \u003cb\u003eon\u003c/b\u003e X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra,\u003c/h2\u003e\u003cp\u003eN\u003csub\u003e2\u003c/sub\u003e adsorption on catalyst surface is a prerequisite for NRR process. In the adsorption process, it is necessary to find a suitable adsorption site to ensure the stability of the adsorption process and the smooth progress of the subsequent nitrogen removal process. For the adsorption of N\u003csub\u003e2\u003c/sub\u003e on X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra all possible configurations are considered comprehensively, it is found that N\u003csub\u003e2\u003c/sub\u003e can be adsorbed on metal atoms in two forms, namely end-on and side-on, with a total of 12 configurations. By comparison, it is found that the adsorption energy of N\u003csub\u003e2\u003c/sub\u003e on all X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra configurations is negative (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), which is an exothermic reaction, reflecting that the adsorption process can be spontaneous. However, we found that the adsorption energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e) of four configurations, including MnV\u003csub\u003e2\u003c/sub\u003e@Gra-side, MnV\u003csub\u003e2\u003c/sub\u003e@Gra-end, VCr\u003csub\u003e2\u003c/sub\u003e@Gra-end and CrV\u003csub\u003e2\u003c/sub\u003e@Gra-side, is lower than \u003cem\u003e\u0026minus;\u0026thinsp;2\u003c/em\u003e.0 eV, and \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e value is too negative, which lead to the difficult removal of N\u003csub\u003e2\u003c/sub\u003e adsorption. Therefore, the possibility of these four configurations as efficient catalysts is excluded. Among all configurations, the \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e difference between the side-on and end-on configurations adsorbed by N\u003csub\u003e2\u003c/sub\u003e at MnV\u003csub\u003e2\u003c/sub\u003e@Gra, MnCr\u003csub\u003e2\u003c/sub\u003e@Gra, VMn\u003csub\u003e2\u003c/sub\u003e@Gra and CrMn\u003csub\u003e2\u003c/sub\u003e@Gra is less than 0.01 eV, and the final simulated configurations are all end-on configurations, so they are combined for further calculation and simulation.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e\u003cb\u003e3.2 Screening of electrocatalyst\u003c/b\u003e X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra\u003c/h2\u003e\u003cp\u003eThe most important steps in the NRR process are the synthesis of first N\u003csub\u003e2\u003c/sub\u003eH and the dissociation of last NH\u003csub\u003e3\u003c/sub\u003e. This is because N\u003csub\u003e2\u003c/sub\u003e has an inert triple bond and it takes a lot of energy to generate *N\u003csub\u003e2\u003c/sub\u003eH. In addition, the production of the last NH\u003csub\u003e3\u003c/sub\u003e is generally an endothermic process, which is very unfavorable to the dissociation of NH\u003csub\u003e3\u003c/sub\u003e. These two steps are the potential-determining step (PDS) of the NRR process. In order to find efficient catalysts, the adsorption free energies of *N\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*N\u003csub\u003e2\u003c/sub\u003eH and *NH\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*NH\u003csub\u003e3\u003c/sub\u003e processes were studied to quickly screen out the most suitable catalysts. We need to ensure that the energy barrier of PDS under the action of the catalyst is the lowest, and such catalyst has the highest activity, which can catalyze the NRR process more efficiently. From Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, the lowest adsorption free energy of PDS is VMn\u003csub\u003e2\u003c/sub\u003e@Gra-end, which has the best performance. That is, the values of Δ\u003cem\u003eG\u003c/em\u003e(*N\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*N\u003csub\u003e2\u003c/sub\u003eH) and Δ\u003cem\u003eG\u003c/em\u003e(*NH\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*NH\u003csub\u003e3\u003c/sub\u003e) are 0.28 eV and 0.56 eV. However, the surface PDS of other catalysts were all greater than 0.6 eV, indicating that their catalytic activity was relatively poor and no further study was needed.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eIn addition, in order to further determine the catalytic activity of the catalyst, we compared the relationship between the N\u003cem\u003e\u0026ndash;\u003c/em\u003eN bond length and the charge transfer amount (Table\u0026nbsp;1). According to the tabular analysis, the length of N\u003cem\u003e\u0026ndash;\u003c/em\u003eN bond becomes shorter when the amount of charge transfer increases. When N atom is doped on the catalyst surface, the amount of charge transfer increase, so that N\u003csub\u003e2\u003c/sub\u003e can be firmly adsorbed on X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra and the N\u003cem\u003e\u0026ndash;\u003c/em\u003eN bond can be shortened, which is consistent with the results shown in the simulation.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e3.3 Reaction mechanism of VMn\u003csub\u003e2\u003c/sub\u003e@Gra\u003c/h2\u003e\u003cp\u003eAfter determining the potential of VMn\u003csub\u003e2\u003c/sub\u003e@Gra as a catalyst, we investigated distal and alternative pathways. The calculated free energy and optimized geometric structures are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. For N\u003csub\u003e2\u003c/sub\u003e adsorption, the Δ\u003cem\u003eG\u003c/em\u003e value is \u0026minus;\u0026thinsp;0.95 eV for both distal and alternative pathways. For the distal pathway, the first and second hydrogenation step is *N\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*N\u0026minus;*NH and *N\u0026minus;*NH\u0026rarr;*NH\u0026minus;*NH with the free energy barrier of 0.24 and 0.17 eV. In the next three to five hydrogenation steps, *N, *NH, *NH\u003csub\u003e2\u003c/sub\u003e intermediates are formed, and the Δ\u003cem\u003eG\u003c/em\u003e values are reduced by 0.93, 0.35, 0.53 eV, respectively. At the last hydrogenation step (*NH\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*NH\u003csub\u003e3\u003c/sub\u003e), the free energy is the highest (Δ\u003cem\u003eG\u0026thinsp;=\u003c/em\u003e\u0026thinsp;0.54 eV), indicating that this step is the PDS of the distal pathway. Following the alternative pathway, the hydrogenation step of *N\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*N\u0026minus;*NH, *N\u0026minus;*NH\u0026rarr;*NH\u0026minus;*NH, and *NH\u0026thinsp;\u0026minus;\u0026thinsp;NH\u0026rarr;*NH\u0026thinsp;\u0026minus;\u0026thinsp;NH\u003csub\u003e2\u003c/sub\u003e requires 0.24, 0.13, 0.10 eV input, respectively. These hydrogenation steps are non-spontaneous. On the contrary, this process of *NH\u0026thinsp;\u0026minus;\u0026thinsp;NH\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*NH\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;NH\u003csub\u003e2\u003c/sub\u003e is exothermic (Δ\u003cem\u003eG\u0026thinsp;=\u0026thinsp;\u0026minus;\u003c/em\u003e\u0026thinsp;1.91 eV). The subsequent hydrogenation reaction produces *NH\u003csub\u003e2\u003c/sub\u003e and *NH\u003csub\u003e3\u003c/sub\u003e, with corresponding Δ\u003cem\u003eG\u003c/em\u003e values increase of 0.04 and 0.54 eV. Therefore, the PDS in the alternative pathway is also the last hydrogenation step of *NH\u003csub\u003e2\u003c/sub\u003e\u0026rarr;*NH\u003csub\u003e3\u003c/sub\u003e with the limiting potential of \u0026minus;\u0026thinsp;0.54 V.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e3.4 VMn\u003csub\u003e2\u003c/sub\u003e@Gra Performance Research\u003c/h2\u003e\u003cp\u003eIn order to more accurately analyze the charge distribution of N-containing intermediates during the catalyst surface adsorption process, we used VESTA software to calculate and draw the charge density difference (CDD) diagram. The CDD allows a more realistic display of changes in the charge distribution in space. The yellow region represents the accumulation of charge, and the cyan region represents the dissipation of charge. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e, charge is transferred from VMn\u003csub\u003e2\u003c/sub\u003e@Gra to *NH\u003csub\u003e2\u003c/sub\u003e and *NH\u003csub\u003e3\u003c/sub\u003e, and there is both accumulation and dissipation of charge on N atom, which shows that during the process of charge transfer, the electrons are transferred bidirectional between the N-containing intermediate and VMn\u003csub\u003e2\u003c/sub\u003e@Gra, which promotes the NRR process.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe 3d orbitals in V and Mn atom have occupied orbitals and unoclocked orbitals, which have a crucial influence on the activation of N\u003csub\u003e2\u003c/sub\u003e. To facilitate the analysis of the interaction between 3d orbitals of V and Mn atomr and 2p orbitals of N and C atom, we plotted the partial density of states (PDOS). In Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e, the vertical and horizontal coordinates represent the density number of electronic states, and the Fermi energy level, respectively. Comparing PDOS, it can be found that in the range near and below the Fermi level, many hybrid peaks are formed between Mn-3d, V-3d and C-2p, and there is an obvious polarization phenomenon. This indicates that VMn\u003csub\u003e2\u003c/sub\u003e@Gra is has a strong catalytic activity. In addition, we find that between \u003cem\u003e\u0026minus;\u0026thinsp;5\u003c/em\u003e eV and \u003cem\u003e\u0026minus;\u0026thinsp;1\u003c/em\u003e0 eV, there is a tiny hybrid peak, which is due to the non-occupied 3d orbitals of Mn combining the electrons of the 2π and 3σ orbitals of the N atom to form a bond. At the same time, the strong coupling of the d-2π orbital also causes N\u003csub\u003e2\u003c/sub\u003e to occupy part of the 2π* orbital near the Fermi level, which is also consistent with the previous CDD description.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eNH\u003csub\u003e3\u003c/sub\u003e is an important component of many industrial materials and agricultural supplies. At present, most NH\u003csub\u003e3\u003c/sub\u003e synthesis still relies on Haber-Bosch method, which has low efficiency, high energy consumption and high pollution, so it is urgent to develop a green and efficient method to prepare NH\u003csub\u003e3\u003c/sub\u003e. Electrocatalytic NRR is an ideal alternative method. In this study, we adopted the DFT calculation method, using X\u003csub\u003em\u003c/sub\u003eY\u003csub\u003en\u003c/sub\u003e@Gra as the support carrier to find the catalyst with the best activity. During the screening, VMn\u003csub\u003e2\u003c/sub\u003e@Gra-end was refined to be an excellent NRR catalytic system with the highest energy barrier of 0.54 eV. In our further study, we found that there is an effective charge transfer between VMn\u003csub\u003e2\u003c/sub\u003e@Gra and N\u003csub\u003e2\u003c/sub\u003e, which promotes the activation of N\u003csub\u003e2\u003c/sub\u003e and the occurrence of NRR process. This study promotes more applications of triatomic cluster catalysts in the field of NRR, and these findings provide new insights into the theory and experiment of new cluster catalytic systems.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eEthical Approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis study mainly obtained data through computational simulation and did not conduct experiments on humans or animals.Therefore,this statement is not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the [Natural Science Foundation of Henan Department of Education], [Grant No.25A150037]; the [Natural Science Foundation of Henan Province, China ], [Grant No. 252300420021 and 252300420317].\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and materials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data sources of this study were mainly calculated through Vasp software, and then the data were organized. The data were integrated and summarized through the plotting software Orgin and VESTA.Data can be accessed upon reasonable request from the corresponding author at [[email protected] ].\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors thank Natural Science Foundation of Henan Department of Education (No. 25A150037), Natural Science Foundation of Henan Province, China (Grant No. 252300420021 and 252300420317).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCredit author statement\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eJiale\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eLiu:\u0026nbsp;\u003c/strong\u003eConceptualization, Data curation, Writing-Original draft preparation.\u0026nbsp;\u003cstrong\u003eJinqiang Li\u003c/strong\u003e: Data curation, Visualization, Methodology, Software, Validation.\u0026nbsp;\u003cstrong\u003eXiao Liu\u003c/strong\u003e: Investigation, Formal analysis\u003cstrong\u003e.\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Wei Song:\u003c/strong\u003e Conceptualization, Writing-Reviewing and Editing, Writing-Original draft preparation.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eS.F.Li,X.B.Fu,J.K.Norskov, I. 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Phys. 319 (2005) 178\u0026ndash;184.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table","content":"\u003cp\u003eTable 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"structural-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"stuc","sideBox":"Learn more about [Structural Chemistry](https://www.springer.com/journal/11224)","snPcode":"11224","submissionUrl":"https://submission.nature.com/new-submission/11224/3","title":"Structural Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Nitrogen reduction reaction, Metal clusters, Graphene, DFT calculations, Electrocatalyst","lastPublishedDoi":"10.21203/rs.3.rs-7179356/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7179356/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eNH\u003csub\u003e3\u003c/sub\u003e is the most basic raw material in industrial and agricultural production, and it is also an excellent hydrogen carrier, which plays a vital role in the global economy. NH\u003csub\u003e3\u003c/sub\u003e synthesis usually adopts the traditional Haber-Bosch method, which not only consumes a lot of energy but also causes damage to the ecological environment. Electrocatalytic nitrogen reduction reaction (NRR) can produce NH\u003csub\u003e3\u003c/sub\u003e at normal temperature and pressure, so it has attracted a lot of attention. In this study, density functional theory was used to calculate the NRR catalytic mechanism and electrocatalytic performance of graphene-supported triatomic metal clusters. The results showed that VMn\u003csub\u003e2\u003c/sub\u003e@Gra has potential as an NRR catalyst, and the lowest energy barrier simulated was 0.56 eV. Through the analysis of electronic properties, it was found that there was charge transfer between metal and N atom, which further promoted the catalytic process. This study promotes the application of triatomic cluster catalysts in the field of NRR, and these findings provide a new understanding of the theory and experiment of new cluster catalytic systems.\u003c/p\u003e","manuscriptTitle":"First-principles study of the conversion of N 2 to NH 3 bygraphene- supported transition metal catalyst","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-07-29 10:13:17","doi":"10.21203/rs.3.rs-7179356/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-08-09T22:05:29+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-08-08T15:37:19+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-08-08T12:34:02+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-08-04T06:54:58+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"329410790681071671267675743393551547528","date":"2025-07-30T03:30:28+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"247526515045865753884554277493114488806","date":"2025-07-30T02:53:27+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"266740786949790423751524248631610442255","date":"2025-07-28T02:22:50+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-07-28T02:16:46+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-07-26T06:39:56+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-07-25T16:36:29+00:00","index":"","fulltext":""},{"type":"submitted","content":"Structural Chemistry","date":"2025-07-21T16:01:33+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"structural-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"stuc","sideBox":"Learn more about [Structural Chemistry](https://www.springer.com/journal/11224)","snPcode":"11224","submissionUrl":"https://submission.nature.com/new-submission/11224/3","title":"Structural Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"ec48e0a2-023a-40e6-bd99-523aafdbe7f7","owner":[],"postedDate":"July 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-11-03T16:04:51+00:00","versionOfRecord":{"articleIdentity":"rs-7179356","link":"https://doi.org/10.1007/s11224-025-02655-8","journal":{"identity":"structural-chemistry","isVorOnly":false,"title":"Structural Chemistry"},"publishedOn":"2025-10-29 15:57:50","publishedOnDateReadable":"October 29th, 2025"},"versionCreatedAt":"2025-07-29 10:13:17","video":"","vorDoi":"10.1007/s11224-025-02655-8","vorDoiUrl":"https://doi.org/10.1007/s11224-025-02655-8","workflowStages":[]},"version":"v1","identity":"rs-7179356","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7179356","identity":"rs-7179356","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}