Study on the Electrochemical Performance of MOF-Derived Mn2O3 Electrode Materials on Magnesium Ion Capacitors

Study on the Electrochemical Performance of MOF-Derived Mn2O3 Electrode Materials on Magnesium Ion Capacitors | 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 Study on the Electrochemical Performance of MOF-Derived Mn 2 O 3 Electrode Materials on Magnesium Ion Capacitors Ping-Ping Sun, Yun-Heng Li, Bo Yang, Hai-Yan Liu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8691077/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract This study addresses the bottleneck issues of slow magnesium storage kinetics and low capacity of electrode materials in magnesium ion capacitors (MICs) by proposing a MOF-derived strategy to construct high-performance Mn₂O₃ electrode materials.This study addresses the bottleneck issues of slow magnesium storage kinetics and low capacity of electrode materials in magnesium ion capacitors (MICs) by proposing a MOF-derived strategy to construct high-performance Mn₂O₃ electrode materials. This work validates the feasibility of MOF-derived Mn₂O₃ as an electrode material for magnesium ion capacitors, providing a new approach for low-cost, high-safety, and large-scale magnesium energy storage technologies. Magnesium ion capacitor MOF-derived Mn₂O₃ electrode High specific capacitance Long cycle life Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Introduction The dual pressures of energy crisis and environmental issues are driving the global transition to a sustainable energy system. Efficient energy storage technologies, as the core support for the integration of renewable energy into the grid and the construction of smart grids, have become a research hotspot in the current scientific field [ 1 – 3 ]. Among various energy storage devices, magnesium-ion capacitors (Mg-ion Capacitors, MICs) are expected to replace traditional lithium-ion energy storage devices and achieve breakthroughs in large-scale energy storage applications due to their unique advantages such as abundant magnesium resources, high theoretical capacity (2205 mAh·g⁻¹), and excellent safety [ 4 – 6 ]. Magnesium, as the sixth most abundant element in the Earth's crust, has a reserve about 148 times that of lithium and is widely distributed in resources such as seawater and magnesite. Its low mining cost and environmental friendliness solve the supply chain risks caused by the scarcity of lithium resources from the source, providing resource guarantees for the large-scale development of energy storage technologies [ 7 – 10 ]. However, the commercialization of MICs is still constrained by the performance bottlenecks of key materials, particularly the sluggish magnesium storage kinetics and low capacity of electrode materials, which seriously restrict the energy density and cycle stability of the devices [ 11 – 13 ]. Ideal magnesium storage electrode materials should have appropriate interlayer spacing, high specific surface area, and good electrical conductivity to enable rapid magnesium ion intercalation/deintercalation and efficient charge transfer. Among the reported magnesium storage materials, manganese-based oxides have become highly promising candidates due to their abundant resources, high theoretical capacity, and good environmental compatibility. Among them, manganese trioxide (Mn 2 O 3 ) has demonstrated excellent magnesium storage activity due to its unique crystal structure and moderate magnesium ion adsorption energy [ 14 – 15 ]. However, pure-phase Mn 2 O 3 suffers from poor electrical conductivity, significant volume expansion, and structural collapse during cycling, which makes its actual magnesium storage performance difficult to meet the requirements of devices, and there is an urgent need to break through these limitations through material design and structural regulation. Metal-organic frameworks (MOFs), as a class of porous materials with high specific surface area, controllable pore size and abundant metal active sites, offer an effective approach for the structural optimization of functional electrode materials [ 16 – 18 ]. MOF-derived materials not only inherit the porous structure characteristics of the parent materials, which can shorten the ion transport path and alleviate volume expansion, but also achieve uniform dispersion and valence state regulation of metal active components through the pyrolysis process, significantly enhancing the conductivity and structural stability of the materials [ 19 – 22 ]. Applying the MOF-derived strategy to the preparation of manganese-based materials can precisely construct a synergistic system of "porous structure - active sites - electron transport channels", providing a new solution to the performance shortcomings of Mn 2 O 3 in magnesium storage. Existing studies have shown that MOF-derived manganese oxides, through porous structure regulation and surface defect engineering, have significantly improved magnesium storage capacity and cycling stability compared to traditional preparation methods, verifying the feasibility of this strategy [ 23 – 26 ]. Based on this, this study focuses on the performance breakthrough of Mg-ion capacitor electrode materials, guided by the efficient utilization of magnesium resources. By combining the structural regulation advantages of MOF-derived technology with the magnesium storage potential of Mn 2 O 3 , MOF-derived Mn₂O₃ electrode materials were designed and prepared. Through systematic research on the crystal structure, porous characteristics and surface chemical state of the materials, the magnesium storage mechanism and structure-performance relationship were revealed, providing theoretical support and technical references for the development of high-performance magnesium storage devices [ 27 – 30 ]. This study not only has the potential to break through the performance bottleneck of existing magnesium storage materials, but also promotes the efficient conversion of magnesium resources in the field of energy storage, injecting new impetus into the development of large-scale energy storage technologies. Experimental Part Crystal synthesis All reagents required for the experiment are listed in Table S1 . All chemicals were used as received without further purification. In a typical synthesis, Mn(CH₃COO)₂·4H₂O (0.5 mmol, 0.1225 g) and 2,6-pyridinedicarboxylic acid (0.5 mmol, 0.0835 g) were dissolved in 10 mL of deionized water. The mixture was stirred for 30 min to obtain a homogeneous solution, which was then transferred into a 25 mL Teflon-lined stainless-steel autoclave and heated at 150°C for 24 h. After cooling to room temperature, colorless rod-like single crystals were collected, washed three times with deionized water (20 mL each time), and dried at room temperature. The resulting product was designated as 26p-Mn-MOF. Capacitors performance tests The supercapacitor working electrodes were fabricated by pressing metal oxide materials (mass loading ≈ 2.0 mg cm⁻²) onto nickel foam substrates (1×1 cm) at 10 MPa. Electrochemical performance was evaluated in a three-electrode system with 1 M MgSO 4 electrolyte, using Pt foil and Hg/HgO as counter and reference electrodes, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted on a CHI660E electrochemical workstation, while galvanostatic charge-discharge (GCD) tests and cycling stability assessments were performed using a LAND-CT3001 battery testing system. The specific capacitance (C, F g⁻¹) was calculated from GCD data using the Eq. (1): C = (I × Δt)/(m × ΔV), where I is discharge current (A), Δt is discharge time (s), m is active material mass (g), and ΔV represents the operational voltage window (V). Energy density (E, Wh kg-1) using the Eq. (2): E = CV 2 /7.2, and power density (P, W kg-1) using Eq. (3) P = 3600E/t. Result and discussion Preparation of active substances Figure 1 outlines the preparation of heterogeneous structures. The active substances precursor was synthesized using a hydrothermal method, followed by drying at 25 ℃. Subsequently, the dried precursor was annealed at 500 − 700°C for 2 h in an air atmosphere. The products were named based on the specific annealing temperatures: Mn 2 O 3 -500, Mn 2 O 3 -600 and Mn 2 O 3 -700. Analysis of Precursor Structure The structure of 26p-Mn-MOF was in monoclinic C2/c space group (table S2 ), the formula was C 14 H 10 Mn 2 N 2 O 11 . The simplified unit cell structure and the different coordination environments of Mn atom are shown in Fig. 1 . Figure 1 a is the asymmetric unit comprises a unique cobalt atom (Mn1), a 2,6-pyridine dicarboxylic acid ligands, a half of O atom (O3) and a coordinate water molecule (O6). Mn1 atom has 7 coordination numbers and is bonded with one N atom (N1) from ligand and six O atoms, of which one is from water molecule (O6), four are from three ligands (O2, O2’, O4 and O4’), the other one is from O 2− in water (O3) (Fig. 1 b). The bond distances and bond angles of Mn-O and Mn-N are in the normal range [ 31 – 32 ]. The result of bond distances, bond angles of Mn-O and Mn-N are list in tables S3 and S4. Figure S1 is unit cell from a, b and c axis views. It is obvious that 26p-Mn-MOF is a one dimensional structure. The one coordinate water molecule (O6) share its H atoms with the neighboring oxygen atom (O5) to form H bond (figure S2 ). The H-bonds are list in table S5. Figure S3 is powder XRD pattern of 26p-Mn-MOF and the simulated pattern from the single crystal structure. Compared with the simulated pattern from the single crystal structure, all of the main peaks are well consistent, demonstrating the crystal has a high purity. TG and XRD analysis of electrode material powder Figure 3 a shows the TG curves of the precursor.The TG process can be divided into two stages. The first stage is 30–200°C, which is mainly the loss of free water in the precursor; the second stage is 200–430°C, which is the collapse of the ligand and the gradual transformation of the precursor from MOF to oxide. Figure 1 b shows the powder XRD patterns of the calcination products at different temperatures. It can be seen from the figure that all samples have diffraction peaks at approximately 28.74°, 33.12°, 36.84°, 47.46° and 56.52°, which are consistent with the positions of the diffraction peaks of the Mn 2 O 3 standard card (No. 24–0508), indicating that the calcination products at all temperatures are Mn 2 O 3 . In addition, as the calcination temperature increases, the intensity of the diffraction peaks gradually increases, suggesting that the crystallinity of the products gradually enhances. XPS analysis Figure 4 shows the XPS test results of Mn 2 O 3 -600. Figure 4 a is the total spectrum of Mn 2 O 3 -600, Mn 2 O 3 -600, and Mn 2 O 3 -600. From the figure, it can be seen that this sample contains elements such as Mn, O, and C (the C element mainly comes from the conductive glue used during the test). The high-resolution energy spectra of Mn2p for the three samples (Fig. 4 b) have four main peaks. Through software peak fitting, the peaks at the central positions of 641.2 eV and 642.8 eV correspond to Mn2p 3/2 , and the peaks at the central positions of 653.4 eV and 653.4 eV correspond to Mn 2p 1/2 . These results are consistent with the XPS spectra of Mn 3+ reported in other literatures [ 31 – 32 ]. Figure 4 c is the high-resolution energy spectrum of O1s. Through software peak fitting, it can be fitted into three main peaks. At the binding energy of 529.6 eV, it is the Mn-O bond, and at the binding energy of 531.4 eV, it is the existence of oxygen vacancies [ 33 – 35 ]. In Fig. 4 d, it is the ESP test result of three oxides, which can also prove the existence of oxygen vacancies. Morphology analysis The morphology of the precursor was obtained under different magnifications (50 µm and 10 µm) by scanning electron microscopy (SEM), as shown in Figure S4. The product morphology was uniform and arranged in a staggered manner, presenting as strip-shaped crystalline blocks. The crystal surface was smooth and the purity was high. Figures 5 a-b and Figure S5 show the SEM morphologies after different calcination temperatures. The morphologies of the products obtained at the three temperatures could all maintain the morphology of the precursor, while the products became more fragmented as the temperature increased. From the images under larger magnifications, it can be seen that the oxide morphology maintained a relatively complete surface with some roughness, and some holes appeared on the oxide surface, which was mainly caused by the collapse of the organic ligands during the high-temperature calcination process. Figure 5 c is TEM of Mn 2 O 3 -600. Figures 5 d-e demonstrates HRTEM image of Mn 2 O 3 -600 structure, the spacings with 0.203 nm correspond to (200) plane of Mn 2 O 3 . Electrochemical performance test analysis The electrochemical properties of the oxides were evaluated in a three-electrode system, with the oxides sample as the working electrode, a saturated calomel electrode as the reference, a platinum electrode as the counter electrode, and 1 mol L⁻¹ MgSO 4 as the electrolyte. Figure 6 a shows the cyclic voltammetry (CV) curves of the three oxides at a sweep rate of 50 mV s⁻¹. The CV curve of Mn 2 O 3 -600 exhibits a slightly larger integral area than those of other two, suggesting superior electrochemical performance. Therefore, Mn 2 O 3 -600 was further investigated. Figure 6 b displays the CV curves of Mn 2 O 3 -600 at varying sweep rates. The integral area increases with sweep rate, while the overall shape remains consistent, indicating good structural stability. Similar CV behavior for Mn 2 O 3 -500 and Mn 2 O 3 -700 is illustrated in Figure S6. Figure 6 c presents the logarithmic relationship between sweep rate and peak current for Mn 2 O 3 -600. Linear fitting yields b values of 0.81 and 0.74 for the anodic and cathodic processes, respectively. The corresponding b values for Mn 2 O 3 -500 and Mn 2 O 3 -700 are shown in Figure S7. A b value near 0.5 suggests dominant pseudocapacitive behavior, whereas a value near 1 indicates double-layer capacitance dominance. Values between 0.5 and 1 reflect a combined contribution from both mechanisms [ 36 – 38 ]. Figure d shows the comparison of the contribution of the two mechanisms at a sweep speed of 50 mV − 1 . The contributions of pseudocapacitance and double-layer capacitance at various sweep rates are shown in Fig. 6 e and Figures S8–S10. An increase in sweep rate leads to a higher proportion of double-layer capacitance due to shortened reaction time and reduced diffusion layer thickness [ 38 ]. Figure 7 a compares the galvanostatic discharge curves of the three materials at identical current density. Mn 2 O 3 -600 shows a discharge time of 384 s, outperforming both Mn 2 O 3 -500 (260s) and Mn 2 O 3 -700 (325s). Discharge curves at various current densities (Fig. 7 b and Figure S11) exhibit quasi-symmetric profiles, indicating good reversibility across all samples. Specific capacitance values, calculated using Eq. (1), are plotted in Fig. 7 c. Mn 2 O 3 -600 (326, 326, 296, 273 and 276 F g − 1 ) consistently exhibits higher capacitance than Mn2O3-500 (257, 260, 243, 240 and 236 F g − 1 ) and Mn 2 O 3 -700 (222, 221, 210, 207 and 200 F g − 1 ) across all current densities. Electrochemical impedance spectroscopy (EIS) results are shown in Fig. 7 d. The Nyquist plots display a semicircle in the high-frequency region and a linear segment in the low-frequency range, characteristic of capacitive behavior. The high-frequency intercept represents the ohmic resistance (Rs), while the semicircle diameter corresponds to the charge transfer resistance (Rct). The specific fitting values of the three oxide electrode materials are presented in Table S6. Figure 7 e presents the cycling performance of the materials over 10,000 charge–discharge cycles. All samples maintained coulombic efficiency close to 100%. However, retention varied: Mn 2 O 3 -600 retained 83% of its initial capacitance, while Mn 2 O 3 -500 and Mn 2 O 3 -700 retained approximately 81% and 72%. To evaluate the practical applicability of Mn 2 O 3 -600, an asymmetric hybrid capacitor was constructed using Mn 2 O 3 -600 as the positive electrode and activated carbon (AC) as the negative electrode, with 1 M MgSO 4 aqueous solution as the electrolyte (Fig. 8 a), The mass ratio between the positive and negative electrodes was determined based on the charge balance equation: m + / m − = C m− × ΔV / C m+ × ΔV, where C m+ represents the specific capacitance and ΔV represents the potential window. Based on the GCD profile of AC (Figure S12), which showed a specific capacitance of 250 F g − 1 at 1 A g − 1 , the optimal AC mass was calculated to be 2.608 mg. CV analysis (Fig. 8 b) revealed that AC operated within − 1 to 0 V, while Mn 2 O 3 -600 exhibited redox activity from 0 to 0.6 V, enabling a full-cell voltage window of 1.60 V. The CV curves of the assembled Mn 2 O 3 -600 //AC device (Fig. 8 c–d) retained their shape across varying scan rates and voltage windows, indicating good electrochemical stability. GCD measurements (Fig. 8 e) conducted at current densities from 1 to 5 A g − 1 yielded specific capacitances of 62.5, 54.6, 52.3, 49.6 and 47.6 F g − 1 , respectively, as calculated using Eq. (1). These results confirm the device’s strong rate capability and suitability for energy storage applications. The energy density (E) and power density (P) of the Mn 2 O 3 -600//AC device were calculated using Equations (2) and (3), and the results are presented in Fig. 8 f. At a power density of 173.57 W kg − 1 , the device achieved an energy density of 23.16 Wh kg − 1 . Conclusion This study is based on the abundant resources of magnesium and aims to address the key bottlenecks of poor conductivity, severe volume expansion, and low magnesium storage capacity in magnesium ion capacitors (MICs) electrode materials. A new route for constructing high-performance Mn₂O₃ electrodes using the "MOF-derived strategy" was proposed and verified. The 26p-Mn-MOF precursor was obtained through one-step hydrothermal synthesis, and after controlled calcination at 600°C, Mn₂O₃-600 with a hierarchical porous framework of MOF, abundant oxygen vacancies, and moderate crystallinity was successfully prepared. Its unique "pore-channel - active site - electron transport channel" synergistic structure effectively shortens the diffusion path of Mg²⁺, alleviates the volume change during cycling, and significantly improves the efficiency of electron/ion transport. In a three-electrode system, the specific capacitance of Mn₂O₃-600 reached 326 F g⁻¹ (1 A g⁻¹), which was approximately 27% and 47% higher than the samples at 500°C and 700°C, respectively. After 10,000 charge-discharge cycles, the capacity retention was 83%, and the Coulomb efficiency was approximately 100%, demonstrating excellent rate and cycle stability. An asymmetric magnesium ion capacitor constructed with Mn₂O₃-600 as the positive electrode and activated carbon as the negative electrode had a working voltage extended to 1.6 V, with a device-level energy density of 23.16 Wh kg⁻¹ (power density 173.57 W kg⁻¹), and maintained a stable charge-discharge platform at different rates, confirming its practical potential. Declarations Author Contribution Ping-Ping Sun: Investigation, Methodology, Validation, Writing – Original Draft Yun-Heng Li: Investigation, Data Curation, Visualization Bo Yang: Resources, Investigation Hai-Yan Liu: Conceptualization, Funding acquisition, Supervision, Writing – Review & Editing Acknowledgments This work was supported by The Foundation of Liaoning Provincial Key Laboratory of Energy Storage and Utilization (CNNK202410) and Basic Scientific Research Project of Colleges and Universities of Liaoning Province Education Department (LJ232414435004 and LJ212514435002). 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J Electrochem Soc 166:A1799–A1805. https://doi.org/10.1149/2.0291910JES/XML Xu L, Zhao T, Su C (2025) Effect of Double Ligands on the Structure and Electrochemical Performance of Metal–Organic Framework as the Electrode Material of High-Performance Supercapacitors. ACS Appl Energy Mater 8:6510–6519. https://doi.org/10.1021/acsaem.5c00344 Pandey G, Sharma A, Meenakshi, Pandey K, Menezes PW, Awasthi K (2025) MXene integrated metal-organic framework derived cobalt phosphide for supercapacitor applications. ChemCatChem 17(17):e00430. https://doi.org/10.1002/cctc.202500430 Additional Declarations No competing interests reported. Supplementary Files SupportingInformation.docx 26PMn.cif Cite Share Download PDF Status: Posted Version 1 posted 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. 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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-8691077","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":581537541,"identity":"e90aed75-d8cf-42de-bdde-c8d2403465d5","order_by":0,"name":"Ping-Ping Sun","email":"","orcid":"","institution":"Yingkou Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Ping-Ping","middleName":"","lastName":"Sun","suffix":""},{"id":581537542,"identity":"c787a2e9-3d0b-4ebc-83a6-f7c4f4f55a5c","order_by":1,"name":"Yun-Heng Li","email":"","orcid":"","institution":"Yingkou Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Yun-Heng","middleName":"","lastName":"Li","suffix":""},{"id":581537543,"identity":"12e97d39-c5be-4b23-9e3e-9af9ce9497b6","order_by":2,"name":"Bo Yang","email":"","orcid":"","institution":"Shenghong Refining \u0026 Chemical (Lianyungang) Co., Ltd","correspondingAuthor":false,"prefix":"","firstName":"Bo","middleName":"","lastName":"Yang","suffix":""},{"id":581537544,"identity":"850f3267-cc58-4812-9a36-aa23e3a95ed7","order_by":3,"name":"Hai-Yan Liu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABDElEQVRIiWNgGAWjYBACPmYGNgYGAyCLvbHx8Y8KObDogQd4tLDBtfAcPmzMcMYYoiUBnxYwAgGJtDRpxjaIFga8Wth5zB78KDgsb86QYyBdOM9AzuDa4YdAW+zkdBtwOYzH3LDH4LDhzoYzBsYztxkYS85OMwBqSTY2O4BTi5kEj8Fhxg0HewwSeLf9SeyXTgBpOZC4DY8WyT8Gh+03HOYxOMA7xyCxTTr9A0Et0kBbEjccY0ts5m0wANqSQ8gWtjJpGYP05A1nmA8zzjgG8ktOwYEEA9x+4ec/vE3yzR9r2w33H7b/+FADDLHb6Zs/fKiwk8OlBQqa0QUM8CoHgTqCKkbBKBgFo2AEAwDDMFyJV47W/wAAAABJRU5ErkJggg==","orcid":"","institution":"Yingkou Institute of Technology","correspondingAuthor":true,"prefix":"","firstName":"Hai-Yan","middleName":"","lastName":"Liu","suffix":""}],"badges":[],"createdAt":"2026-01-25 08:23:10","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8691077/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8691077/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":101395221,"identity":"9236326f-4efd-4e4e-9020-167de8e5fb61","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":151907,"visible":true,"origin":"","legend":"\u003cp\u003eExperimental flowchart\u003c/p\u003e","description":"","filename":"image1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/f182d80fca626088ed2c8958.jpeg"},{"id":101395213,"identity":"a4cc79e4-fe86-4846-a81c-49f68fb28175","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":140956,"visible":true,"origin":"","legend":"\u003cp\u003ea) The asymmetric unit of 26p-Mn-MOF; b)The coordination environment of Mn atom.\u003c/p\u003e","description":"","filename":"image2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/f377166fb80d5683585d87d7.jpeg"},{"id":101395215,"identity":"317356e7-434a-479f-b87d-39582ce78fb5","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":126183,"visible":true,"origin":"","legend":"\u003cp\u003eThe TG test results of 26p-Mn-MOF, b)The XRD patterns of the oxides obtained under different calcination temperatures and the comparison results with the standard cards\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/93ec9bdc167b89ee26da892b.png"},{"id":101398653,"identity":"587052ae-ff54-4606-9c18-59230d0e8a15","added_by":"auto","created_at":"2026-01-29 09:43:31","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":259229,"visible":true,"origin":"","legend":"\u003cp\u003ea) total XPS spectra of three oxides, b) Mn spectra, c) O spectra, d) ESP test result of three oxides.\u003c/p\u003e","description":"","filename":"image4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/6d249299795f5022911ded31.jpeg"},{"id":101395223,"identity":"b2eeec92-046c-4855-a867-5c897815fef0","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":355394,"visible":true,"origin":"","legend":"\u003cp\u003eThe morphologies of the samples after being calcined at 600 ℃ (a-b), TEM test result of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 (c-d).\u003c/p\u003e","description":"","filename":"image5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/59ac9906e8c7d71c3e8a07ae.jpeg"},{"id":101398686,"identity":"b2273455-6ef4-45ad-bd4c-1f2d530c6b22","added_by":"auto","created_at":"2026-01-29 09:44:02","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":269602,"visible":true,"origin":"","legend":"\u003cp\u003ea) Comparison of CV curves of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 at the scanning range of 100 mV s-1, b)CV curves of Mn2O3-600, c) CV curve fitting b-value diagram of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600. d) Comparison of the contribution of the two mechanisms at a sweep speed of 100 mV-1 of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600, e) Comparison of contribution rates of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 at different sweep speeds.\u003c/p\u003e","description":"","filename":"image6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/aee9812516675a5bebfbd352.jpeg"},{"id":101395219,"identity":"8d847204-77cb-45c5-bd05-ad972d0e32af","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":321899,"visible":true,"origin":"","legend":"\u003cp\u003ea) Comparison of GCD curves of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 at the current density of 1 A g\u003csup\u003e-1\u003c/sup\u003e, b) GCD curves of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600, c) Specific capacitance under different current densities, d) EIS test results, e) Cyclic performance test of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 under the three-electrode system\u003c/p\u003e","description":"","filename":"image7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/9dd5e050591c99da9598e26f.jpeg"},{"id":101395218,"identity":"11664ccc-cf1d-455e-99a5-dbe30c6ad8ca","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":99394,"visible":true,"origin":"","legend":"\u003cp\u003ea) Two-electrode capacitor model, b) CV curves of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 and AC electrodes at 50 mV s\u003csup\u003e-1\u003c/sup\u003e; c) CV curves of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600//AC device at different scan rates; d) The comparison of CV curves for all devices when the sweep speed is 80 mV s\u003csup\u003e-1\u003c/sup\u003e in different potential, e) GCD curves of FC600//AC device at different current densities.\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/c084373c7a108a742e573b94.png"},{"id":103505316,"identity":"0d1d5b5a-cc22-4209-bd1e-5f3fcf4f0e58","added_by":"auto","created_at":"2026-02-26 13:29:49","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2277701,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/4148a3e1-a7e4-471c-a319-6c06a0e50b60.pdf"},{"id":101398489,"identity":"420869c7-3049-4b2b-b663-78b106a90858","added_by":"auto","created_at":"2026-01-29 09:41:53","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":1590120,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/4dc8e7414f07d8a6fa241e02.docx"},{"id":101395216,"identity":"36365cd2-4b89-42fa-9872-78ee0e9d6256","added_by":"auto","created_at":"2026-01-29 09:03:51","extension":"cif","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":275453,"visible":true,"origin":"","legend":"","description":"","filename":"26PMn.cif","url":"https://assets-eu.researchsquare.com/files/rs-8691077/v1/8ee28e0cadb2cf9a0a31b1c3.cif"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eStudy on the Electrochemical Performance of MOF-Derived Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e Electrode Materials on Magnesium Ion Capacitors\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe dual pressures of energy crisis and environmental issues are driving the global transition to a sustainable energy system. Efficient energy storage technologies, as the core support for the integration of renewable energy into the grid and the construction of smart grids, have become a research hotspot in the current scientific field [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Among various energy storage devices, magnesium-ion capacitors (Mg-ion Capacitors, MICs) are expected to replace traditional lithium-ion energy storage devices and achieve breakthroughs in large-scale energy storage applications due to their unique advantages such as abundant magnesium resources, high theoretical capacity (2205 mAh\u0026middot;g⁻\u0026sup1;), and excellent safety [\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Magnesium, as the sixth most abundant element in the Earth's crust, has a reserve about 148 times that of lithium and is widely distributed in resources such as seawater and magnesite. Its low mining cost and environmental friendliness solve the supply chain risks caused by the scarcity of lithium resources from the source, providing resource guarantees for the large-scale development of energy storage technologies [\u003cspan additionalcitationids=\"CR8 CR9\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eHowever, the commercialization of MICs is still constrained by the performance bottlenecks of key materials, particularly the sluggish magnesium storage kinetics and low capacity of electrode materials, which seriously restrict the energy density and cycle stability of the devices [\u003cspan additionalcitationids=\"CR12\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Ideal magnesium storage electrode materials should have appropriate interlayer spacing, high specific surface area, and good electrical conductivity to enable rapid magnesium ion intercalation/deintercalation and efficient charge transfer. Among the reported magnesium storage materials, manganese-based oxides have become highly promising candidates due to their abundant resources, high theoretical capacity, and good environmental compatibility. Among them, manganese trioxide (Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e) has demonstrated excellent magnesium storage activity due to its unique crystal structure and moderate magnesium ion adsorption energy [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. However, pure-phase Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e suffers from poor electrical conductivity, significant volume expansion, and structural collapse during cycling, which makes its actual magnesium storage performance difficult to meet the requirements of devices, and there is an urgent need to break through these limitations through material design and structural regulation.\u003c/p\u003e \u003cp\u003eMetal-organic frameworks (MOFs), as a class of porous materials with high specific surface area, controllable pore size and abundant metal active sites, offer an effective approach for the structural optimization of functional electrode materials [\u003cspan additionalcitationids=\"CR17\" citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. MOF-derived materials not only inherit the porous structure characteristics of the parent materials, which can shorten the ion transport path and alleviate volume expansion, but also achieve uniform dispersion and valence state regulation of metal active components through the pyrolysis process, significantly enhancing the conductivity and structural stability of the materials [\u003cspan additionalcitationids=\"CR20 CR21\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. Applying the MOF-derived strategy to the preparation of manganese-based materials can precisely construct a synergistic system of \"porous structure - active sites - electron transport channels\", providing a new solution to the performance shortcomings of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e in magnesium storage. Existing studies have shown that MOF-derived manganese oxides, through porous structure regulation and surface defect engineering, have significantly improved magnesium storage capacity and cycling stability compared to traditional preparation methods, verifying the feasibility of this strategy [\u003cspan additionalcitationids=\"CR24 CR25\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eBased on this, this study focuses on the performance breakthrough of Mg-ion capacitor electrode materials, guided by the efficient utilization of magnesium resources. By combining the structural regulation advantages of MOF-derived technology with the magnesium storage potential of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, MOF-derived Mn₂O₃ electrode materials were designed and prepared. Through systematic research on the crystal structure, porous characteristics and surface chemical state of the materials, the magnesium storage mechanism and structure-performance relationship were revealed, providing theoretical support and technical references for the development of high-performance magnesium storage devices [\u003cspan additionalcitationids=\"CR28 CR29\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. This study not only has the potential to break through the performance bottleneck of existing magnesium storage materials, but also promotes the efficient conversion of magnesium resources in the field of energy storage, injecting new impetus into the development of large-scale energy storage technologies.\u003c/p\u003e"},{"header":"Experimental Part","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eCrystal synthesis\u003c/h2\u003e \u003cp\u003eAll reagents required for the experiment are listed in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. All chemicals were used as received without further purification. In a typical synthesis, Mn(CH₃COO)₂\u0026middot;4H₂O (0.5 mmol, 0.1225 g) and 2,6-pyridinedicarboxylic acid (0.5 mmol, 0.0835 g) were dissolved in 10 mL of deionized water. The mixture was stirred for 30 min to obtain a homogeneous solution, which was then transferred into a 25 mL Teflon-lined stainless-steel autoclave and heated at 150\u0026deg;C for 24 h. After cooling to room temperature, colorless rod-like single crystals were collected, washed three times with deionized water (20 mL each time), and dried at room temperature. The resulting product was designated as 26p-Mn-MOF.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eCapacitors performance tests\u003c/h3\u003e\n\u003cp\u003eThe supercapacitor working electrodes were fabricated by pressing metal oxide materials (mass loading\u0026thinsp;\u0026asymp;\u0026thinsp;2.0 mg cm⁻\u0026sup2;) onto nickel foam substrates (1\u0026times;1 cm) at 10 MPa. Electrochemical performance was evaluated in a three-electrode system with 1 M MgSO\u003csub\u003e4\u003c/sub\u003e electrolyte, using Pt foil and Hg/HgO as counter and reference electrodes, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted on a CHI660E electrochemical workstation, while galvanostatic charge-discharge (GCD) tests and cycling stability assessments were performed using a LAND-CT3001 battery testing system. The specific capacitance (C, F g⁻\u0026sup1;) was calculated from GCD data using the Eq.\u0026nbsp;(1): C = (I\u0026thinsp;\u0026times;\u0026thinsp;Δt)/(m\u0026thinsp;\u0026times;\u0026thinsp;ΔV), where I is discharge current (A), Δt is discharge time (s), m is active material mass (g), and ΔV represents the operational voltage window (V). Energy density (E, Wh kg-1) using the Eq.\u0026nbsp;(2): E\u0026thinsp;=\u0026thinsp;CV\u003csup\u003e2\u003c/sup\u003e/7.2, and power density (P, W kg-1) using Eq.\u0026nbsp;(3) P\u0026thinsp;=\u0026thinsp;3600E/t.\u003c/p\u003e"},{"header":"Result and discussion","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003ePreparation of active substances\u003c/h2\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e outlines the preparation of heterogeneous structures. The active substances precursor was synthesized using a hydrothermal method, followed by drying at 25 ℃. Subsequently, the dried precursor was annealed at 500\u0026thinsp;\u0026minus;\u0026thinsp;700\u0026deg;C for 2 h in an air atmosphere. The products were named based on the specific annealing temperatures: Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eAnalysis of Precursor Structure\u003c/h3\u003e\n\u003cp\u003eThe structure of 26p-Mn-MOF was in monoclinic C2/c space group (table \u003cspan refid=\"MOESM2\" class=\"InternalRef\"\u003eS2\u003c/span\u003e), the formula was C\u003csub\u003e14\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003eMn\u003csub\u003e2\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e11\u003c/sub\u003e. The simplified unit cell structure and the different coordination environments of Mn atom are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea is the asymmetric unit comprises a unique cobalt atom (Mn1), a 2,6-pyridine dicarboxylic acid ligands, a half of O atom (O3) and a coordinate water molecule (O6). Mn1 atom has 7 coordination numbers and is bonded with one N atom (N1) from ligand and six O atoms, of which one is from water molecule (O6), four are from three ligands (O2, O2\u0026rsquo;, O4 and O4\u0026rsquo;), the other one is from O\u003csup\u003e2\u0026minus;\u003c/sup\u003e in water (O3) (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). The bond distances and bond angles of Mn-O and Mn-N are in the normal range [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. The result of bond distances, bond angles of Mn-O and Mn-N are list in tables S3 and S4. Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e is unit cell from a, b and c axis views. It is obvious that 26p-Mn-MOF is a one dimensional structure. The one coordinate water molecule (O6) share its H atoms with the neighboring oxygen atom (O5) to form H bond (figure \u003cspan refid=\"MOESM2\" class=\"InternalRef\"\u003eS2\u003c/span\u003e). The H-bonds are list in table S5. Figure S3 is powder XRD pattern of 26p-Mn-MOF and the simulated pattern from the single crystal structure. Compared with the simulated pattern from the single crystal structure, all of the main peaks are well consistent, demonstrating the crystal has a high purity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eTG and XRD analysis of electrode material powder\u003c/h2\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea shows the TG curves of the precursor.The TG process can be divided into two stages. The first stage is 30\u0026ndash;200\u0026deg;C, which is mainly the loss of free water in the precursor; the second stage is 200\u0026ndash;430\u0026deg;C, which is the collapse of the ligand and the gradual transformation of the precursor from MOF to oxide. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb shows the powder XRD patterns of the calcination products at different temperatures. It can be seen from the figure that all samples have diffraction peaks at approximately 28.74\u0026deg;, 33.12\u0026deg;, 36.84\u0026deg;, 47.46\u0026deg; and 56.52\u0026deg;, which are consistent with the positions of the diffraction peaks of the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e standard card (No. 24\u0026ndash;0508), indicating that the calcination products at all temperatures are Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. In addition, as the calcination temperature increases, the intensity of the diffraction peaks gradually increases, suggesting that the crystallinity of the products gradually enhances.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eXPS analysis\u003c/h3\u003e\n\u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows the XPS test results of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea is the total spectrum of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600, and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600. From the figure, it can be seen that this sample contains elements such as Mn, O, and C (the C element mainly comes from the conductive glue used during the test). The high-resolution energy spectra of Mn2p for the three samples (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb) have four main peaks. Through software peak fitting, the peaks at the central positions of 641.2 eV and 642.8 eV correspond to Mn2p\u003csub\u003e3/2\u003c/sub\u003e, and the peaks at the central positions of 653.4 eV and 653.4 eV correspond to Mn 2p\u003csub\u003e1/2\u003c/sub\u003e. These results are consistent with the XPS spectra of Mn\u003csup\u003e3+\u003c/sup\u003e reported in other literatures [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec is the high-resolution energy spectrum of O1s. Through software peak fitting, it can be fitted into three main peaks. At the binding energy of 529.6 eV, it is the Mn-O bond, and at the binding energy of 531.4 eV, it is the existence of oxygen vacancies [\u003cspan additionalcitationids=\"CR34\" citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. In Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed, it is the ESP test result of three oxides, which can also prove the existence of oxygen vacancies.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eMorphology analysis\u003c/h3\u003e\n\u003cp\u003eThe morphology of the precursor was obtained under different magnifications (50 \u0026micro;m and 10 \u0026micro;m) by scanning electron microscopy (SEM), as shown in Figure S4. The product morphology was uniform and arranged in a staggered manner, presenting as strip-shaped crystalline blocks. The crystal surface was smooth and the purity was high. Figures\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-b and Figure S5 show the SEM morphologies after different calcination temperatures. The morphologies of the products obtained at the three temperatures could all maintain the morphology of the precursor, while the products became more fragmented as the temperature increased. From the images under larger magnifications, it can be seen that the oxide morphology maintained a relatively complete surface with some roughness, and some holes appeared on the oxide surface, which was mainly caused by the collapse of the organic ligands during the high-temperature calcination process. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec is TEM of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600. Figures\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed-e demonstrates HRTEM image of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 structure, the spacings with 0.203 nm correspond to (200) plane of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eElectrochemical performance test analysis\u003c/h2\u003e \u003cp\u003eThe electrochemical properties of the oxides were evaluated in a three-electrode system, with the oxides sample as the working electrode, a saturated calomel electrode as the reference, a platinum electrode as the counter electrode, and 1 mol L⁻\u0026sup1; MgSO\u003csub\u003e4\u003c/sub\u003e as the electrolyte. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea shows the cyclic voltammetry (CV) curves of the three oxides at a sweep rate of 50 mV s⁻\u0026sup1;. The CV curve of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 exhibits a slightly larger integral area than those of other two, suggesting superior electrochemical performance. Therefore, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 was further investigated. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb displays the CV curves of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 at varying sweep rates. The integral area increases with sweep rate, while the overall shape remains consistent, indicating good structural stability. Similar CV behavior for Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 is illustrated in Figure S6. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec presents the logarithmic relationship between sweep rate and peak current for Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600. Linear fitting yields b values of 0.81 and 0.74 for the anodic and cathodic processes, respectively. The corresponding b values for Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 are shown in Figure S7. A b value near 0.5 suggests dominant pseudocapacitive behavior, whereas a value near 1 indicates double-layer capacitance dominance. Values between 0.5 and 1 reflect a combined contribution from both mechanisms [\u003cspan additionalcitationids=\"CR37\" citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. Figure d shows the comparison of the contribution of the two mechanisms at a sweep speed of 50 mV\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The contributions of pseudocapacitance and double-layer capacitance at various sweep rates are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee and Figures S8\u0026ndash;S10. An increase in sweep rate leads to a higher proportion of double-layer capacitance due to shortened reaction time and reduced diffusion layer thickness [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea compares the galvanostatic discharge curves of the three materials at identical current density. Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 shows a discharge time of 384 s, outperforming both Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500 (260s) and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 (325s). Discharge curves at various current densities (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb and Figure S11) exhibit quasi-symmetric profiles, indicating good reversibility across all samples. Specific capacitance values, calculated using Eq.\u0026nbsp;(1), are plotted in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec. Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 (326, 326, 296, 273 and 276 F g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) consistently exhibits higher capacitance than Mn2O3-500 (257, 260, 243, 240 and 236 F g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 (222, 221, 210, 207 and 200 F g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) across all current densities. Electrochemical impedance spectroscopy (EIS) results are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ed. The Nyquist plots display a semicircle in the high-frequency region and a linear segment in the low-frequency range, characteristic of capacitive behavior. The high-frequency intercept represents the ohmic resistance (Rs), while the semicircle diameter corresponds to the charge transfer resistance (Rct). The specific fitting values of the three oxide electrode materials are presented in Table S6. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ee presents the cycling performance of the materials over 10,000 charge\u0026ndash;discharge cycles. All samples maintained coulombic efficiency close to 100%. However, retention varied: Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 retained 83% of its initial capacitance, while Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-500 and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-700 retained approximately 81% and 72%.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo evaluate the practical applicability of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600, an asymmetric hybrid capacitor was constructed using Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 as the positive electrode and activated carbon (AC) as the negative electrode, with 1 M MgSO\u003csub\u003e4\u003c/sub\u003e aqueous solution as the electrolyte (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ea), The mass ratio between the positive and negative electrodes was determined based on the charge balance equation: m\u003csub\u003e+\u003c/sub\u003e / m\u003csub\u003e\u0026minus;\u003c/sub\u003e = C\u003csub\u003em\u0026minus;\u003c/sub\u003e \u0026times; ΔV / C\u003csub\u003em+\u003c/sub\u003e\u0026thinsp;\u0026times;\u0026thinsp;ΔV, where C\u003csub\u003em+\u003c/sub\u003e represents the specific capacitance and ΔV represents the potential window. Based on the GCD profile of AC (Figure S12), which showed a specific capacitance of 250 F g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 1 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the optimal AC mass was calculated to be 2.608 mg. CV analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003eb) revealed that AC operated within \u0026minus;\u0026thinsp;1 to 0 V, while Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 exhibited redox activity from 0 to 0.6 V, enabling a full-cell voltage window of 1.60 V. The CV curves of the assembled Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600 //AC device (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ec\u0026ndash;d) retained their shape across varying scan rates and voltage windows, indicating good electrochemical stability. GCD measurements (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ee) conducted at current densities from 1 to 5 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e yielded specific capacitances of 62.5, 54.6, 52.3, 49.6 and 47.6 F g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively, as calculated using Eq.\u0026nbsp;(1). These results confirm the device\u0026rsquo;s strong rate capability and suitability for energy storage applications. The energy density (E) and power density (P) of the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-600//AC device were calculated using Equations (2) and (3), and the results are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ef. At a power density of 173.57 W kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the device achieved an energy density of 23.16 Wh kg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThis study is based on the abundant resources of magnesium and aims to address the key bottlenecks of poor conductivity, severe volume expansion, and low magnesium storage capacity in magnesium ion capacitors (MICs) electrode materials. A new route for constructing high-performance Mn₂O₃ electrodes using the \"MOF-derived strategy\" was proposed and verified. The 26p-Mn-MOF precursor was obtained through one-step hydrothermal synthesis, and after controlled calcination at 600\u0026deg;C, Mn₂O₃-600 with a hierarchical porous framework of MOF, abundant oxygen vacancies, and moderate crystallinity was successfully prepared. Its unique \"pore-channel - active site - electron transport channel\" synergistic structure effectively shortens the diffusion path of Mg\u0026sup2;⁺, alleviates the volume change during cycling, and significantly improves the efficiency of electron/ion transport. In a three-electrode system, the specific capacitance of Mn₂O₃-600 reached 326 F g⁻\u0026sup1; (1 A g⁻\u0026sup1;), which was approximately 27% and 47% higher than the samples at 500\u0026deg;C and 700\u0026deg;C, respectively. After 10,000 charge-discharge cycles, the capacity retention was 83%, and the Coulomb efficiency was approximately 100%, demonstrating excellent rate and cycle stability. An asymmetric magnesium ion capacitor constructed with Mn₂O₃-600 as the positive electrode and activated carbon as the negative electrode had a working voltage extended to 1.6 V, with a device-level energy density of 23.16 Wh kg⁻\u0026sup1; (power density 173.57 W kg⁻\u0026sup1;), and maintained a stable charge-discharge platform at different rates, confirming its practical potential.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003ePing-Ping Sun: Investigation, Methodology, Validation, Writing \u0026ndash; Original Draft Yun-Heng Li: Investigation, Data Curation, Visualization Bo Yang: Resources, Investigation Hai-Yan Liu: Conceptualization, Funding acquisition, Supervision, Writing \u0026ndash; Review \u0026amp; Editing\u003c/p\u003e\u003ch2\u003eAcknowledgments\u003c/h2\u003e \u003cp\u003eThis work was supported by The Foundation of Liaoning Provincial Key Laboratory of Energy Storage and Utilization (CNNK202410) and Basic Scientific Research Project of Colleges and Universities of Liaoning Province Education Department (LJ232414435004 and LJ212514435002).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eTang M, Liu Q, Zou X, Zhang B, An L (2025) High-energy-density aqueous zinc-ion batteries: recent progress, design strategies, challenges and perspectives. 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ACS Appl Energy Mater 8:6510\u0026ndash;6519. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsaem.5c00344\u003c/span\u003e\u003cspan address=\"10.1021/acsaem.5c00344\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePandey G, Sharma A, Meenakshi, Pandey K, Menezes PW, Awasthi K (2025) MXene integrated metal-organic framework derived cobalt phosphide for supercapacitor applications. ChemCatChem 17(17):e00430. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/cctc.202500430\u003c/span\u003e\u003cspan address=\"10.1002/cctc.202500430\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Magnesium ion capacitor, MOF-derived, Mn₂O₃ electrode, High specific capacitance, Long cycle life","lastPublishedDoi":"10.21203/rs.3.rs-8691077/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8691077/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study addresses the bottleneck issues of slow magnesium storage kinetics and low capacity of electrode materials in magnesium ion capacitors (MICs) by proposing a MOF-derived strategy to construct high-performance Mn₂O₃ electrode materials.This study addresses the bottleneck issues of slow magnesium storage kinetics and low capacity of electrode materials in magnesium ion capacitors (MICs) by proposing a MOF-derived strategy to construct high-performance Mn₂O₃ electrode materials. This work validates the feasibility of MOF-derived Mn₂O₃ as an electrode material for magnesium ion capacitors, providing a new approach for low-cost, high-safety, and large-scale magnesium energy storage technologies.\u003c/p\u003e","manuscriptTitle":"Study on the Electrochemical Performance of MOF-Derived Mn2O3 Electrode Materials on Magnesium Ion Capacitors","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-29 09:03:46","doi":"10.21203/rs.3.rs-8691077/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"348fb79f-bc75-45c4-aacb-208fea1d53be","owner":[],"postedDate":"January 29th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-02-22T21:53:42+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-29 09:03:46","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8691077","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8691077","identity":"rs-8691077","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}