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Investigation of structural, electronic and magnetic properties of breathing metal-organic framework MIL-47(Mn): a first principles approach.

ABSTRACT: The structural, electronic and magnetic properties of the MIL-47(Mn) metal-organic framework are investigated using first principles calculations. We find that the large-pore structure is the ground state of this material. We show that upon transition from the large-pore to the narrow-pore structure, the magnetic ground-state configuration changes from antiferromagnetic to ferromagnetic, consistent with the computed values of the intra-chain coupling constant. Furthermore, the antiferromagnetic and ferromagnetic configuration phases have intrinsically different electronic behavior: the former is semiconducting, the latter is a metal or half-metal. The change of electronic properties during breathing posits MIL-47(Mn) as a good candidate for sensing and other applications. Our calculated electronic band structure for MIL-47(Mn) presents a combination of flat dispersionless and strongly dispersive regions in the valence and conduction bands, indicative of quasi-1D electronic behavior. The spin coupling constants are obtained by mapping the total energies onto a spin Hamiltonian. The inter-chain coupling is found to be at least one order of magnitude smaller than the intra-chain coupling for both large and narrow pores. Interestingly, the intra-chain coupling changes sign and becomes five times stronger going from the large pore to the narrow pore structure. As such MIL-47(Mn) could provide unique opportunities for tunable low-dimensional magnetism in transition metal oxide systems.

SUBMITTER: Hosseini M

PROVIDER: S-EPMC9049066 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Investigation of structural, electronic and magnetic properties of breathing metal-organic framework MIL-47(Mn): a first principles approach.

Hosseini Mohammadreza M Vanpoucke Danny E P DEP Giannozzi Paolo P Berahman Masoud M Hadipour Nasser N

RSC advances 20200129 8

The structural, electronic and magnetic properties of the MIL-47(Mn) metal-organic framework are investigated using first principles calculations. We find that the large-pore structure is the ground state of this material. We show that upon transition from the large-pore to the narrow-pore structure, the magnetic ground-state configuration changes from antiferromagnetic to ferromagnetic, consistent with the computed values of the intra-chain coupling constant. Furthermore, the antiferromagnetic ...[more]

PMID: 35495241

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Project description:The vanadium-based metal-organic framework MIL-47 distinguishes itself among other MOFs for its distinctive structure and unique properties (e.g., flexible structure, high thermal stability, and high surface area). The synthesis of MIL-47 has been reported from various metal precursors, including vanadium(iii) chloride (VCl3) as a rich source of metal ions. Attempts have been made to include other starting materials, a step forward towards large-scale production. Synthesis from various solid materials is encouraged, seeking an economic and greener approach. In this study, vanadium pentoxide (V2O5), a readily abundant low-cost and thermodynamically stable metal source, was used to synthesize the MIL-47(V) framework via a facile solvothermal route. This precursor provides a controllable rate of metal ion production depending on the applied reaction conditions. In our method, the synthesis took place at a low temperature and reaction time (180 °C for 20 h, instead of 220 °C for 72 h), yielding MIL-47 microrods. Moreover, among its unique properties, the metal centers of MIL-47 oxidize under the influence of thermal or chemical treatments, preserving the framework structure. This unusual character is not commonly witnessed in comparable MOF structures. This property can be leveraged in anti-corrosion applications, whereby a redox reaction would sacrifice the framework components, protecting the metal in contact. However, the chemical stability of MIL-47 is doubted against a corrosive medium. Thus, an epoxy coating with 10 wt% MOF loading was incorporated in our investigation to extend the aluminum alloy (AA2024) surface protection for prolonged exposure duration. The uniformity of distribution of the prepared MOF within the epoxy matrix was confirmed using SEM/EDX. Electrochemical impedance spectroscopy (EIS) was used to evaluate the corrosion performance of the coated samples. The results showed that the inclusion of V-MOF offers extended corrosion prevention, over 60 days, for the AA2024 alloy against artificial seawater. The neat epoxy coating could not prevent the corrosion of AA2024 over two weeks of immersion, whereby pitting corrosion was clearly observed. The V-MOF could induce a series of redox reactions leading to the precipitation of vanadium on the cathodic sites of metal surfaces.

Dataset Information

Investigation of structural, electronic and magnetic properties of breathing metal-organic framework MIL-47(Mn): a first principles approach.

Publications

Investigation of structural, electronic and magnetic properties of breathing metal-organic framework MIL-47(Mn): a first principles approach.

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