RESUMO
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.
RESUMO
The post-synthetic exchange (PSE) method is a well-proven route to replace, modify, and add different functionalities to metal-organic frameworks (MOFs). Particularly, the solvent-assisted cation substitution (SACS) technique has been reported to prepare mixed-metal multivariate metal-organic frameworks (MTV-MOFs). However, such a technique does not apply to all types of MOFs. In 2013, Szilágyi et al. reported the achievement of the mixed-metal MTV-MIL-101 framework via PSE. Since then, a debate has been taking place about the validity of these findings. On the other hand, the attainment of the mixed-metal MIL-101 was reported to be obtainable through the direct synthesis, which is, to some, the only way to achieve it. Here, we settle this dispute by investigating Szilágyi's method not only as described, but also at extended conditions of time and different metal precursors: all attempts were vain. However, by reconsidering the refluxing solvent (dimethylformamide "DMF" instead of water) and the applied reaction conditions (110 °C-20 h), mixed-metal MIL-101(Cr/Fe) was achieved via a simple PSE method.
RESUMO
We present the synthesis of a new cerium(iii)-melamine coordination polymer (CMCP) by a mixed-solvothermal method and its characterization. Characterization techniques included Raman, Fourier Transformation Infra-Red (FTIR), X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM), in which the change in the electronic environment and the crystallinity were tracked. The characterization results confirm the coordination of cerium(iii) with melamine through -NH2 groups, instead of the N atoms of the triazine ring, for which we propose a mechanism of interaction. In addition, Biovia Materials Studio package was applied to determine and investigate the molecular structure of the CMCP. All simulations were done using COMPASS force-field theory and atom-based method for summation of electrostatic and van de Waals forces. The application of the CMCP for the corrosion inhibition of AA2024 in 3.5% NaCl solution was tested using the potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results point out that the presence of cerium as cerium(iii) in the CMCP structure plays the fundamental role of inhibition, whereby the inhibition mechanism occurs by cathodic oxidation of Ce(iii) to Ce(iv) and cyclic reduction of Ce(iv) to Ce(iii) by melamine part of CMCP.
RESUMO
Cerium is a rare earth element that has been widely proposed for the corrosion protection of aluminium alloys (AA). Both cerium salts, Ce3+ and Ce4+, have been used in combination with other compounds to offer synergistic inhibition, however, the inhibitive corrosion mechanism when using Ce4+ with organic compounds is still not clear. In this study, the synergistic inhibition effect of Ce4+ and melamine (M) on the corrosion of aluminium alloy 2024 (AA2024) in 3.5% NaCl solution was investigated. Potentiodynamic Polarization (PDP) and Electrochemical Impedance Spectroscopy (EIS) techniques were used to study the synergistic effect of different Ce4+/M ratios on the corrosion behaviour of AA2024. The PDP study showed that a combination of 50% Ce4+ and 50% M leads to the lowest corrosion rates, both acting as cathodic inhibitors. Both PDP and EIS results indicated that M or Ce4+ in isolation did not offer effective corrosion protection, while the combination of M and Ce4+ significantly enhances the corrosion protection with a synergism parameter equal to 3.5. SEM and EDX observations confirm the findings from the electrochemical techniques. XPS was used to investigate the mechanism of protection, revealing that the reduction of Ce4+ to Ce3+ occurs during protection of AA2024. A new mechanism of corrosion synergistic inhibition by Ce4+ and organic compounds is postulated where the role of the organic compounds is to enhance the reduction of Ce4+.