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Evaluation of the synthetic methods for preparing metal organic frameworks with transition metals

  • Received: 31 December 2017 Accepted: 11 April 2018 Published: 18 May 2018
  • In this study, preparation of metal-organic frameworks (Cu3BTC2, Fe3BTC2, Ni3BTC2 and Co3BTC2) (BTC = benzene-1,3,5-tricarboxylate) was performed by five different synthetic methods (solvothermal under autoclave, reflux, domestic microwave, ultrasonic, and mechanochemical conditions) and the results were compared in order to evaluate the advantages and disadvantages of each method with a focus on the domestic microwave method. All the results showed correlations between the reaction conditions and the yield, morphology, crystalline phases, and specific surface area. Characterization of the samples was performed by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and physisorption analysis. Experimental results have shown that the conventional method is a good choice for the preparation of M-BTCs, but it takes a long time and requires high temperature. With this work, we show that the domestic microwave is the best choice because it promotes the same MOF structures in a shorter time while achieving high purity, high specific area, and good quantitative yield. Notably, these transition metal-BTCs are promising candidates to be applied as catalysts in further studies.

    Citation: Laís Weber Aguiar, Cleiser Thiago Pereira da Silva, Hugo Henrique Carline de Lima, Murilo Pereira Moises, Andrelson Wellington Rinaldi. Evaluation of the synthetic methods for preparing metal organic frameworks with transition metals[J]. AIMS Materials Science, 2018, 5(3): 467-478. doi: 10.3934/matersci.2018.3.467

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  • In this study, preparation of metal-organic frameworks (Cu3BTC2, Fe3BTC2, Ni3BTC2 and Co3BTC2) (BTC = benzene-1,3,5-tricarboxylate) was performed by five different synthetic methods (solvothermal under autoclave, reflux, domestic microwave, ultrasonic, and mechanochemical conditions) and the results were compared in order to evaluate the advantages and disadvantages of each method with a focus on the domestic microwave method. All the results showed correlations between the reaction conditions and the yield, morphology, crystalline phases, and specific surface area. Characterization of the samples was performed by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and physisorption analysis. Experimental results have shown that the conventional method is a good choice for the preparation of M-BTCs, but it takes a long time and requires high temperature. With this work, we show that the domestic microwave is the best choice because it promotes the same MOF structures in a shorter time while achieving high purity, high specific area, and good quantitative yield. Notably, these transition metal-BTCs are promising candidates to be applied as catalysts in further studies.


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    [1] Hoskin BF, Robson R (1990) Design and construction of a new class of scaffolding-like materials comprising infinite polymeric frameworks of 3D-linked molecular rods. A reappraisal of the zinc cyanide and cadmium cyanide structures and the synthesis and structure of the diamond-related frameworks [N(CH3)4][CuIZnII(CN)4] and CuI[4,4',4'',4'''-tetracyanotetraphenylmethane]BF4xC6H5NO2. J Am Chem Soc 112: 1546–1554.
    [2] Batten SR, Champness NR, Chen XM, et al. (2013) Terminology of metal-organic frameworks and coordination polymers (IUPAC Recommendations 2013). Pure Appl Chem 85: 1715–1724. doi: 10.1351/PAC-REC-12-11-20
    [3] Furukawa H, Cordova KE, O'Keeffe M, et al. (2013) The chemistry and applications of metal-organic frameworks. Science 341: 1230444. doi: 10.1126/science.1230444
    [4] Adhikari AK, Lin KS, Tu MT (2016) Hydrogen storage capacity enhancement of MIL-53(Cr) by Pd loaded activated carbon doping. J Taiwan Inst Chem E 63: 463–472. doi: 10.1016/j.jtice.2016.02.033
    [5] Rodenas T, Luz I, Prieto G, et al. (2015) Metal-organic framework nanosheets in polymer composite materials for gas separation. Nat Mater 14: 48–55. doi: 10.1038/nmat4113
    [6] Ma J, Guo X, Ying Y, et al. (2017) Composite ultrafiltration membrane tailored by MOF@GO with highly improved water purification performance. Chem Eng J 313: 890–910. doi: 10.1016/j.cej.2016.10.127
    [7] Timofeeva MN, Panchenko VN, Khan NA, et al. (2017) Isostructural metal-carboxylates MIL-100(M) and MIL-53(M) (M: V, Al, Fe and Cr) as catalysts for condensation of glycerol with acetone. Appl Catal A-Gen 529: 167–174. doi: 10.1016/j.apcata.2016.11.006
    [8] Loera-Serna S, Ortiz E (2016) Catalytic Applications of Metal-Organic Frameworks, in: Luis N, Advanced Catalytic Materials-Photocatalysis and Other Current Trends, IntechOpen, 95–122.
    [9] Ji L, Cheng Q, Wu K, et al. (2016) Cu-BTC frameworks-based electrochemical sensing platform for rapid and simple determination of sunset yellow and tartrazine. Sensor Actuat B-Chem 231: 12–17. doi: 10.1016/j.snb.2016.03.012
    [10] Da Silva CTP, Veregue FR, Aguiar LW, et al. (2016) AuNp@MOF composite as electrochemical material for determination of bisphenol A and its oxidation behavior study. New J Chem 40: 8872–8877. doi: 10.1039/C6NJ00936K
    [11] Yi FY, Zhang R, Wang H, et al. (2017) Metal-organic frameworks and their composites: Synthesis and electrochemical applications. Small Methods 1: 1–24.
    [12] Ebrahimi AK, Sheikhshoaie I, Mehran M (2017) Facile synthesis of a new metal-organic framework of copper(II) by interface reaction method, characterization, and its application for removal of malachite green. J Mol Liq 240: 803–809. doi: 10.1016/j.molliq.2017.06.097
    [13] Safarifard V, Morsali A (2018) Facile preparation of nanocubes zinc-based metal-organic framework by an ultrasound-assisted synthesis method; precursor for the fabrication of zinc oxide octahedral nanostructures. Ultrason Sonochem 40: 921–928. doi: 10.1016/j.ultsonch.2017.09.014
    [14] Kowalewski E, Zienkiewicz-Machnik M, Lisovytskiy D (2017) Turbostratic carbon supported palladium as an efficient catalyst for reductive purification of water from trichloroethylene. AIMS Mater Sci 4: 1276–1288. doi: 10.3934/matersci.2017.6.1276
    [15] Kim DW, Kim HG, Cho DH (2016) Catalytic performance of MIL-100(Fe, Cr) and MIL-101(Fe, Cr) in the isomerization of endo- to exo-dicyclopentadiene. Catal Commun 73: 69–73. doi: 10.1016/j.catcom.2015.10.006
    [16] Xu B, Li X, Chen Z (2018) Pd@MIL-100(Fe) composite nanoparticles as efficient catalyst for reduction of 2/3/4-nitrophenol: Synergistic effect between Pd and MIL-100(Fe). Micropor Mesopor Mater 255: 1–6. doi: 10.1016/j.micromeso.2017.07.008
    [17] Horcajada P, Surble S, Serre C, et al. (2007) Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores. Chem Commun 100: 2820–2822.
    [18] Silva P, Vilela SMF, Tome JPC, et al. (2015) Multifunctional metal-organic frameworks: from academia to industrial applications. Chem Soc Rev 44: 6774–6803. doi: 10.1039/C5CS00307E
    [19] Tan F, Liu M, Li K, et al. (2015) Facile synthesis of size-controlled MIL-100(Fe) with excellent adsorption capacity for methylene blue. Chem Eng J 281: 360–367. doi: 10.1016/j.cej.2015.06.044
    [20] Zhang F, Shi J, Jin Y, et al. (2015) Facile synthesis of MIL-100(Fe) under HF-free conditions and its application in the acetalization of aldehydes with diols. Chem Eng J 259: 183–190. doi: 10.1016/j.cej.2014.07.119
    [21] Duan S, Li J, Liu X, et al. (2016) HF-Free synthesis of nanoscale metal-organic framework NMIL-100(Fe) as an efficient dye adsorbent. ACS Sustain Chem Eng 4: 3368–3378. doi: 10.1021/acssuschemeng.6b00434
    [22] Márquez AG, Demessence A, Platero-Prats AE, et al. (2012) Green Microwave synthesis of MIL-100(Al, Cr, Fe) nanoparticles for thin-film elaboration. Eur J Inorg Chem 100: 5165–5174.
    [23] Zukal A, Opanasenko M, Rubes M, et al. (2015) Adsorption of pentane isomers on metal-organic frameworks Cu-BTC and Fe-BTC. Catal Today 243: 69–75. doi: 10.1016/j.cattod.2014.07.003
    [24] Yaghi OM, Li H, Groy TL (1996) Construction of porous solids from hydrogen-bonded metal complexes of 1,3,5-tricarboxylic acid. J Am Chem Soc 118: 9096–9101. doi: 10.1021/ja960746q
    [25] Khan NA, Haque MM, Jhung SH (2010) Accelerated syntheses of porous isostructural lanthanide-benzenetricarboxylates (Ln-BTC) under ultrasound at room temperature. Eur J Inorg Chem 2: 4975–4981.
    [26] Singco B, Liu LH, Chen YT, et al. (2016) Approaches to drug delivery: Confinement of aspirin in MIL-100(Fe) and aspirin in the de novo synthesis of metal-organic frameworks. Micropor Mesopor Mater 223: 254–260. doi: 10.1016/j.micromeso.2015.08.017
    [27] Schlesinger M, Schulze S, Hietschold M, et al. (2010) Evaluation of synthetic methods for microporous metal-organic frameworks exemplified by the competitive formation of [Cu2(btc)3(H2O)3] and [Cu2(btc)(OH)(H2O)]. Micropor Mesopor Mater 132: 121–127. doi: 10.1016/j.micromeso.2010.02.008
    [28] Israr F, Kim DK, Kim Y, et al. (2016) Synthesis of porous Cu-BTC with ultrasonic treatment: Effects of ultrasonic power and solvent condition. Ultrason Sonochem 29: 186–193. doi: 10.1016/j.ultsonch.2015.08.023
    [29] Lanchas M, Arcediano S, Aguayo AT, et al. (2014) Two appealing alternatives for MOFs synthesis: solvent-free oven heating vs. microwave heating. RSC Adv 4: 60409–60412.
    [30] Da Silva CTP, Safadi BN, Moisés MP, et al. (2016) Synthesis of Zn-BTC metal organic framework assisted by a home microwave oven and their unusual morphologies. Mater Lett 182: 231–234. doi: 10.1016/j.matlet.2016.06.015
    [31] Howarth AJ, Peters AW, Vermeulen NA, et al. (2017) Best practices for the synthesis, activation, and characterization of metal-organic frameworks. Chem Mater 29: 26–39. doi: 10.1021/acs.chemmater.6b02626
    [32] Sun Y, Zhou HC (2015) Recent progress in the synthesis of metal-organic frameworks. Sci Technol Adv Mat 16: 1–11.
    [33] Israr F, Chun D, Kim Y, et al. (2016) High yield synthesis of Ni-BTC metal-organic framework with ultrasonic irradiation: Role of polar aprotic DMF solvent. Ultrason Sonochem 31: 93–101. doi: 10.1016/j.ultsonch.2015.12.007
    [34] Tan H, Liu C, Yan Y, et al. (2015) Simple preparation of crystal Co3(BTC)2·12H2O and its catalytic activity in CO oxidation reaction. J Wuhan Univ Technol 3: 71–75.
    [35] Israr F, Kim DK, Kim Y, et al. (2016) Scope of various solvents and their effects on solvothermal synthesis of Ni-BTC. Quim Nova 39: 669–675.
    [36] Shamaei S, Abbasi AR, Noori N, et al. (2013) Ultrasound-assisted coating of silk yarn with nano-porous Co3(BTC)2·12H2O with iodine adsorption affinity. Colloid Surface A 431: 66–72.
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