Metalli-orgaanisten kehysten (MOF) ultraäänivalmistus
- Metal-Organic Frameworks are compounds formed from metal ions and organic molecules so that a one-, two, or three-dimensional hybrid material is created. These hybrid structures can be porous or non-porous and offer manifold functionalities.
- The sonochemical synthesis of MOFs is a promising technique as the metal-organic crystals are produced very efficient and environmental-friendly.
- The ultrasonic production of MOFs can be linearly scaled-up from the preparation of small samples in the lab to full commercial production.
metalli-orgaaniset kehykset
Crystalline metal-organic frameworks (MOFs) fall within the category of high potential porous materials, which can be used in gas storage, adsorption/ separation, catalysis, as adsorbents, in magnetism, sensor design, and drug delivery. MOFs are typically formed by self-assembly where secondary building units (SBUs) get connected with organic spacers (ligands) to create complex networks. The organic spacers or the metallic SBUs can be modified in order to control the porosity of the MOF, which is crucial regarding its functionalities and its utility for particular applications.
Sonochemical Synthesis of MOFs
Ultrasonic irradiation and the thereby generated kavitaatio are well known for its unique effects on chemical reactions, known as Sonokemia. The violent implosion of cavitation bubbles generates localized hot spots with exceedingly high transient temperatures (5000 K), pressures (1800 atm), and cooling rates (1010Ks-1) as well as shock waves and resulting liquid jets. At these kavitaatio hot spots, the crystal nucleation and growth, e.g. by Ostwald ripening, is induced and promoted. However, the particle size is limited since those hot spots are characterized by extreme cooling rates meaning that the temperature of the reaction medium falls within milliseconds.
Ultrasound is known to synthesize MOFs rapidly under mild process conditions, such as liuotinvapaa, at room temperature and under ambient pressure. Studies have shown that MOFs can be produced cost-effectively At korkea saanto via sonochemical route. Finally, the Sonokemiallinen synthesis of MOFs is a vihreä, environmentally friendly method.
Preparation of MOF-5
In the study of Wang et al (2011), Zn4O[1,4-benzenedicarboxylate]3 was synthesized via Sonokemiallinen route. 1.36g H2BDC and 4.84g Zn(NO3)2·6H2O were inilially dissolved in 160mL DMF. Then 6.43g TEA was added to the mixture under ultrasonic irradiation. After 2 h the colorless precipitate was collected by filtration and washed by DMF. The solid was dried at 90°C in vacuum and then stored in a vacuum desiccator.
Preparation of microporous MOF Cu3(BTC)2
Li et al. (2009) report the efficient ultrasonic synthesis of three-dimensional (3-D) metal–organic framework (MOF) with 3-D channels, such as Cu3(BTC)2 (HKUST-1, BTC = benzene-1,3,5-tricarboxylate). The reaction of cupric acetate and H3BTC in a mixed solution of DMF/EtOH/H2O (3:1:2, v/v) under ultrasonic irradiation at ambient temperature ja atmospheric pressure varten short reaction times (5–60 min) gave Cu3(BTC)2 in korkea saanto (62.6–85.1%). These Cu3(BTC)2 nano-crystals have dimensions of a size range of 10–200 nm, which are much smaller than those synthesized using conventional solvothermal method. There were no significant differences in physicochemical properties, e.g. BET surface area, pore volume, and hydrogen storage capacity, between Cu3(BTC)2 nano-crystals prepared using ultrasonic method and the microcrystals obtained by using improved solvothermal method. Compared with traditional synthetic techniques, such as solvent diffusion technique, hydrothermal and solvothermal methods, the ultrasonic method for the construction of porous MOFs was found to be highly Tehokas ja more environmentally friendly.
Preparation of a One-Dimensional Mg(II) MOF
Tahmasian et al. (2013) report an Tehokas, Edullisiaja ympäristöystävällinen route to produce a 3D supramolecular metal-organic framework (MOF) based on MgII, {[Mg(HIDC)(H2O)2]⋅1.5H2O}n (H3L = 4,5-imidazole-dicarboxylic acid) by using an ultrasonically-assisted route.
Nanostructured {[Mg(HIDC)(H2O)2]⋅1.5H2O}n was synthesized via the following Sonokemiallinen route. To prepare nanosized {[Mg(HIDC)(H2O)2]⋅1.5H2O}n (1), 20 mL of an solution of the ligand H3IDC (0.05M) and potassium hydroxide (0.1 M) was positioned a high-density ultrasonic probe with a maximum power output of 305 W. Into this solution 20 mL of an aqueous solution of magnesium nitrate (0.05M) was added dropwise. The obtained precipitates were filtered off, washed with water andethanol, and air-dried (m.p.> 300ºC. (Found: C, 24.84; H, 3.22; N, 11.67%.). IR (cm-1) selected bands: 3383 (w), 3190 (w), 1607 (br), 1500 (m), 1390 (s), 1242 (m), 820 (m), 652 (m)).
For studying the effect of concentration of initial reagents on size and morphology of nanostructured compound, the above processes were done under the following concentration condition of initial reagents: [HL2−] = [Mg2+] = 0.025 M.
Sono-Synthesis of fluorescent microporous MOFs
Qiu et al. (2008) found a Sonokemiallinen route for the rapid synthesis of fluorescent microporous MOF, Zn3(BTC)2⋅12H2O (1) and selective sensing of organoamines using nanocrystals of 1. The results reveal that ultrasonic synteesi is a simple, efficient, low cost, and environmentally friendly approach to nanoscale MOFs.
MOF 1 was synthesized using the ultrasonic method at an ambient temperature and atmospheric pressure for different reaction times of 5, 10, 30, and 90 min, respectively. A control experiment was also carried out to synthesize compound 1 using the hydrothermal method, and the structures were confirmed by IR, elemental analysis and Rietveld analysis of the powder X-ray diffraction (XRD) patterns using WinPLOTR and Fullprof13. Surprisingly, the reaction of zinc acetate dihydrate with benzen-1,3,5-tricarboxylic acid (H3BTC) in 20% of ethanol in water (v/v) under ultrasonic irradiation at ambient temperature and pressure for 5 min gave 1 in a remarkably korkea saanto (75.3%, based on H3BTC). Also, the yield of 1 increased gradually from 78.2% to 85.3% with increasing the reaction time from 10 to 90 min. This result suggests that rapid synthesis of MOF can be realized in a significantly korkea saanto using ultrasonic method. Compared with hydrothermal synthesis of the same compound MOF 1, which is carried out at 140°C at high pressure for 24 h,12 ultrasonic synthesis is found to be a highly efficient method with high yield and Edullisia.
Since no product was obtained by mixing zinc acetate with H3BTC in the same reaction medium at ambient temperature and pressure in the absence of ultrasound, Ultraäänellä must play an important role during the formation of MOF 1.
Sonokemialliset laitteet
Hielscher Ultrasonics has long-time experience in the design and manufacturing of powerful and reliable ultrasonicators and sonochemical reactors. Hielscher covers your application requirements with its broad range of ultrasonic devices – from small lab devices over Penkki-Top ja lentäjä ultrasonicators up to full-industrial systems for sonochemical production on commercial scale. A large variety of sonotrodes, booster, reactors, flow cells, noise cancellation boxes and accessories allow to configurate the optimal setup for your Sonokemiallinen reaction. Hielscher’s ultrasonic devices are very robust, built for 24/7 operation and need only very little maintenance.
Kirjallisuus/viitteet
- Dey, Chandan; Kundu,Tanay; Biswal, Bishnu P.; Mallick, Arijit; Banerjee, Rahul (2014): Crystalline metal-organic frameworks (MOFs): synthesis, structure and function. Acta Crystallographica Section B 70, 2014. 3-10.
- Hashemi, Lida; Morsali, Ali; Yilmaz, Veysel T.; Büyükgüngor, Orhan; Khavasi, Hamid Reza; Ashouri, Fatemeh; Bagherzadeh, Mojtaba (2014): Sonochemical syntheses of two nano-sized lead(II) metal–organic frameworks; application for catalysis and preparation of lead(II) oxide nanoparticles. Journal of Molecular Structure 1072, 2014. 260-266.
- Li, Zong-Qun; Qiu, Ling-Guang; Xu, Tao; Wu, Yun; Wang, Wei; Wu, Zhen-Yu; Jiang, Xia (2009): Ultrasonic synthesis of the microporous metal–organic framework Cu3(BTC)2 at ambient temperature and pressure: An efficient and environmentally friendly method. Materials Letters 63/1, 2009. 78-80.
- Qiu, Ling-Guang; Li, Zong-Qun; Wu, Yun; Wang, Wei; Xu, Tao; Jiang, Xia (2008): Facile synthesis of nanocrystals of a microporous metal–organic framework by an ultrasonic method and selective sensing of organoamines. Chemical Communication 2008, 3642–3644.
- Stock, Norbert; Biswas, Syam (2012): Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chemical Review 112/2, 2012. 933–969.
- Suslick, Kenneth S. (ed.) (1988): Ultrasound: Its Chemical, Physical and Biological Effects. VCH: Weinheim, Germany. 1988.
- Tahmasian, Arineh; Morsali, Ali; Joo, Sang Woo (2013): Sonochemical Syntheses of a One-Dimensional Mg(II) Metal-Organic Framework: A New Precursor for Preparation of MgO One-Dimensional Nanostructure. Journal of Nanomaterials 2013.
- Thompson, Joshua A.; Chapman, Karena W.; Koros, William J.; Jones, Christopher W.; Nair, Sankar (2012):Sonication-induced Ostwald ripening of ZIF-8 nanoparticles and formation of ZIF-8/polymer composite membranes. Microporous and Mesoporous Materials 158, 2012. 292-299.
- Wang, LiPing; Xiao, Bin; Wang, GongYing; Wu, JiQian (2011): Synthesis of polycarbonate diol catalyzed by metal-organic framework Zn4O[CO2-C6H4-CO2]3. Science China Chemistry 54/9, 2011. 1468-1473.