Ionothermal

A. Vecchi, B. Melai, A. Marra, C. Chiappe, and A. Dondoni, Microwave-enhanced ionothermal CuAAC for the synthesis of glycoclusters on a calix[4] arene platform, J. Org. Chem., 73 (2008) 6437-6440. 

Recent developments in zeolite synthesis and new materials include (i) the use of combinatorial methodologies, microwave heating, multiple templates or SDAs and concentrated fluoride media in synthesis, (ii) synthesis using the charge density mismatch (COM) concept, (iii) synthesis in ionothermal media, (iv) synthesis with complex designer templates or SDAs, (v) synthesis of nanozeohtes, (vi) zeoUte membranes and thin films (vii) and germanosilicate zeoHtes [76]. Several of these developments are discussed here. 

It is also possible to carry out reactions in ionic liquids at temperatures much higher than the melting point of the IL. Called ionothermal reactions, these differ from hydrothermal and solvothermal reactions in that they may be carried out at atmospheric pressure, due to the low vapor pressures of ionic liquids. Ionothermal reactions have led to novel materials containing cations with unusual coordination numbers (e.g., four-, five-, and six-coordinate aluminum) and morphologies. 

Parnham ER, Morris RE. Ionothermal synthesis of zeolites, metal-organic frameworks, and inorganic-organic hybrids. Accounts of Chemical Research. 2007 40 1005-1013. 

Subsequently, Xu et al. studied the microwave-enhanced ionothermal synthesis of aluminophosphate molecular sieves.[113] By using the ionic liquid l-ethyl-3-... 

Very recently, Tian and coworkers studied the structure-directing role of amines in the ionothermal synthesis of AFI-type molecular sieves in 1-butyl-3-methylimidazolium bormide ([bmimJBr) ionic liquid.[114] Their results indicated that the original crystallization process can be altered by the addition of amine. The 1H NMR spectra of [bmimJBr and amine liquid mixtures revealed that the presence of amine caused a downfield shift of the signal corresponding to the proton of the imidazolium ring, which was considered to be strong evidence for the formation of hydrogen bonds between the ionic liquid and the added amine. 

Triazine-based networks have been produced under ionothermal conditions in molten ZnClj, followed by extraction of residual salt from the materials [15], It is certainly possible that the salt acts here as a template for pore formation indeed, ZnCl has been used previously as a porogen for the formation of activated carbon [27-29],... 

Fig. 13 Proposed structure for polytriazine CTF-1 prepared by ionothermal synthesis [15]...

The gel is made up in a solvent medium which enables the frameworkforming species to come into solution, but should dissolve the crystalline product only sparingly. By far the most widely used solvent is water, which possesses a suitably high dipole moment (8 = 78) to permit dissolution of ionic and partially ionic solids, as well as acceptably low vapour pressures at the temperatures at which synthesis occurs at convenient rates (usually 100-200 °Q. Under these conditions the syntheses are described as hydrothermal. A more limited set of syntheses has been performed in other, non-aqueous, solvents such as alcohols, pyridine-based solvents and ionic liquids, and these are generally described as solvothermal and ionothermal. ... 

Very recently, TSILs having a bis-imidazolium motif linked with various organic groups may allow for the synthesis of hierarchical nanoporous nitrogen-doped carbons (Fig. 1.5). Microporous-mesoporous carbon with the specific surface area up to 1,300 m g was facilely obtained through the ionothermal synthesis process as well [34], Besides the potential good CO2 uptake abilities of these N-doped mesoporous carbons, they may also be considered as the baskets for polyamines-derived CO2 adsorbents based on their good mesoporous architectures. 

Lee JS, Wang X, Luo H, Baker GA, Dai S (2009) Fadle ionothermal synthesis of miciopoious and mesoporous carbons from task specific ionic liquids. J Am Chem Soc 131 4596-4597... 

Kuhn P, Antonietti M, Thomas A (2008) Porous, covalent triazine-based frameworks prepared by ionothermal synthesis. Angew Chem Int Edit 47 3450-3453... 

Kuhn P, Forget A, Hartmann J et al (2009) Template-free tuning of nanopores in carbonaceous polymers through ionothermal synthesis. Adv Mater 21 897-901... 

Wang W, Ren H, Sun F et al (2012) Synthesis of porous aromatic framework with tuning porosity via ionothermal reaction. Dalton Trans 41 3933-3936... 

Park Ho et al. applied this method to [BMIM][BF4] which was enclosed in aluminum hydroxide hybrids by an ionothermal process at several I L/inorganic precursor ratios [19]. The analysis ofthe concentration-dependent 2-D IR spectra of the aforementioned system gave diflerent changes of intensities due to intermolecular... 

The synthesis is performed under ionothermal conditions and was elaborated by Kuhn et al. In this process, anhydrous ZnCla is mixed and heated in a sealed Pyrex ampoule for 48 h at 400 C. The product obtained from the reaction is stirred for 24 h in 1 M HCl and cleaned with water and THF several times. Three aromatic nitrile groups are trimerized to form a C3N3 ring by the eatalytic action of ZnCla. This ring and tetraphenylmethane form a covalently conneeted open organie framework. This reaction, when followed by FTIR, demonstrates the eompletion of the trimerization reaction as denoted by the loss of intensity of the C=N vibration at 2234 em (PAF-2 Figure 3.11). ... 

There are various routes of hydrothermal crystallisation such as the ionothermal synthetic route, micro-emulsion-based hydrothermal route, dry gel conversion synthetic route, solvo-thermal S5mthetic route and so forth, which can be studied. 

The term upconversion describes an effect [1] related to the emission of anti-Stokes fluorescence in the visible spectral range following excitation of certain (doped) luminophores in the near infrared (NIR). It mainly occurs with rare-earth doped solids, but also with doped transition-metal systems and combinations of both [2, 3], and relies on the sequential absorption of two or more NIR photons by the dopants. Following its discovery [1] it has been extensively studied for bulk materials both theoretically and in context with uses in solid-state lasers, infrared quantum counters, lighting or displays, and physical sensors, for example [4, 5]. Substantial efforts also have been made to prepare nanoscale materials that show more efficient upconversion emission. Meanwhile, numerous protocols are available for making nanoparticles, nanorods, nanoplates, and nanotubes. These include thermal decomposition, co-precipitation, solvothermal synthesis, combustion, and sol-gel processes [6], synthesis in liquid-solid-solutions [7, 8], and ionothermal synthesis [9]. Nanocrystal materials include oxides of zirconium and titanium, the fluorides, oxides, phosphates, oxysulfates, and oxyfluoiides of the trivalent lanthanides (Ln ), and similar compounds that may additionally contain alkaline earth ions. Wang and Liu [6] have recently reviewed the theory of upconversion and the common materials and methods used. 

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