Ionothermal synthesis

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. 

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

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... 

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. 

Barpanda P, Djellab K, Recham N, Armand M, Tarascon JM (2011) Direct and modified ionothermal synthesis of LiMnP04 with tunable morphology for rechargeable Li-ion batteries. J Mater Chem 21 10143-10152... 

Barpanda P, Recham N, Chotard JN, Djellab K, Walker W, Armand M, Tarascon JM (2010) Structure and electrochemical properties of novel mixed Li(Fei zMj[)S04F (M = Co, Ni, Mn) phases fabricated by low temperature ionothermal synthesis. J Mater Chem 20 1659—1668... 

Lin, Z., Li, Y., Slawin, AJAJL., and Morris, R.E. (2008) Hydrogen-bond-directing effect in the ionothermal synthesis of metal coordination polymers. Dalton Transactions, 3989 3994. 

Ju Q, Campbell PS, Murdring AV (2013) Interface-assisted ionothermal synthesis, phase tuning, surface modification and bioapplication of Ln -doped NaGdp4 nanocrystals. J Mater Chem B 1 179-185... 

Finally, the ionothermal synthesis route developed since 2004 by Morris et al. [187] was not successful for the silica-based materials but the ionic liquids themselves can act as classical OSDAs in aqueous media. Thus, by using the fluoride route, Zones et al. synthesized pure silica zeolites of TON, ITW and MTT topologies using the OSDAs l,3-dimethyl-37/-imidazol-l-ium, l,2,3-trimethyl-3//-imidazol-l-ium and 1,3-diisopro-pyl-3//-imidazol-l-ium, respectively [12]. Then, in 2009, we reported the synthesis of IM-16 (UOS) a germanosilicate prepared with the ionic liquid 3-ethyl-l-methyl-3//-imidazol-l-ium as OSD A in aqueous media. This microporous material possesses a new topology built from d4r and mtw composite building units [165]. The ionothermal synthesis route, up to now, was only successful in the formation of new phosphate-based microporous materials, as mentioned in the next paragraph. 

As opposed to traditional hydrothermal/solvothermal synthesis, where the solvents are predominantly molecular, ionothermal synthesis is based on the use of ionic liquids as solvents, and in many cases also as templates. Ionic Uquids are a class of molten salts, composed of organic cations and matching anions. At room temperature or near room temperature, ionic Uquids are traditionally defined as Uquids and can safely be used as solvents. In 2004, Morris and coworkers Urst developed the ionothermal synthesis approach to prepare zeoUte materials [54]. Since then, ionothermal synthesis has received great attention due to its potential advantages over traditional hydrothermal synthesis. 

Ionic liquid l-methyl-3-ethylimidazolium bromide ([EMim][Br]) is the most commonly used ionic Uquid in the ionothermal synthesis of zeoUte materials, leading to the formation of cobalt aluminophosphate zeolites SIZ-7 (SIV), SIZ-8 (AEI), and SIZ-9 (SOD) [56]. 

Importantly, ionic liquids show excellent properties on the adsorption of microwave. The combination of microwave-assisted synthesis and ionothermal synthesis opens up an efficient and safe route to prepare zeolite materials [60]. Tian and coworkers reported the microwave-assisted ionothermal synthesis of AlPO-ll using [EmimJBr [61]. Silicon element was also successfully introduced to the framework forming SAPO-11 with potential catalytic applications. In addition, Yan and coworkers developed the ambient pressure synthesis method for silicate zeolites by combining the advantages of ionothermal synthesis, dry-gel conversion, and microwave irradiation [62]. With the assistance of microwave-assisted synthesis, the safe and fast process of ionothermal synthesis has shown to be a promising synthetic route for a variety of zeolite structures. 

Pamham ER, Morris RE. The ionothermal synthesis of cobalt alnminophosphate zeolite frameworks. J Am Chem Soc 2006 128 2204-5. 

Wei Y Tian Z, Gies H, Xu R, Ma H, Pei R, et al. Ionothermal synthesis of an aluminophosphate molecular sieve with 20-ring pore openings. Angew Chem Int Ed 2010 49 5367-70. 

Xu Y Tian Z, Wang S, Hu Y, Wang L, Wang B, et al. Microwave-enhanced ionothermal synthesis of aluminophosphate molecular sieves. Angew Chem Int Ed 2006 45 3965-70. 

Lin Z, Slawin AMZ, Morris RE. Chiral induction in the ionothermal synthesis of a 3-D coordination polymer. J Am Chem Soc 2007 129 4880-1. 

Three-dimensional or layered zinc phosphates can be selectively synthesized via ionothermal approaches using the eutectic mixtures ChCl/hnidazoline or ChCl/Oxalic acid as solvents. Dong and co-workers, demonstrated that by using eutectic mixtures of oxalic acid with different ammonium salts [(Pr4N)Br or (Et4N)Cl], both layered or open-framework zirconium phosphates can be selective prepared by ionothermal synthesis. Finally, tin(II) phosphates were prepared in the eutectic mixture ChCl/Pyrazol. ... 

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