Synthesis, Characterization Of Boron-containing Ionic Lquids And Their Application In The Synthesis Of Borophosphates

Inorganic microporous materials have uniform pore structure and large specific surface area which can serve as a kind of new structural materials and be extensively applied in such fields as ion-exchange, adsorption, separation, catalysis and host-guest assemblies. Ionothermal synthesis is a novel method for the preparation of porous materials. It makes it possible to synthesize inorganic microporous compounds with novel morphologies, new structures and special functions by providing nearly "pure" ionic condition and in the role of both solvent and template. In this dissertation, a series of task-specific boron containing ionic liquids (ILs), quaternary ammonium bis(oxalato)borate have been prepared and used to synthesize new borophosphates. The most significant feature of this ionothermal synthesis system is that the cations of ILs probably act as solvent and structure-directing agents, while the anion as boron source. Combined with traditional boric acid flux synthesis method, several new borophosphates and phosphites have been synthesized successfully. The crystal structures and properties have been studied in detail.The main contents are as following:1. Two kinds of quaternary ammonium bis(oxalato)borate ionic liquids and two phosphor-containing ionic liquids were designed and prepared. The products were characterized by NMR, MS, TG-DTG and DSC, which indicated that each was prepared successfully in high purity except EmimH2PO3, which a little impurity was detected in the sample by NMR. Their thermal stabilities were studied.2. Mn12P17B6O68H9(Ⅰ) with novel structure and MnHP03(Ⅱ) were prepared by ionothermal synthesis. Compound(Ⅰ) is antiferromagnetic. Part of the atoms occupied positions displayed disorderliness which may be possessed by B atoms and trivalent P atoms. It was also indicated that the amount of Mn(OAc)2·4H2O played a significant role in the synthesis.3. LiCu2[BP2O8(OH)2](Ⅳ) with novel structure, LiCu2[BP2O8(OH)2](Ⅴ) and (NH4)2Co2(HPO3)3(Ⅲ) were prepared by boric acid flux method. Compound(Ⅳ) with contorted9-ring is antiferromagnetic. It has the same oligomeric units and one-dimensional chain structure as compound(Ⅴ), but their different space groups result in the difference of their structures. Compound(Ⅲ) has two-dimensional layered structure and the negative charge is balanced by NH4+between the layers.