Alkali Metal Boron Gallium Salts Microporous Crystalline Materials Preparation, Characterization And Thermochemical Study

Microporous crystalline material has a very excellent properties, such as catalytic activity, ion exchange, and adsorption, etc, so it has important application in petrochemistry engineering, fine chemistry industry, and enviromental protection. For a long time, designing synthesis, properity and application of new inorganic microporous materials with novel structure and different chemical composition are the very active area of frontier research. In recent years, the inorganic microporous crystalline materials on the synthesis, characterization and structure of studies have reported a lot, but on the thermodynamics properties of microporous materials have reported relatively rare, especially the studies of the thermochemistry of the boron-containning inorganic microporous crystalline materials are not reported in the literature.Thermodynamic properties play very important roles in scientific research and industrial applications. Thermochemical data can provide information on stabilities and reactivities of molecules that are used, and also are a key factor in the safe and successful scale-up of chemical processes in the chemical industry. As for the thermochemistry of borates, the standard molar enthalpies of formation of many alkaline and alkaline-earth metal borates and part of transition metal borate have been reported. As part of the continuing study of metal borates, the thermochemistry of the zeolite-like alkaline metal galloborates have been investigated.In this thesis, two novel alkaline metal templeted borogallates microporous materials constructed by B-O clusters and Ga-O units, K2[Ga(B5O10)]·4H2O and Rb2[Ga(B5O10)]-4H20, have been synthesized successfully under mild hydrothermal/solvothermal conditions by a new synthesizing path. The products have been identified and characterized by FT-IR, EDS, XRD,simultaneous DTA-TG and chemical analysis, which have been proved to be the pure samples and suitable for the calorimetric experiments. At the same time, we have also studied the NLO and photoluminescent properties of the microporous crystalline materials.The molar enthalpies of solution of KGa(SO4)2·12H2O(s) in the mixture of 1 mol dm-3 HCl and calculated amount of K2B4O7·4H2O, of K2SO4 (s) in the mixture of 1 mol dm-3 HCl and calculated amount of H3BO3, of K2[Ga(B5O10)]·4H2O (s) in the mixture of 1 mol dm-3 HCl and calculated amount of K2SO4 and H3BO3 at 298.15K were measured, respectively. With the incorporation of the previously determined enthalpies of solution of H3BO3(s) and K2B4O7·4H2O(s) in 1 mol dm-3 HCl, together with the use of the standard molar enthalpies of formation for K2B4O7·4H2O(s), KGa(SO4)2·12H2O(s), K2SO4(s), H3BO3(s), and H2O(1), the standard molar enthalpy of formation of-(5768.5±9.1) kJ·mol-1 for K2[Ga(B5O10)]·4H2O(s) was obtained on the basis of the appropriate thermochemical cycle. In addition, the standard molar enthalpy of formation of-(5757.6±0.8) kJ·mol-1 for KGa(SO4)2·12H2O(s) was also obtained according to its molar enthalpy of solution of (45.15±0.11) kJ·mol-1 in H2O at 298.15K.The molar enthalpies of solution of Rb2[Ga(B5O10)]·4H2O in the mixture of 1 mol dm-3 HCl (aq) and calculated amount of KCl(s), of K2[Ga(B5O10)]·4H2O (s) in the mixture of 1 mol dm-3 HCl and calculated amount of RaCl (s) were measured, respectively. The molar enthalpies of solution of RaCl (s) in 1 mol dm-3 HCl and KC1 (s) in 1 mol dm-3 HCl were also measured, respectively. Together with the use of the standard molar enthalpies of formation for RaCl (s), KCl (s) and K2[Ga(B5O10)]·-4H2O, the standard molar enthalpy of formation of-(5762.9±9.1) kJ·mol-1 for Rb 2[Ga(B5O10)]·4H2O(s) was obtained on the basis of the appropriate thermochemical cycle.The results of this study can provide a new synthesis method, physico-chemical base data and theoretical basis on the application of microporous material of alkaline metal galloborates materials. This results of this thesis enrich the research scope of boron-containning inorganic microporous crystalline materials, which are of significance to promote the growing development of thermochemistry and inorganic microporous material.