Hydrothermal Synthesis And Research Of Gallium Phosphates (Gallium Phosphite) With Open-framework Under The Low Reactant System

Inorganic microporous materials have popular application in catalysis,adsorption, ion-exchange, separation and host-guest assemblies due to their uniquepore architectures. And the rational design and synthesis of new microporouscompounds, as well as the development of new synthetic ways are becoming thetopics of microporous chemistry. In the last decade, the synthesis of new materialsthat might combine the nanoporosity of zeolites with the magnetic and opticalproperties, electronic conductivity and ferrodlectricity of transition metal phosphatessuch as TiPOs, VPOs, FePOs, ZnPOs and CoPOs have been reported in the literature.Many of these materials exhibit unique structures and may have potentialapplications in catalysis and magnetic field. In addition to phosphates, openframework metal arsenates, phosphite, selenite, germinates, sulfates and carbonatehave also been reported in the literature. The successful syntheses of these newcompounds with open-framework open a new field for the microporous compounds. This research focused on the hydrothermal synthesis and structuralcharacterization of gallium phosphates (gallium phosphite) templated by organicamine. During the attempts to prepare new microporous gallium phosphates, a new 2-Dlayered gallium phosphate JGP-L1 with a Ga/P ratio of 6/7 and a new 3-D galliumphosphate JGP-4 with a Ga/P ratio of 7/8 have been synthesized hydrothermally 153摘 要 吉林大学博士学位论文using polyamine (TEPA and TETA, respectively) as structure-directing agent,showing vast structural and compositional diversities. The course of thesingle-crystal growth of JGP-L1 and JGP-4 were explored in the various H2O/Gamolar ratios. The initial gel was well dispersed in large amounts of water for thegrowth of big single crystal. Therefore, the low reactant concentration is necessaryfor the syntheses of single crystals of JGP-L1 and JGP-4, and provide new route forsmall growth of single crystal. A 2-D chiral layered inorganic-organic hybrid gallophosphate JGP-7 and a 1-Dinorganic-organic hybrid gallium phosphates JGP-2 have been synthesizedhydrothermally with luminescence properties. The layered structure of JGP-7 isconstructed from CSC chains and Ga(2)2F4(H2O)2 dimers, in which CSC chain isisostructural to CSC chain of JGP-2. It is noteworthy that JGP-7 exhibits chiralenantiomers of the structure between layers. JGP-7 and JGP-2 exhibit a strongemission band at 412 and 388 nm, respectively, which can be assigned toligand-to-metal charge transfer (LMCT) and ligand-to-ligand charge transfer (LLCT)via π-π stacking interactions of the 1,10-phen or 2,2'-bipy ligands. JGP-7 and JGP-2may find wide applications in blue light emitting devices, since it possesses goodthermal stability and is insoluble in common polar and non-polar solvents. Two new 3-D gallophosphate compounds JGP-8 and JGP-9 have beensynthesized hydrothermally by using racemic organic amines (1,3-diaminopentaneand 1,2-diaminopropane) as the template. The 3-D anionic framework of JGP-8 isconstructed from a repetition of novel Ga2P2O10 single four-rings (S4Rs) and HPO4tetrahedra, in which the S4Rs is composed of one GaO6 octahedron, one GaO4tetrahedron and two PO4 tetrahedra fused together via vertex-sharing Ga–O–P bonds.The 3-D anionic framework of JGP-9 is built up from a repetition of an enneamericstructural fragment Ga5(PO4)4O6 and HPO4 tetrahedra. This enneameric structural 154摘 要 吉林大学博士学位论文fragment is very close to the Ga5(PO4)4O4F2 structural unit in MIL-1. The fashion ofJGP-9 linked is different to layer structure of MIL-1, forming a new anionicframework. A gallophosphate compound JGP-5 has been synthesized hydrothermally usingtrans-1,4-diaminocyclohexane as the template. The organic...