The Hydrothermal/Solvothermal Combinatorial Synthesis Of Aluminophosphate Microporous Compounds In Fluorine System

In the last few decades, extensive research has been focused on the explorationof new microporous materials because of their wide applications in the field ofcatalysis, environment and functional material. The combinatorial approach influorine system is preponderant to group for new microporous materials.Flanigen E. M.'s group introducted fluorine into the system, they used F-ionsinstead of OH-ions to synthesize the zeolites under hydrothermal condition. Afterthat, Guth J. L. and Kesser H performanced the systmetic research in this field. F-ions are frequently employed in the reaction mixture to promote the formation oflarge single crystals or novel structures. Three roles for F-in the synthesis ofmicroporous solids have been described by Guth et al., i.e., (a) mineralizing, (b)structure directing, and (c) templating, so F-can direct to product big crystal andplay a important roal in exploitation of new compounds. Influoroaluminophosphates, F-is incorporated into their networks or frameworks.Compared to the traditional synthesis methods for materials, the combinatorialapproach has been proven as a fast experimentation method for the discovery of newmaterials. In addition, the systematic investigation of large parts of the respectiveparameter space in made possible and thus reaction trends are easily established.The advantages of the application of the combinatorial methodology can besummarized as follows: The combinatorial method allows the fast and systematicinvestigation of a large number of reactions since automatic dispensing, mixing ofreagents, as well as automatic separation and identification of the products arepossible;The use of minimal amounts of starting materials leads to a cost and wastereduction and makes systematical investigations using expensive or hard to besynthesized starting materials feasible;The use of parallel reactors guarantees thatall samples are treated identically, e.g., the same solutions are used, reacted at thesame temperature and for the identical time. Thus it is possible to find optimumreaction conditions and evaluate reaction trends in parameter space.1) Synthesis fluoridealuminophosphate compoundsA) Applying combinatorial approach, in the fluorine system at the proportion of1.0Al(OPri)?a(3.0-4.0)H3PO4?a(5.0-6.0)2-amino-2-methyl-1-propanol?a55triethylene glycol-0.5hydrofluoric acid, A new layered fluoridaluminophosphate Al4P5O20F[C4H12NO]3.5.[H3O]0.5with an Al/P ratio of 4/5 has been synthesized undersolvothermal conditions. The structure is the first compound that has the largest ring,and it is the second layered aluminophosphate after Mu-4.The noval crystal structure of Al4P5O20F [C4H12NO]3.5.[H3O] 0.5 is composed ofsingle aluminophosphate layers, which contain a extra large 16-mr ring window witha network topology. The space group is C2c and layers stack in the ABAB sequenceso a straight pore can be formed. In this compound, aluminum atoms aretetrahedrally coordinated and four aluminum atoms are connected to four oxygenatoms and the other one is connected to a fluorine atom within the layers. Phosphorusatoms possess only three bonds within the layer and one terminal oxygen (P=O bond)pointing into the interlayer space. All 6-rings in the layers are capped with aP-tetrahedron, thus forming ????capped 6-MR?ˉ?ˉ or ????half-cube?ˉ?ˉ units. The corners ofthese capped 6-MR units point alternatively above and below the layer.On the opposite position three four-member rings are inset between two sixcapped six-member rings, and one the other opposition one four-member ring is insetbetween two six capped six-member rings, which form 16-MR window. Thestructure accord with that we have ever designed. Even we can design more newstructures with extra large window which can be composed of four-member ringsand six capped six-member rings via the information of Al4P5O20F[C4H12NO]3.5.[H3O] 0.5. Different location and different number of four-member ringbetween two capped six-member rings can form different new structures.B) Synsesized the known compound of AlPO-CHA-F used the template oftetrametylethylenediamine. Triclinic and the space group is P-1 (No. 2). The cellparameter: a = 9.1431(18) ? b = 9.1760(18) ? c = 9.2971(19) ? |á = 88.32(3)??,|?= 79.17(3)??, |? = 87.65(3)??,Z = 2?￡2) Synthesis aluminophosphate compoundA) Synthesized a layered compound Al3P4O16[C4H12ON]2?H3O by tempate of2-amino-2-methyl-1-propanol in the triethylene glycol which contain 4-,6-,8-MR.monoclinic,space group is pmna,the cell parameter: a = 18.511(3) ?, b =14.649(2) ?,c = 9.0928(12) ?,|á = 90??,|? = 90??, |? =90??,Z = 4?￡In the inorganiclayer of Al3P4O16[C4H10ON]2?H3O, the between the capped six-member rings fourmember ring and the bond of Al-O-P connect alternately forming eight member ring.Layers stack in the ABAB sequence on Y axes.B) The template N, N?ˉ-dimethylpyridine, tetraethylenediamine,2-methylpiperazine and N-ethylmorpholine can produce the compound AlPO-21.The templates disassembled to dimethylamine after the Structure Determination wasfound. The study shows that the organic amines having lower interaction energieswith framework, such as ethanolamine and trimethylamine, are suitable templatesthat can successfully direct the formation of aluminophosphate AlPO4-21. The largerorganic amines like N, N, N', N'-tetramethylethylenediamine and N, N, N',N'-tetramethyl-1, 3-propanediamine tend to decompose to small and suitable aminesto direct the formation of AlPO4-21.C) Synthesized three similar structures with Al/P=3/4 which have 12-MR bythree different chiral templates and reseached their experiment methods andstructures. It is found that their 12-rings are formed by four member rings and cappedsix member rings connect alternately. Comparing these three structures we knowtheir space goups and stack quomodoes are different. Al3P4O16[C4H12NO]3,Rhombohedral, in R-3 space group, the cell parameter: a =12.7194(3)?, b =12.7194(3)?, c = 32.6462(11) ?, |á = 90??, |? = 90??, |? =120??, Z = 6. Layers stack inthe ABAB sequence inside crystal lattice. Al3P4O16 [NH3CH2CH(OH)CH3]3+,Rhombohedral, a =13.0987?, b =13.0987?, c = 26.9653?, |á = 90??, |? = 90??, |? =120??,Z = 6. Layers stack in the ABAB sequence on crystal lattice. [Al6P8O32(H2O)2][C5N2H14]3?[H2O]10 trigonal, P-1, a =13.2038?, b =13.2038?, c = 9.517 ?, |á = 90??,|? = 90??, |? =120??, Z = 4. Layers stack in the AAA sequence on crystal lattice.3) Other compoundsA) Synthesized aluminofluorid AlF6[C4H12NO]2?H3O using triethylene glycolas the solvent and 2-amino-2-methyl-1-propanol as the structure directing agentunder solvothermal conditions when the proportion of hydronfluorine is very high.Monoclinic, the space group is Cc, a =6.4882(14) ?, b =21.947(2)?, c = 9.517 ?, |á= 90??, |? = 90.094??, |? =90??, Z = 4.B)Synthesized the compound CoAlPO-GIS using 2-amino-2-methyl-1-propanolor2-methylpiperazine. CoAlPO-GIS synthesized by 2-amino-2-methyl-1-propanolwhose parameter as follows: monoclinic, Fddd, a = 10.197(2) ?, b = 14.038(3) ?, c= 14.490(3) ?, |á = 90??, |? = 90??, |? =90?? , Z=32. The template organic molarculor isdisassembled into NH4+, and Al and Co occupy the same locations.Combinatorial method demonstrates great potential for the discovery of newopen-framework materials, as well as in helping to understand the synthetic factorson the influence of the crystallization of such materials. The investigations to thecrystallization process and rational synthesis give some new insight into theformation mechanism of microporous aluminophosphates. Fluorine system andcombinatorial approach are useful techniques in the study of inorganic microporouscompounds. To combine these two methods should be applicable to otherorganically templated microporous materials and extend to other fields ofchemistry?￡...