Application Of Hydrothermal/Solvothermal Combinatorial Technique To The Syntehsis Of Microporous Aluminophosphates

In the last few decades, extensive research has been focused on the exploration of new microporous materials because of their wide applications in the field of catalysis, environment and functional material. However, the formation of these materials, which is normally facilitated by organic templates, is not yet well understood due to the complexity of hydrothermal or solvothermal reactions. The reaction systems for these kinetic crystalline compounds are very complex and their crystallization processes are manipulated by various factors, such as gel composition, organic template, pH value, temperature and crystallization time. So far the preparations of microporous materials are still through traditional trial and error method, this means, in a sense, the synthesis is blindness.Compared to the traditional synthesis methods for materials, the combinatorial approach has been proven as a fast experimentation method for the discovery of new materials. In addition, the systematic investigation of large parts of the respective parameter space in made possible and thus reaction trends are easily established. The advantages of the application of the combinatorial methodology can be summarized as follows: The combinatorial method allows the fast and systematic investigation of a large number of reactions since automatic dispensing, mixing of reagents, as well as automatic separation and identification of the products are possible; The use of minimal amounts of starting materials leads to a cost and waste reduction and makes systematical investigations using expensive or hard to be synthesized starting materials feasible; The use of parallel reactors guarantees that all samples are treated identically, e.g., the same solutions are used, reacted at the same temperature and for the identical time. Thus it is possible to find optimum reaction conditions and evaluate reaction trends in parameter space.1. Developed techniques and equipment for combinatorial hydrothermal/solvothermal synthesis of open-framework aluminophosphates including process of reagent transfer, separation and characterization.2. Study the synthesis rulers1) We study the system 1.0 Al(iOPr)3-x H3PO4-y Diisobutylamine-EtOH/H2O by clear-solution way combining combinatorial synthesis and conventional synthesis in detail. It has not been reported that aluminophosphates was synthesized using diisobutylamine as template. In this thesis, diisobutylamine was used as template in the hydrothermal/solvothermal synthesis of aluminophosphates. wanter or alcohol. And optimum reaction conditions and evaluate reaction trends in parameter space was investigated thoroughly.Three compounds were obtained in presence of alcohol:When y/(x-2)>1,the main phase is AlPO₄-11;When y/(x-2) >1 slightly and x belong to (3.5～5.7),the main phase is AlPO4-5;When y/(x-2) <1 slightly and x belong to (5.6～8) , the main phase is (Al₃P₄O₁₆)(NH₃(CH₂)₅NH₃)(C₅H₁₀NH₂), a 2D aluminophosphate。Three compounds were obtained in presence of alcohol:When y/x>1/2,the main phase is dense phase;When y/x >1/2 slightly and x belong to (3～8),the main phase is AlPO₄-52;When y/x<1/2 slightly and x belong to (4.5～11),the main phase is UiO₆.2) We study the system 1.0 Al(iOPr)3-x H₃PO_4-y phenylhydrazine-EtOH/H₂O by clear-solution way combining combinatorial synthesis and conventional synthesis in detail. It has not been reported that aluminophosphates was synthesized using phenylhydrazine as template.Hydrazine and its ramification are believed to be dangerous for the process of synthesis for its unstable properties. However, appling of combinatorial synthesis into the system decrease the danger greatly for its micro-amount of reagent. Also, transferring reageat by machine make it possible to isolate the reaction. So, it is safely to say that combinatorial is an effective way to synthesis compounds in more specific conditions than traditional synthesis.Three compounds was obtained in this process: AlPO₄-CJ4,AlPO₄-15 and [Al₂P₃O₁₀(OH)₂][C₆NH₈], a 2D aluminophosphate.Combinatorial method demonstrates great potential for the discovery of new open-framework materials, as well as in helping to understand the synthetic factors on the influence of the crystallization of such materials. The investigations to the crystallization process and rational synthesis give some new insight into the formation mechanism of microporous aluminophosphates. Combinatorial approach is a useful technique in the study of inorganic microporous compounds. This method should be applicable to other organically templated microporous materials and extend to other fields of chemistry.