Synthesis, Characterization Of The Novel Hierarchical Aluminum Phenylphosphonate Microspheres

Metal phosphonates as an important branch of organic-inorganic hybrid materials haveexhibit large potential application in the fields of adsorption, separation, catalysis, andbiology and medicine for their abundant chemical composition, diverse structure andmorphology, and unique tailorable frameworks. As so far, the research works focus on thesynthesis and application of new metal phosphonate materials, however, the control ofmaterials’ morphology is yet scarce. Hence, we devote ourselves to synthesize metalphosphonates with special morphology and their morphological control. Aluminumphosphonates with zeolite properties as object, we successfully synthesized two novelaluminum phenylphosphonates with spherical morphology, hierarchical structure offlower-like and fur-covered aluminum phenylphosphonate microspheres, which werecharacterized by SEM, HRSEM, TEM, HRTEM, N2adsorption, FT-IR, MAS NMR, ICP,TG-DTA and Zeta potential analysis. In addition, the preliminary application of thesematerials in the detection of low abundance of peptides/proteins was investigated in thedissertation.1.Hierarchical flower-like aluminum phenylphosphonate microspheres were synthesizedunder acidic conditions by using phenylphosphonic acid and aluminum nitrate as organic andinorganic precursor and adjusting the pH value of synthetic system with NaOH. As a result,new types of porous organic inorganic hybrids consisting of aluminum phenylphosphonatelayered structures and spherical morphology have been obtained for the first time. The sizeand morphology of the resultant aluminum phenylphosphonates could be modulated byvarying the reaction time. The self-assembly of the flower-like microspheres has beenidentified to a synergistic Ostwald ripening and oriented attachment growth. By calcinationsof these flower-like aluminum phenylphosphonate microspheres, mesoporous amorphousaluminum phosphates micro-flowers with uniform pore size of~5.5nm can be prepared. Foran application demonstration, the hierarchical flower-like aluminum phenylphosphonatemicrospheres have been assessed as a candidate material for the detection of low abundanceof peptide/protein.2.Hierarchical fur-covered aluminum phenylphosphonate microspheres were synthesizedby using urea as precipitant and using phenylphosphonic acid and aluminum nitrate as organicand inorganic precursor. The system’s pH value was controlled through the decomposition of urea under high temperature. The change of morphology during the synthesis wasaccompanied by structural change, the essence of which was phase transform. The differentmorphology, such as flower-like microspheres, scraggly and smooth surface microspheres,and fur-covered microspheres, can be obtained by adjusting the hydrothermal reaction time.The hierarchical fur-covered microspheres exhibit positive-potential in a broad range of pHvalue indicating that they possess rarely cationic frameworks. Similarily, inorganicaluminophosphate microspheres can be obtained by calcinations of these hierarchicalfur-covered aluminum phenylphosphonate microspheres and their morphology can becompletely retained during the calcinations.The synthesis and morphological control of hierarchical phenylphosphonatemicrospheres in the dissertation provide a new idea and method for control of metalphosphonates’ morphology and preparation of inorganic aluminophosphates with sphericalmorphology.