醇体系磷酸铝的合成化学

【作者】 高秋明；

【导师】 徐如人；

【作者基本信息】 吉林大学 ， 无机化学， 1997， 博士

【摘要】 在醇体系中，成功地合成出系列一维链状磷酸铝单晶[AlP₂O₈]·[NH₄]·[H₃NCH₂CH₂NH₃]、[AlP₂O₈H]·[H₃NCH₂CH₂NH₃]和[AlP₂O₈H]·2[C₅H₁₀NH₂]、系列二维层状磷酸铝单晶[Al₆P₈O₃₂]·3[NH₃CHMeCH₂NH₃]·H₂O、[Al₃P₄O₁₆]·3[CH₃CH₂NH₃]和[Al₃P₄O₁₆H₂]·[C₁₂H₁₀NH₂]，以及多种三维微孔磷酸铝粉末及单晶AlPO₄-17、AlPO₄-JDF、JDF-2、AlPO₄-41、AlPO₄-12、Al₃P₃O₁₆·0.5C₄H₉OH·H₂O和CoAlPO₄-34，并结析出单晶结构。对其合成条件进行了研究，认为体系中磷的浓度和铝的浓度对生成不同维数磷酸铝起关键作用，对典型的磷酸铝分子筛AlPO₄-5、AlPO₄-41及AlPO₄-25异丁烷脱氢氧化为异丁烯进行了详细研究，认为AlPO₄-5是较合适的催化剂。开发出一类具有较大层间距和独特吸附性质的层状磷酸铝中介相APO-Ln，对其结构、性质进行了详细表征。 在合成的基础上，对一维链状磷酸铝、二维层状磷酸铝以及三维微孔磷酸铝的晶格能进行了计算，并对二维层状磷酸铝的结构进行了初步设计和稳定性研究， 此外，又成功地合成出系列微孔磷酸钴化合物NaCoPO₄和CoHPO₄·0.5H₂O，对于过渡金属磷酸盐微孔化合物的开发具有较大的推动作用。更多还原

【Abstract】 Scientists at Union Carbide Corporation have firstly synthesized a series of aluminophosphates （AlPO₄-n where n signifies a distinct framework structure） in 1980s. Structurally, most AlPO₄-n phases are exclusively composed of PO₄ and AlO₄ primary building units although a few contain AlO₅ and AlO₆ units. The structure is based on a network of strictly alternating P and Al with no P-O-P and Al-O-Al bands for the Lowenstein rule when there no structural water or OH.Hydrothermal techniques have been the main methods of synthesis employed for microporous materials. The synthesis of silica-sodalite and aluminosilicate sodalite from alcoholic systems, described by Bibby and Dale, developed a new route for the synthesis of the materials. In 1988, R. Xu and coworkers reported that several kinds of aluminophosphates, gallophosphates and their metal-substituted derivatives have been synthesized from non-aqueous systems. Recently, R. Xu et al reported the synthesis of JDF-20 with twenty member-ring, the largest ring among the known synthetic microporous materials, from alcoholic systems. The non-aqueous synthetic technique has also been used in the field of giant single crystals and novel structural or character materials.We are trying to study the synthesis, characterization and structural designation of 1-dimensional （1-D） chain, 2-d layered and 3-D microporous aluminophosphates by solvothermal techniques on the basis of the known experiences and results.A series of 1-D chain, 2-D layered and 3-D microporous aluminophosphates have been synthesized, including 1-D: [AlP₂O₈][NH₄][H₃NCH₂CH₂NH₃], [AlP₂O₈H][H₃NCH₂CH₂NH₃], and [AlP₂O₈H]2[C₅H₁₂N]; 2-D: Al₃P₄O₁₆]1.5[NH₃CHMeCH₂NH₃]0.5H₂O,更多还原