离子热法合成铁掺杂的开放骨架化合物及其表征
发布时间：2018-07-26 16:57
【摘要】：无机开放骨架化合物因其优异的物理化学性质在气体的吸附、分离与催化等领域有着广泛的应用前景,合成新型开放骨架化合物成为多孔材料科学领域的重要研究课题。(亚)磷酸盐开放骨架微孔材料因其骨架组成的丰富性、拓扑学结构的多样性和优异性,近些年来备受科研工作者的关注。随着合成技术的进步,(亚)磷酸盐开放骨架化合物的骨架元素已经从主族元素拓展到过渡金属元素,研究过渡金属掺杂的开放骨架材料的合成与性质以及应用成为研究热点。离子液体是一种以阴阳离子配伍形式存在的离子型化合物,在离子热合成体系中,其不仅可以作为溶剂,还可以作为无机材料的模板剂和前驱体。与传统的水热/溶剂热合成方法相比,离子热合成方法具有低熔点、高沸点、可循环利用等优点。本论文利用离子热合成方法在铁掺杂开放骨架亚磷酸盐、磷酸-草酸盐等领域进行了合成研究,主要研究成果包括:1.在离子液体溴代1-甲基-3-乙基咪唑[Emim]Br体系中,合成出一例具有十二元环孔道结构的开放骨架亚磷酸铁化合物Fe_5~п(NH_4)_2(HPO_3)_6,并通过高通量的方法调变铁磷比、温度、时间以及离子液体种类和用量的之间关系,摸索出相同原料下三种不同晶体的晶化区域图。三种不同的晶体是通过离子热法合成出来的,根据结构分析显示离子液体在合成中起到了溶剂和模板剂的双重作用。2.以离子液体溴代1-甲基-3-乙基咪唑[Emim]Br为溶剂,L-组氨酸为模板剂,合成出了一例新型磷酸-草酸铁开放骨架化合物[C6H9N3O2]Fe(H2PO_4)_2(C2O4)0.5(JU-109),该化合物结晶于单斜晶系C2/c空间群,四元环次级结构单元(SBU)经草酸根连接形成的一维链状结构,在ab平面上,该一维链状结构经由四配位的[H2PO4]连接形成无限延伸的二维层状结构,组氨酸分子坐落在层间起着支撑骨架的作用。粉末样品磁性测试表明,化合物在高温区表现为反铁磁相互作用,在低温区(低于30K)表现为铁磁性。
[Abstract]:Inorganic open matrix compounds have been widely used in gas adsorption, separation and catalysis because of their excellent physical and chemical properties. The synthesis of new open matrix compounds has become an important research topic in the field of porous material science. Phosphate open matrix microporous materials have attracted much attention in recent years because of their richness of skeleton composition, diversity and excellence of topological structures. With the progress of synthesis technology, the skeleton elements of (hypophosphate) open skeleton compounds have been extended from the main group elements to transition metal elements. The study on the synthesis, properties and applications of transition metal doped open skeleton materials has become a hot topic. Ionic liquid is an ionic compound in the form of anion and anion compatibility. It can be used not only as solvent but also as template and precursor of inorganic materials in ionic thermal synthesis system. Compared with the traditional hydrothermal / solvothermal synthesis method, the ionic thermal synthesis method has the advantages of low melting point, high boiling point and recyclable utilization. In this paper, the synthesis of iron doped open skeleton phosphite and phosphoric acid oxalate was studied by ion-thermal synthesis. The main research results include: 1. In the ionic liquid 1-methyl-3-ethylimidazole [Emim] Br system, an open skeleton ferric phosphite compound Fe5- (NH_4) _ 2 (HPO_3) _ 6 with a 12-member annular pore structure was synthesized, and the iron-phosphorus ratio and temperature were adjusted by high-flux method. The crystallization regions of three different crystals under the same raw material were found out by the relationship between the time, the kinds and the amount of ionic liquids. Three different crystals were synthesized by ion-thermal method. According to the structure analysis, ionic liquids played a dual role of solvent and template in the synthesis. A new open framework compound of [C6H9N3O2] Fe (H2PO_4) _ 2 (C2O4) _ 0.5 (JU-109) was synthesized by using ionic liquid 1-methyl-3-ethylimidazole [Emim] Br as the solvent L- histidine as template. The compound crystallized in the monoclinic C _ 2 / c space group, and a new type of [C6H9N3O2] Fe (H2PO_4) _ 2 (C2O4) _ (0.5) (JU-109) was synthesized from the open matrix of [C6H9N3O2] Fe (H2PO_4) _ 2 (C2O4) _ 0.5 (JU-109). A one-dimensional chain structure formed by a four-member ring secondary structure unit (SBU) connected by oxalate. On the ab plane, the one-dimensional chain structure is joined by a four-coordinated [H2PO4] to form an infinitely extended two-dimensional layered structure. Histidine molecules are located in the interlaminar to support the skeleton. The magnetic properties of the powder samples show antiferromagnetic interaction at high temperature and ferromagnetism at low temperature (below 30K).
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2146671
[Abstract]:Inorganic open matrix compounds have been widely used in gas adsorption, separation and catalysis because of their excellent physical and chemical properties. The synthesis of new open matrix compounds has become an important research topic in the field of porous material science. Phosphate open matrix microporous materials have attracted much attention in recent years because of their richness of skeleton composition, diversity and excellence of topological structures. With the progress of synthesis technology, the skeleton elements of (hypophosphate) open skeleton compounds have been extended from the main group elements to transition metal elements. The study on the synthesis, properties and applications of transition metal doped open skeleton materials has become a hot topic. Ionic liquid is an ionic compound in the form of anion and anion compatibility. It can be used not only as solvent but also as template and precursor of inorganic materials in ionic thermal synthesis system. Compared with the traditional hydrothermal / solvothermal synthesis method, the ionic thermal synthesis method has the advantages of low melting point, high boiling point and recyclable utilization. In this paper, the synthesis of iron doped open skeleton phosphite and phosphoric acid oxalate was studied by ion-thermal synthesis. The main research results include: 1. In the ionic liquid 1-methyl-3-ethylimidazole [Emim] Br system, an open skeleton ferric phosphite compound Fe5- (NH_4) _ 2 (HPO_3) _ 6 with a 12-member annular pore structure was synthesized, and the iron-phosphorus ratio and temperature were adjusted by high-flux method. The crystallization regions of three different crystals under the same raw material were found out by the relationship between the time, the kinds and the amount of ionic liquids. Three different crystals were synthesized by ion-thermal method. According to the structure analysis, ionic liquids played a dual role of solvent and template in the synthesis. A new open framework compound of [C6H9N3O2] Fe (H2PO_4) _ 2 (C2O4) _ 0.5 (JU-109) was synthesized by using ionic liquid 1-methyl-3-ethylimidazole [Emim] Br as the solvent L- histidine as template. The compound crystallized in the monoclinic C _ 2 / c space group, and a new type of [C6H9N3O2] Fe (H2PO_4) _ 2 (C2O4) _ (0.5) (JU-109) was synthesized from the open matrix of [C6H9N3O2] Fe (H2PO_4) _ 2 (C2O4) _ 0.5 (JU-109). A one-dimensional chain structure formed by a four-member ring secondary structure unit (SBU) connected by oxalate. On the ab plane, the one-dimensional chain structure is joined by a four-coordinated [H2PO4] to form an infinitely extended two-dimensional layered structure. Histidine molecules are located in the interlaminar to support the skeleton. The magnetic properties of the powder samples show antiferromagnetic interaction at high temperature and ferromagnetism at low temperature (below 30K).
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
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1 王志秀;离子热法合成铁掺杂的开放骨架化合物及其表征[D];吉林大学;2017年
，本文编号：2146671
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