離子熱法合成鐵摻雜的開(kāi)放骨架化合物及其表征
發(fā)布時(shí)間：2018-07-26 16:57
【摘要】：無(wú)機(jī)開(kāi)放骨架化合物因其優(yōu)異的物理化學(xué)性質(zhì)在氣體的吸附、分離與催化等領(lǐng)域有著廣泛的應(yīng)用前景,合成新型開(kāi)放骨架化合物成為多孔材料科學(xué)領(lǐng)域的重要研究課題。(亞)磷酸鹽開(kāi)放骨架微孔材料因其骨架組成的豐富性、拓?fù)鋵W(xué)結(jié)構(gòu)的多樣性和優(yōu)異性,近些年來(lái)備受科研工作者的關(guān)注。隨著合成技術(shù)的進(jìn)步,(亞)磷酸鹽開(kāi)放骨架化合物的骨架元素已經(jīng)從主族元素拓展到過(guò)渡金屬元素,研究過(guò)渡金屬摻雜的開(kāi)放骨架材料的合成與性質(zhì)以及應(yīng)用成為研究熱點(diǎn)。離子液體是一種以陰陽(yáng)離子配伍形式存在的離子型化合物,在離子熱合成體系中,其不僅可以作為溶劑,還可以作為無(wú)機(jī)材料的模板劑和前驅(qū)體。與傳統(tǒng)的水熱/溶劑熱合成方法相比,離子熱合成方法具有低熔點(diǎn)、高沸點(diǎn)、可循環(huán)利用等優(yōu)點(diǎn)。本論文利用離子熱合成方法在鐵摻雜開(kāi)放骨架亞磷酸鹽、磷酸-草酸鹽等領(lǐng)域進(jìn)行了合成研究,主要研究成果包括:1.在離子液體溴代1-甲基-3-乙基咪唑[Emim]Br體系中,合成出一例具有十二元環(huán)孔道結(jié)構(gòu)的開(kāi)放骨架亞磷酸鐵化合物Fe_5~п(NH_4)_2(HPO_3)_6,并通過(guò)高通量的方法調(diào)變鐵磷比、溫度、時(shí)間以及離子液體種類和用量的之間關(guān)系,摸索出相同原料下三種不同晶體的晶化區(qū)域圖。三種不同的晶體是通過(guò)離子熱法合成出來(lái)的,根據(jù)結(jié)構(gòu)分析顯示離子液體在合成中起到了溶劑和模板劑的雙重作用。2.以離子液體溴代1-甲基-3-乙基咪唑[Emim]Br為溶劑,L-組氨酸為模板劑,合成出了一例新型磷酸-草酸鐵開(kāi)放骨架化合物[C6H9N3O2]Fe(H2PO_4)_2(C2O4)0.5(JU-109),該化合物結(jié)晶于單斜晶系C2/c空間群,四元環(huán)次級(jí)結(jié)構(gòu)單元(SBU)經(jīng)草酸根連接形成的一維鏈狀結(jié)構(gòu),在ab平面上,該一維鏈狀結(jié)構(gòu)經(jīng)由四配位的[H2PO4]連接形成無(wú)限延伸的二維層狀結(jié)構(gòu),組氨酸分子坐落在層間起著支撐骨架的作用。粉末樣品磁性測(cè)試表明,化合物在高溫區(qū)表現(xiàn)為反鐵磁相互作用,在低溫區(qū)(低于30K)表現(xiàn)為鐵磁性。
[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).
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4
本文編號(hào)：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).
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4
【相似文獻(xiàn)】
相關(guān)碩士學(xué)位論文 前1條
1 王志秀;離子熱法合成鐵摻雜的開(kāi)放骨架化合物及其表征[D];吉林大學(xué);2017年
，本文編號(hào)：2146671
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