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  • 學位論文

新穎結構鈷磷酸鹽和鈷亞磷酸鹽的合成及性質

Synthesis, Characterization and Properties of Novel Cobalt Phosphates and Cobalt Phosphites

指導教授 : 王素蘭
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摘要


本論文主要對鈷磷酸鹽和鈷亞磷酸鹽新化合物的合成、結構及性質進行研究,依結構特性及組成可以區分為三類 : ( 1 ) 層狀鈷磷酸鹽:我們發現一個穩定之層狀鈷磷酸鹽,以此作為基礎結構,可以自行縮合或插入釩的三角雙錐體形成三維的骨架結構;另外,也可以再連接額外的鈷四面體單元在此層狀鈷磷酸鹽上作為活化位置,在此位置上,有機雙胺DACH 和APPIP可以配位連接之方式與層狀鈷磷酸鹽交互連接成為三維的微孔材料,在排除部份孔洞水時,其可以吸附線性有機溶劑的分子。若在鈷四面體活化位置上配位環己胺(CHA)則形成中性的二維結構,因為是由有機物來修飾層間內表面使其呈現親油性,因此具有插層或剝離的特性。 ( 2 ) 氟鈷磷酸鹽:我們在CoO-P2O5-HF-Amine-H2O系統中得到五個化合物。化合物B1和B2是有機支柱型鈷氟磷酸鹽,分別是以PYZ和BPE連接相同的鈷氟磷酸鹽層。此無機層具有氧鐵磁性。因為BPE分子夠長足以消除無機層間的反鐵磁作用,使得化合物B2顯現無機層的氧鐵磁性。但PYZ分子較短使得無機層間的反鐵磁作用較強而形成鐵磁與反鐵磁競爭之情況。化合物B3和B4是有機模板鈷氟磷酸鹽,兩者都是用乙二胺當模板。B3是純磷酸鹽,B4是磷酸鹽混合亞磷酸鹽。這兩個化合物具有相同的雙四環(double-four-ring)建構單元,但雙四環單元連接方式之不同導致結構和磁性不同。化合物B5則是一個層狀的氟鈷釩磷酸鹽。 ( 3 ) 鈷亞磷酸鹽:我們在CoO-P2O3- Amine(ammonium)-H2O系統中得到五個化合物,其中四個是鈷亞磷酸鹽,另外一個是鈷焦磷酸鹽。四個鈷亞磷酸鹽分別是0、1 、2和3維的結構。四個化合物中胺(銨)之作用各有不同,零維的分子錯合物是以imidazole作為配位子,一維的鍊狀結構是以DACH當有機陽離子,二維的層狀結構是以銨離子當陽離子,3維的有機支柱型鈷亞磷酸鹽是以PYZ配位子連接鈷亞磷酸鹽的層。鈷焦磷酸鹽則是一個2維的結構。

並列摘要


This thesis focuses on the syntheses, structures, and properties of new cobalt phosphates and cobalt phosphites. According to their structure features and compositions, they can be categorized into three groups. (1) Layer Cobalt Phosphates (LCPO) We found that a stable cobalt phosphate layer, (H3O)Co2(OH)2(HPO4)(H2PO4), can be used as a basic structure unit for the construction of 3-D structures via either the self condensation or insertion of extra metal polyhedral units. Moreover, extra cobalt ions can be attached to the LCPO through sharing three oxygen corner and leave the forth corner as the active coordination sites for bifunction organic amine ligands such as DACH or APPIP, which interlink with LCPO to form a 3-D microporous structure. Replacing the bifunction amines by monofunctional amines such as CHA, a neutral 2-D structure is fabricated with a hydrophobic and expandable interlayer space, which finds application in intercalatioin and exfoliation. (2) Fluorinated Cobalt Phosphates In the system of CoO-P2O5-HF-Amine-H2O, five new compounds were acquired. Compound B1 and B2 belong to the organic-pillar type. These two compounds consist of the same inorganic layer of the fluorinated cobalt phosphates which are interlinked by the PYZ and BPE, respectively. Because the BPE molecule is long enough to eliminate the interlayered antiferromagnetic interaction, B2 become ferrimagnatic based on the faced-shared trimeric cobalt units below 20K. However, in the case of the shorter PYZ, the interlayered antiferromagnetic interaction is stronger. B1 show a metamagnetic behavior below 20K because of the competition between the ferrimagnetic and the antiferromagnetic interaction. B3 and B4 consist of similar D-4R units of fluorinated CPOs. However, the connections between the D-4R units are through strictly coner-sharing connection in B3 but coner- and edged-sharing connection in B4. B5 is a layered fluorinated cobalt vanadium phosphate. (3) Cobalt Phosphites In the system of CoO-P2O3- Amine-H2O, five new compounds were acquired. Among them, four are cobalt phosphites, and the other one is a cobalt pyrophosphate. The four cobalt phosphites are with zero-, one-, two- and three-dimensional structures, respectively. The imidazole is the coordination ligand of the zero-dimensional complex. The DACH is the organic cation of the one-dimensional chain structure. The ammonium is functioned as the interlayered cations of the two-dimensional layer structure. The three-dimensional cobalt phosphite is pillared with the PYZ ligand. The cobalt pyrophosphate belongs to a two-dimensional structure.

參考文獻


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被引用紀錄


吳韋昌(2007)。有機/無機複合鋅磷酸亞磷酸鹽的水熱合成、晶體結構與性質研究〔碩士論文,國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-1411200715124448

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