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研究生: 王郁文
Yu-Wen Wang
論文名稱: 鈾氧氫氧化物與磷酸鈾 之合成、晶體結構與性質研究
Synthesis, Crystal Structures and Properties of a Uranyl Oxyhydroxide and a Uranyl Phosphate
指導教授: 李光華
Kwang-Hwa Lii
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學學系
Department of Chemistry
論文出版年: 2014
畢業學年度: 102
語文別: 中文
論文頁數: 69
中文關鍵詞: 鈾氧氫氧化物磷酸鈾
外文關鍵詞: Uranyl Oxyhydroxide, Uranyl Phosphate
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  • 本篇論文利用高溫高壓水熱合成法合成一個六價鈾氧氫氧化物K5[U5O17(OH)] ( A1)及六價鈾磷酸鹽化合物K4[(UO2)3O2(PO4)2] (A2),利用單晶X光繞射儀鑑定出化合物的晶體結構,以粉末X光繞射儀得知樣品的純度,再以X光能量散佈分析、UV-vis吸收光譜分析、EPMA元素分析等方式來做定性與定量的分析。
    化合物A1為六價鈾氧氫氧化物,屬於單斜晶系(Monoclinic),空間群為P21/m(No. 11),結構利用兩種不同配位數的六價鈾氧單元UO6與UO7以共邊方式形成的五聚體單元串聯成長鏈,再利用共點的方式並聯形成二維的鈾氧多面體層,金屬離子K+則散布在曾與層之間和兩個不同層的氧連結。
    化合物A2為六價鈾磷酸鹽化合物,屬於單斜晶系(Monoclinic),空間群為P21/c(No. 14)。結構利用兩種不同配位數的六價鈾氧多面體UO8與UO7共邊方式形成二聚單元體串聯成長鏈,PO4四面體以並聯方式連接每一個長鏈並形成二維的層狀結構。金屬離子K+則散布在曾與層之間和兩個不同層的氧連結。


    A uranyl(VI) oxyhydrate K5[U5O17(OH)] ( A1) , and a uranyl (VI) phosphate K4[(UO2)3O2(PO4)2] (A2) , were synthesized under hydrothermal condition at 600 OC and 1650 atm , and structurally characterized by powder and single X-ray diffraction , these compounds were further characterized by EDS , EPMA , and UV-vis spectroscopy.

    Compound A1 monoclinic , P21/m(No. 11), a = 6.985(1) Å, b = 19.992(5) Å, c = 7.002(1) Å, β= 109.84°,V=919.80 Å3, Z=2, R1=0.0298, A1is a uranyl oxyhydroxide , The structure contains UO6 tetragonal bipyramids and UO7 pentagonal bipyramids to form thick layers. The K+ cations are located between the layers. The sheet anion topology, which is closely the same to that of the Na+ compound, contains chains of edge-sharing pentagons as well as dimers of corner-sharing squares.

    Compound A2 monoclinic , P21/c(No. 14), a = 6.7323(4) Å, b = 16.8465(1) Å, c = 7.0415(4) Å, β= 99.250(2)°,V=788.23(8) Å3, Z=2, R1=0.0277, A2 is a uranyl phosphate, contain dimers of edge
    -sharing UO7 pentagonal bipyramids, UO8 hexagonal bipyramids and PO4 tetrahedrals to form sheets , the sheets of uranyl phosphates which are separated by K+ cations .

    摘要 I ABSTRACT III 目錄 IV 圖目錄 VI 表目錄 X 第一章 1 緒論 1 1-1簡介 1 1-1-1鈾化合物簡介 1 1-2 論文研究動機 9 1-3 合成方法簡介 10 1-3-1 水熱法 10 1-3-2 藥品一覽表 12 1-4 鑑定方法 13 1-4-1 儀器測量簡介 13 1-4-2 單晶X光繞射與結構分析 14 1-4-3 粉末 X 光繞射分析 (PXRD) 20 1-4-4 X光能量散佈分析(EDS) 20 1-4-5 UV-Vis 吸收光譜儀(UV-Vis) 21 1-4-6元素分析EPMA 21 1-5 研究成果 22 第二章 23 高溫高壓水熱合成之六價鈾氧氫氧化物 23 2-1簡介 23 2-2實驗部分 30 2-3化合物鑑定 31 2-3-1單晶X-ray 結構解析 31 2-4結果與討論 33 2-4-1 K5[U5O17(OH)] (A1) 之結構描述 33 2-4-2 X光能量散佈分析 38 2-4-3粉末X-ray繞射分析 39 2-5結論 40 第三章 41 高溫高壓水熱合成之鈾磷酸鹽化合物 41 3-1簡介 41 3-2實驗部分 45 3-3化合物鑑定 46 3-3-1單晶X-ray 結構解析 46 3-4結果與討論 48 3-4-1 K4[(UO2)3O2(PO4)2] (A2)之結構描述 48 3-4-2粉末X-ray 繞射分析 52 3-4-3 X光能量散佈分析 53 3-4-4元素分析 54 3-4-5UV-vis光譜 55 3-5結論 56 第四章 57 總結 57 參考文獻 59

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