| 研究生: |
張育誌 Yu-chih Chang |
|---|---|
| 論文名稱: |
矽酸與磷酸鈾之合成、晶體結構與性質研究 Synthesis,Crystal Structures and Properties of a Uranium Silicate and a Uranium 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: | 2013 |
| 畢業學年度: | 101 |
| 語文別: | 中文 |
| 論文頁數: | 99 |
| 中文關鍵詞: | 矽酸 、磷酸 、鈾 、水熱法 、晶體合成 、晶體結構 |
| 外文關鍵詞: | silicate, phosphate, uranium, hydrothermal synthesis, crystal, structure data |
| 相關次數: | 點閱:9 下載:0 |
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本 論 文 利 用 高 溫 高 壓 水 熱 法 合成一個新的鈾矽酸鹽[Na9F2][(UVO2)(UVIO2)2(Si2O7)2] (A1)及一個鈾磷酸鹽化合物Na10UIV2(PO4)6
(A2)。藉由單晶X 光繞射方法鑑定出化合物的晶體結構,以粉末X 光繞射分析儀確定樣品純度以利後續分析,再以X 光能量散佈分析、電子探測微分析和X 光光電子光譜等方式進行定性與定量之分析。
A1 結構為一新穎的五、六混價鈾矽酸鹽,結構中罕見的包含一條利用Na+ 和F- 鍵結之無限延伸的鏈狀結構。結構中的矽酸鹽形成一個 [Si2O7]的Sorosilicate 並且和UO6 利用共角的方式形成二維的層狀結構。此化合物為第一個利用高溫高壓水熱法成功合成的Salt-inclusion 結構,同時也是第一個混價的salt-inclusion 結構。
A2 為一新穎的磷酸鈾結構,具有一個連體十二面體的UO8 單元,利用共角或共邊的方式和單一的磷酸鹽進行連結,因此形成一個三維的開放式骨架。結構中具有12 員環孔道,而所有10 個陽離子都座落在孔道當中。此化合物為第一個利用高溫高壓水熱法合成得到的新鈾磷酸鹽。
A salt-inclusion mixed-valence uranium(V,VI) silicate,[Na9F2][(UVO2)(UVIO2)2(Si2O7)2](A1), and a uranium(IV) phosphate,Na10UIV2(PO4)6 (A2), was synthesized under hydrothermal condition at 585oCand 160MPa, and structurally characterized by powder and single X-raydiffraction. These compounds were further characterized by EDX, EPMA, XPS
and SHG.
Compound A1 is a novel uranium(V,VI) silicate. The structure caotains 2D sheet of uranyl sorosilicate with the composition [UO2Si2O7] which connected by U(1)VO6etragonal bipyramids to form thick layers. The Na+ cations are located at sites in the intralayer and interlayer regions. In adition to Na+ cations,the interlayer region also contains F- anions such that infinite chains with theformula FNa1/1Na4/2 are formed. The compound A1 is not only the first example of salt-inclusion metal silicate synthesized under high-temperature,high-pressure hydrothermal onditions, the first salt-inclusion mixed-valence uranium silicate, but also the first mixed-valence uranium(V,VI) silicate in the
literature.
Compound A2 is a new tetravalent uranium phosphates. The valence state of uranium was established by U 4f X-ray photoelectron spectroscopy. The structure contains UO8 snub-disphenoidal polyhedral which are linked to monophosphate tetrahedral bt vertex- and edge-sharing such that a 3D framework with 12-sided circular and rectangular channels is fromed. All ten sodium sites are situated inside the channels and are fully occupied. These are the first uranium(IV) phosphate synthesized under high-temperature, high-pressure hydrothermal condition.
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