高溫高壓水熱合成矽酸鈾與結構研究

High-Temperature, High-Pressure Hydrothermal Synthesis and Structural Study of Uranyl Silicates

陳怡欣(Yi-Hsin Chen)

指導教授 ： 李光華

國立中央大學/理學院/化學系/碩士(2015年)

摘要

本論文利用高溫高壓水熱法在550℃、1400bar的狀態下，合成出三個鈾矽酸鹽化合物Na3K3[(UO2)3(Si2O7)2]·2H2O (A1)、Na3Rb3[(UO2)3(Si2O7)2](A2)和Na6Rb4[(UO2)4Si12O33] (B1)。藉由單晶X光繞射方法鑑定出化合物的晶體結構，並以粉末X光繞射分析儀確定樣品純度供後續分析，再以全反射式X光螢光光譜儀、光致發光光譜、熱重分析及固態核磁共振儀等儀器進行定性與定量分析。
A1與A2為純六價鈾矽酸鹽的等結構化合物，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層狀結構，Na+坐落在層內的八員環孔道，夾層間填入K+、H2O和Rb+，可依據valence-matching principle 來解釋A2在夾層中缺少的水分子。並將A1與文獻中結構相似的五六混價鈾矽酸鹽[Na9F2][(UVO2)(UVIO2)2(Si2O7)2]做討論。
B1為一新穎的六價鈾矽酸鹽，結構中矽氧四面體以共角方式連接形成一含有八員環孔道的unbrached dreire fourfold chain，其結構分子式可表示成{uB,41}[3Si12O33]，並與UO6利用共角的方式形成三維骨架結構。依據SiO4的配位環境分類，B1同時包含三種矽氧配位環境Q2、Q3及Q4。

關鍵字

高溫高壓水熱法 ； 矽酸鈾

並列摘要

Three new uranyl silicates, Na3K3[(UO2)3(Si2O7)2]·2H2O (A1), Na3Rb3[(UO2)3(Si2O7)2] (A2), and Na6Rb4[(UO2)4Si12O33] (B1), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 oC and 1440 bar. The crystal structures were determined by single-crystal X-ray diffraction. The purity of each compound was confirmed by powder X-ray diffraction. These compounds were further characterized by TXRF, PL, TGA and solid state NMR spectroscopy.
A1 and A2 are isostructural and contain layers of uranyl disilicate.The smaller cation, Na+, is located in the intralayer channels, whereas the larger cations, K+ and Rb+, and water molecule are located in the interlayer region.The absence of lattice water in A2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate,[Na9F2][(UVO2)(UVIO2)2(Si2O7)2].
B1 adopts a three-dimensional framework structure and contains a unique unbrancheddreier fourfold chain with the structural formula {uB,41}[3Si12O33]. The measurement results from 29Si MAS NMR are consistent with the presence of Q2, Q3, and Q4 Si in the structure.

並列關鍵字

High-Temperature, High-Pressure Hydrothermal Synthesis ； Uranyl Silicates

參考文獻

[17.] 高憲明 中國化學會, 2004, 62, 255.

[2.] Sansonetti, J. E.; Martin, W. C. J. Phys. Chem. Ref. Data 2005, 34, 1559.

[4.] Burns, P. C. Rev. Mineral. 1999, 38, 23-90.

[11.] Rabenau, A. Angew. Chem. Int. Ed. 1985, 24, 1026.

[13.] Kennedy, G. C. Am. J. Sci. 1950, 248, 540.