| 研究生: |
陳怡欣 Yi-Hsin Chen |
|---|---|
| 論文名稱: |
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 |
| 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: | 2015 |
| 畢業學年度: | 103 |
| 語文別: | 中文 |
| 論文頁數: | 90 |
| 中文關鍵詞: | 高溫高壓水熱法 、矽酸鈾 |
| 外文關鍵詞: | High-Temperature, High-Pressure Hydrothermal Synthesis, Uranyl Silicates |
| 相關次數: | 點閱:10 下載:0 |
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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。
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.
[1.] Macdonald, M. R.; Fieser, M. E.; Bates, J. E.; Ziller, J. W.; Furche,F.; Evans, W. J.J. Am. Chem. Soc.2013, 135, 13310.
[2.] Sansonetti, J. E.; Martin, W. C. J. Phys. Chem. Ref. Data 2005, 34, 1559.
[3.] Andrews, L.; Zhou, M.; Liang, B.; Li, J.; Bursten, B. E. J. Am.Chem. Soc.2000, 122, 11440.
[4.] Burns, P. C. Rev. Mineral. 1999, 38, 23-90.
[5.] Wang, Z.; Wang, S.; Ling, J.; Morrison, J. M.; Burns, P. C. Inorg. Chem. 2012, 51, 7185-7191.
[6.] (a) Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 5th ed; JohnWiley& Sons: New York, 1988.; (b) Ilton, E. S.; Haiduc, A.; Cahill, C. L.; Felmy,A. R. Inorg. Chem. 2005, 44, 2986.
[7.] Finch, R. J.; Murakami, T. Rev.Mineral. 1999, 38, 24.
[8.] (a) Stieff, L. R.; Stern, T. W.; Sherwood, A. M. Science 1955, 121, 608-609. (b) Speer, J. A. Rev. Mineral. Geochem. 1980, 5, 113-135.
[9.] Drew G. L.; Fein, J. B.; Burns, P. C.; Szymanowskia , J. E. S.; Conversea , J. J. Chem. Thermodynamics,2008, 40, 980-990.
[10.] Ojovan. M.; Lee. W. Metallurgical and Materials Transactions A, 2011, 42, 837
[11.] Rabenau, A. Angew. Chem. Int. Ed. 1985, 24, 1026.
[12.] 徐如人;龐文琴編著, 無機合成與製備化學(Inorganic Synthesis andPreparative Chemistry),五南圖書出版股份有限公司, 2004
[13.] Kennedy, G. C. Am. J. Sci. 1950, 248, 540.
[14.] Ladd, M. F.; Palmer, R. A. Structure Determination by X-ray Crystallography, Plenum, New York, 1994.
[15.] Burns, P. C.; Ewing, R. C.; Hawthorne, F. C. Can. Mineral. 1997, 35, 1551.
[16.] Brown, I. D.; Altermann, D. ActaCrystallogr. 1985, B41, 244.
[17.] 高憲明 中國化學會, 2004, 62, 255.
[18.] 陳振中 科儀新知民國九十五年十二月第二十八卷第三期 p.42-49
[19.] Stieff, L. R.; Stern, T. W.; Sherwood, A. M. Science 1955, 121, 608.
[20.] ActaCrystallographica, Section C: Crystal Structure Communications 1988, 44, 421-424.
[21.] (a) Lin, C.-H.; Chen, C.-S.; Shiryaev, A. A.; Zubavichus, Y. V.; Lii, K.-H. Inorg. Chem.2008, 47, 4445. (b) Nguyen, Q. B.; Chen, C.-L.; Chiang, Y.-W.; Lii, K.-H. Inorg. Chem.2012, 51, 3879.
[22.] Lin, C.-H.; Lii, K.-H. Angew. Chem., Int. Ed. 2008, 47, 8711.
[23.] Lee, C.-S.; Lin, C.-H.; Wang, S.-L.; Lii, K.-H. Angew. Chem., Int. Ed. 2010, 49, 4254.
[24.] Chen, C.-S.; Lee, S.-F.; Lii, K.-H. J. Am. Chem. Soc. 2005, 127, 12208.
[25.] Sheldrick, G. M. SAINT, Version 7.68A, University of Göttingen, Germany, 2009.
[26.] Sheldrick, G. M. SADABS, Version 2008/1, University of Göttingen, Germany, 2008.
[27.] Chang, Y.-C.; Chang, W.-J.; Boudin, S.; Lii, K.-H.Inorg. Chem.2013, 52, 7230-7235.
[28.] Hawthorne, F. C. Z. Kristallogr. 1992,201, 183-206.
[29.] Na6[(U2O3)(UO2)(Si2O7)2]·H2O: orange plate crystal, a = 10.898(3) Å, b = 14.910(3) Å, c = 11.677(2) Å, β = 99.48(4), V = 1871.5(7) Å3, and Z = 4. Liu, H.-K.; Lii, K.-H. unpublished research.
[30.] (a) Smith, D. K.; Gruner, J. W.; Lipscomb, W. N. Am. Mineral.1957, 42, 594-618. (b) Viswanathan, K.; Harnett, O. Am. Mineral. 1986, 71, 1489-1493.
[31.] Ryan, R. R.; Rosenzweig, A. Cryst. Struct. Commun.1977, 6, 611-615.
[32.] (a) Burns, P.; Can. Mineral.2001, 39, 1153-1160. (b) Plasil, J.; Fejfarova, K.; Cejka, J.; Dusek, M.; Skoda, R.; Sejkora, J. Am. Mineral.2013, 98, 718-723.
[33.] Plaisier, J. R.; Ijdo, D. J. W.; Donega, C. M.; Blasse, G. Chem. Mater. 1995, 7, 738-743.
[34.] Liebau, F. Structural Chemistry of Silicates: Structure, Bonding and Classification; Springer-Verlag: Berlin, 1985.
[35.] Santamaria-Perez, D; Vegas, A;Liebau F.Struct.Bond.2005, 118, 121–177.
[36.] Liu, H.-K.; Chang, W.-J.; Lii, K.-H. Inorg. Chem. 2011, 50, 11773-11776.
[37.] Lauren A. Borkowski; Christopher L. CahillCrystal Growth and Design 2006, 6, 2248-2259.
[38.] 高憲明CHEMISTRY(THE CHINESE CHEM. SOC., TAIPEI)2004, 62, 28-5298.
[39.] Frances V. Stohl; Deane K. Smith American Mineralogist 1981, 66, 610-625.
[40.] Lee, C.-S.; Wang, S.-L.; Chen, Y.-H.; Lii, K.-H. Inorg. Chem.2009, 48, 8357-8361.
[41.] Chen, C.-S.; Chiang, R.-K.; Kao, H.-M.; Lii, K.-H. Inorg. Chem. 2005, 44, 3914-3918.
[42.] Chen, C.-S. ; Kao, H.-M.; Lii, K.-H. Inorg. Chem. 2005, 44, 935-940.