含有機模板的錫鍺酸鹽與錫矽酸鹽之合成與其結構鑑定

Synthesis and Structural Characterization of an Organically Templated Stannogermanate and a Stannosilicate: (C4H12N2)3[Sn3Ge6O18F6]·4H2O and Na8SnSi6O18

薛覲(Jin Syue)

指導教授 ： 李光華

國立中央大學/理學院/化學系/碩士(2012年)

摘要

本論文旨在研究含有有機模板的錫鍺酸鹽以及純無機錫矽酸鹽之合成與其結構特性。錫鍺酸鹽(C4H12N2)3[Sn3Ge6O18F6]•4(H2O) (A1) 係以溶劑熱法合成，以質子化的哌嗪 (piperazine, C4H12N2) 做為結構引導試劑，是類沸石結構發展以來，第一個結構中含有有機胺陽離子的錫鍺酸鹽；錫矽酸鹽Na8SnSi6O18 (B1) 則是在高溫高壓水熱狀態下合成，結構具有良好的熱穩定性。研究中所有的晶體皆以單晶X-光繞射儀 (SXRD) 鑑定結構，並且藉由調整實驗參數得到單一相的化合物，以粉末X-光繞射儀 (PXRD) 確定其為純相後，利用熱重分析及變溫粉末繞射實驗研究其結構的熱穩定性，以固態核磁共振光譜的資訊來佐證 SXRD 所得的結構組成。
A1結構中鍺酸鹽的六員環藉由SnIVF2O4八面體以共角的方式連結彼此，形成三維的交錯式孔道結構，分別在結構中a-軸及b-軸方向存在有二維的十員環孔道，孔徑最大值分別為8.76 Å和7.33 Å。質子化的哌嗪及水分子則坐落在結構孔道中。 B1 結構則是以SnIVO6八面體以共角的方式連接矽酸鹽的六員環所形成的三維結構。

關鍵字

孔洞材料 ； 水熱法 ； 溶劑熱法 ； 有機模板 ； 錫鍺(矽)酸鹽

並列摘要

This thesis reports the synthesis and structural characterization of an organically templated stannogermanate and a stannosilicate. The stannogermanate (C4H12N2)3 [Sn3Ge6O18F6] •4H2O (A1) was synthesized by a solvothermal method using piperazine as structure-directing agent. To our knowledge this is the first stannogermanate containing an organic ammonium cation. The stannosilicate Na8SnSi6O18 (B1) was synthesized under high-temperature, high-pressure hydrothermal conditions. Both structures were characterized by single-crystal X-ray diffraction. Single phase products were obtained as indicated by powder X-ray diffraction. The thermal stability was studied by thermogravimetric analysis and variable-temperature powder diffraction. Solid state NMR spectroscopy was also performed to further characterize the compounds.
The structure of A1 consists of 6-membered germanate rings linked via corner-sharing by SnIVF2O4 octahedra to form a 3-D framework with 10-ring channels parallel to the a-axis and b-axis, where the protonated piperazinium cations and H2O molecules are located. The structure of B1 consists of 6-membered silicate rings linked via corner-sharing by SnIVO6 octahedra to form a 3-D framework.

並列關鍵字

stannogermanates(silicates) ； organically templated ； solvothermal ； hydrothermal ； porous materials

參考文獻

1. Kitagawa, S.; Kitaura, R.; Noro, S. I., Angew.Chem.Int.Ed. 2004, 43, 2334.

2. Cheetham, A. K.; Férey, G.; Loiseau, T., Angew. Chem., Int. Ed. 1999, 38, 3268.

3. Claire-Deville, H. C. R., Acad. Sci. 1862, 54, 324.

4. Wang, X.; Jacobson, A. J., Chem. Commun. 1999, 973.

5. Davis, M. E., Nature. 2002, 417, 813.