含胺官能基奈米孔洞碳材及含R2(dabco)官能基SBA-15的合成、鑑定及陰離子交換的研究

Synthesis, characterization and aion-exchange study of SBA-15 tethered with R2(dabco) and nanoporous carbon with amines

賴中一(Chung-Yi Lai)

指導教授 ： 鄭吉豐

中原大學/理學院/化學研究所/碩士(2014年)

https://doi.org/10.6840/cycu201400967

摘要

製備具有高表面積之規則排列中孔洞碳材OMC，並以OMC當作載體，透過表面改質方式將含N的多胺類螯合物導入中孔洞碳材並對於重金屬六價鉻鉻酸鹽的吸附能力進行探討，結果顯示中孔洞碳材經過表面改質後對於Cr(VI)的吸附具有明顯的吸附能力，為了探討pH值對於重金屬Cr(VI)吸附的影響，嘗試改變pH值範圍3-8，多胺類表面改質中孔洞碳材至少要達到pH 4才能完全顯現出重金屬Cr(VI)的吸附能力，因此，pH值在重金屬Cr(VI)的吸附應用上扮演著舉足輕重的角色。在重金屬Cr(VI)最高吸附量方面，改變不同含N數多胺類表面改質中孔洞碳材最高吸附量可高達185 mg/g。
於一鍋反應中以共縮合法成功直接鍵結不同含量矽烷修飾劑於SBA-15，鍵結較高含量矽烷的產物有較高陰離子交換當量應用於HPLC靜相上，有27000到63000左右的理論板數。共縮合產物比後修飾產物具有較高陰離子交換當量。
以共縮合法合成雙邊四級胺矽烷來做六價鉻的離子吸附，吸附一分鐘，吸附量為69%至79% Cr(VI)平衡吸附量(qe)，約在30分鐘內就達到吸附平衡，如此快速的吸附行為是文獻上少見的，主要由於吸附材具有利於擴散及輸送的大奈米孔洞及高表面積，親水性等優點。在不同pH值的條件下，在pH值等於3時吸附量最大(1 kg的吸附材可以吸附157.5 g的Cr(VI))，證明雙邊四級胺矽烷具有吸附六價鉻的能力。
最後本論文嘗試將實驗數據以Langmuir和Freundlich兩種等溫吸附方程式和三種動力學模式pseudo first-order rate equation、peudo second-order rate equation及intraparticle diffusion equation進行曲線擬合，探討改質後中孔洞碳材和雙邊四級胺矽烷的吸附平衡及動力學行為。

關鍵字

中孔洞碳材 ； 動力學模式 ； 重金屬Cr(VI) ； 等溫吸附方程式 ； 共縮合法 ； 吸附

並列摘要

Ordered mesoporous carbon material with high surface area containing different kinds of multi-amine ligands was synthesized to enhance the adsorption capacity of heavy metal Cr (VI)from aqueous environment. Correlation between pH in solution and adsorption capacity was investigated. Results showed pH in solution plays an important role on Cr (VI) adsorption due to the variation of Cr (VI) species at different acidity and the optimum adsorption condition of modified mesoporous carbon is pH < 5. Given the results on different ligands, poly(ethyleneimine) ligand gave the highest absorption of 185 mg/g which can be attributed to the number of nitrogen available that can be attracted to heavy metal Cr (VI). It can be deduced that the adsorption capacity of the mesoporous carbon materials would be determined by the number of available nitrogen.
Furthermore, Langmuir and Freundlich isotherm adsorption were performed. These results shows that Cr(VI) isotherm adsorption on N-OMC is Freundlich type and the adsorption is heterogeneous. The adsorption kinetics was analyzed by three kinetic models, namely pseudo first-order, pseudo second-order and the intraparticle diffusion equations. Pseudo second-order kinetics was well fitted to the of Cr(VI) adsorption kinetics of N-OMC.
Bilateral silane-functionalized mesoporous silicas were also prepared in one pot reaction via the co-condensation of tetraethoxylsilane(TEOS) and bilateral amine silane with different ratio of X = silane/(silane + TEOS).
The anion-exchange liquid chromatography using above home-made stationary phase have higher separation efficiency with the number of theoretical plates about 27000 to 63000 compared with literature report.
Functionalized SBA-15 with bilateral aminewas also used for hexavalent chromium ion exchange. The exchange capacities of amine-SBA-15 for Cr (VI) were 157.5 mg/g. Its isotherm and kinetics of Cr(VI) adsorption were carefully studied.

並列關鍵字

isotherm adsorption ； kinetic models ； co-condensation.adsorption ； Ordered mesoporous carbon ； heavy metal Cr (VI)

參考文獻

McBain, J. W.; The Sorption of Gases and Vapours by Solids, Rutledge and Sons, London, ch. 5. 1932.

IUPAC Manual of Symbols and Terminology, Appendix 2, Part 1,

Colloid and Surface Chemistry.Pure Appl. Chem. 1972, 31, 578.

Lin, Y. C.; Chen, S. H.; Itri, R. J. Phys. Condens. Matels. 1996, 8, 12169.

Zuna, R. Colloids Surf. 1997, 27, 123.