含碳酸鈣之矽膠孔洞材料的合成與應用

Synthesis and Application of CaCO3 Contained Mesoporous Silicas

陳柏丞(Po-Chng Chen)

指導教授 ： 劉緒宗

國立臺灣大學/理學院/化學研究所/碩士(2008年)

https://doi.org/10.6342/NTU.2008.10157

摘要

本論文係利用ATRP(atom transfer radical polymerization)的方法合成出疏水端不等之雙區塊高分子聚合物EO45MAn(n = 45、65、90)，並且以此做為合成中孔洞矽膠材料的模板，經由共縮合法加入TEOS與diethyl 2-(triethoxysilyl)ethylphosphonate(DEPTES)為矽源前驅物，將亞磷酸二乙酯機團修飾於材料的表面。注意到使用模板的不同，材料的介尺度結構(mesophase)也會隨之改變，從EO45MA45的二維六角柱狀堆積(hexagonal)，轉為EO45MA65的立方結構(cubic)，最後轉變為EO45MA90的非結晶構型(disorder)，接著利用鹽酸水解亞磷酸二乙酯機團，經由31P固態光譜確認孔洞內部的修飾業已完成。同樣的，利用共縮合法合成出帶有氰基團的中孔洞材料，之後加入硫酸中水解之，經由紅外線光譜及13C固態光譜確認羧酸根已成功修飾於材料表面。

實驗的過程中也合成出矽奈米微粒(silica nanoparticle)，將上述材料加入氯化鈣水溶液置換鈣離子於其表面，反應結束後置入碳酸氫鈉水溶液，則鈣離子可以輕易的與碳酸根形成碳酸鈣沈積於材料表面，為了進行比較，利用CTAB(cetyl trimethylammonium bromide)合成出摻雜鈣金屬之中孔洞氧化矽球(mesoporous sphere)同樣作為碳酸鈣沈積之載體，在自然界中碳酸鈣是一種很好的金屬離子吸附劑，因此利用上述材料應用於銅離子的吸附，經過互相比較後沈積有碳酸鈣的材料確實大幅提升其吸附量至2~3倍，論文中並且會探討影響銅離子吸附量之因素，並互相比較其個別吸附之能力之優缺點。

關鍵字

CaCO3 : 中孔洞

並列摘要

Organo-functionalized ordered mesoporous silicas were synthesized by co-condensation of tetraethylorthosilicate (TEOS) and diethyl 2-(triethoxysilyl)ethylphosphonate or 3-cyanopropyltriethoxysilane in the presence of the di-block copolymer EO45-b-MAx (x = 45、65、90) as the surfactant. Upon extraction, the phosphonate group and cyano group were transformed into phosphonic acid and carboxylic acid respectively via a simple hydrolysis step. The morphology of these materials varies from hexagonal to cubic to disorder according to the chain length of MA. Characterization of these porous silicas were performed by powder x-ray diffraction(XRD), infrared spectrum(IR), transmission electron microscopy (TEM), solid-state NMR spectroscopy, and nitrogen adsorption/desorption studies (BET).
In order to deposit CaCO3 into the mesoporous channel, Organo group modified materials were first treated with adequate amounts of CaCl2 allowing the exchange of Ca2+ ions onto the surface, which were subsequently reacted with NaHCO3. Upon precipitation, the CaCO3 was deposited onto the surface of materials. This CaCO3 deposited silicas appeared to be a good absorbent for Cu(II) and the intake amount of ions reached to 3 mmole per gram of silica. Various CaCO3 deposited materials including Mesoporous spheres(MS),silica nanoparticles(Si-NP), as well as in situ incorporation of calcium ion were also prepared for comparison.

並列關鍵字

mesoporous

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