劉緒宗臺灣大學:化學研究所陳柏丞Chen, Po-ChngPo-ChngChen2010-06-302018-07-102010-06-302018-07-102008U0001-1410200809235200http://ntur.lib.ntu.edu.tw//handle/246246/187483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。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.錄 ……………………………………………………………………………………I目錄 ………………………………………………………………………………..III目錄 ………………………………………………………………………………VI要 ………………………………………………………………………………….VIIbstract .....................................................................................................................VIII一章 緒論 …………………………………………………………………………1 1-1中孔洞材料的行成機制與簡介…………………………………………………1 1-2 中孔洞材料的修飾與應用..…………………………………………………… 1 1-3 具金屬離子吸附能力材料之簡介......………………………………………….3 1-4 具銅離子吸附能力之中孔洞材料合成與應用...................................................6-4 實驗研究目的 …………………………………………………………………11二章 兩性雙區塊共聚物的合成............…………………………………….……..12 2-1聚乙二醇甲基醚的修飾與巨起始劑的合成………………………………..….12 2-2以原子轉移自合基聚合反應合成兩性高分模板..……………………….……13三章 中孔洞材料的製備與鑑定…………………………………………………...15 3-1 合成亞磷酸二乙酯修飾之中孔洞材料...……………………………………...15 3-1-1材料結構與其物理性質之鑑定…………………………………………....15 3-1-2合成含亞磷酸根之中孔洞材料與其性質之鑑定.………………………...21 3-1-3中孔洞材料之介尺度結構變化與探討……………………………………24 3-1-4以亞磷酸修飾之中孔洞材料進行碳酸鈣的沈積...……………………….24 3-1-5碳酸鈣沈積之含亞磷酸根中孔洞材料的鑑定……………………………28 3-2 合成羧酸根修飾之中孔洞材料.....................………………………………… 30 3-2-1材料結構與其性質之鑑定…………………………………………………30 3-2-2以羧酸根修飾之中孔洞材料進行碳酸鈣沈積與鑑定……………………33 3-3 矽奈米微粒的合成………………………………………...………………...…34 3-3-1 矽奈米微粒之物理性質鑑定………………………………………...……35 3-3-2 以矽奈米微粒進行碳酸鈣的沈積與其鑑定……………………………...35-4 合成含鈣金屬離子中孔洞氧化矽與其鑑定......................................................37-4-1 合成碳酸鈣沈積之中孔洞氧化矽與其鑑定...............................................40第四章 碳酸鈣沈積之材料在銅離子吸附的應用…....………………………..…….45 4-1銅離子的吸附.......................................................………………………………45五章 結論 ………………………………………………………………………...53六章 實驗部分 …………………………………………………………………….55 6-1 測試儀器………………………………………………………………………..55 6-2 溶劑與試劑的純化……………………………………………………………..60 6-3 實驗步驟…………………………………………………….………………….61考文獻 …………………………………………………………………………….69錄.................................................................................................................................74目錄1-1 中孔洞材料在各方面的應用………………………………………………...21-2 利用架接方法修飾中孔洞材料……………………………………………...21-3 利用共縮合法修飾中孔洞材料………………………………………….…...31-4 高嶺土硫醇化的修飾過程…………………………………………………....41-5 DMSA修飾之氧化鐵奈米微粒………………………………………….…...51-6 幾丁質之去乙醯基化反應…………………………………………………...51-7 Soliman團隊對矽膠進行修飾流程…………………………………………..61-8 胺基修飾之MCM-41與Fe3+、Mn3+、Cu2+配位示意圖……………..……....71-9 利用架接法修飾胺基於SBA-15……………………………………..……...71-10 乙二胺修飾之中孔洞矽膠有機材料……………………………….……….81-11 MCM-41之擴孔途徑與選擇性萃取……………………..….……………….81-12乙烯二胺三乙酸修飾之中孔洞材料……………….……………………….91-13 MCM-EDTA之合成與銅離子的配位………...……………………………102-1 Me6-Tren結構式……………………………………………………………...143-1 Cl60 XRD與BET圖……….............................................................................163-2 Cl60 TEM圖………………………………..........................………………….163-3 DP45之XRD與BET圖..........................................................….....................173-4 DP45之TEM圖………………………………..……………….......................183-5 DP45之SEM圖……………………………………………………………….183-6 DP65之XRD與BET圖……………………………………………………...193-7 DP65之TEM圖………………………....…………………………………….193-8 DP65之SEM圖……………………………………………………………….203-9 DP90之XRD與BET圖…………….………………………………………..203-10 DP90之TEM圖...............................................................................................213-11 DP90 之SEM圖……………………………………………...........................213-12 DPx水解前後之31P固態核磁共振光譜圖………………............................223-13 DPx水解前後之13C固態核磁共振光譜圖…………………........................233-14 DPx水解前後之BET圖…………………………………......................…....233-15亞磷酸根修飾之中孔洞材料去質子化反應後之31P固態光譜圖………...243-16二氧化矽不同結構與化學位移之間相對應的關係圖…............................. 253-17亞磷酸根修飾之中孔洞材料29Si NMR光譜圖................................………263-18以亞磷酸根修飾之中孔洞材料進行碳酸鈣的沈積………………………..273-19亞磷酸根修飾之中孔洞材料碳酸鈣沈積前後BET圖……………………273-20碳酸鈣沈積之亞磷酸根中孔洞材料IR光譜圖…...................................…283-21碳酸鈣沈積之亞磷酸根中孔洞材料高角度XRD圖……………………...283-22碳酸鈣沈積於亞磷酸根修飾之中孔洞材料TGA圖.......................………293-23 CA90之XRD與BET圖................................................................................303-24 CA90之TEM圖..............................................................................................313-25氰基團修飾之中孔洞材料與其水解後之IR光譜圖..........……………….323-26氰基團修飾之中孔洞材料與其水解後之13C固態光譜圖………………..323-27碳酸鈣沈積之含羧酸根中孔洞材料IR光譜圖………………...................333-28碳酸鈣沈積之含羧酸根中孔洞材料高角度XRD圖.......................………333-29羧酸根修飾之中孔洞材料碳酸鈣沈積前後BET圖....................................343-30 碳酸鈣沈積於羧酸根修飾之中孔洞TGA圖...............................................343-31 矽奈米微粒之TEM與SEM圖....................................................................353-32 矽奈米微粒XRD與碳酸鈣沈積前後BET圖.............................................363-33 碳酸鈣沈基之矽奈米微粒高角度XRD圖...................................................363-34 碳酸鈣沈積之矽奈米微粒IR光譜圖............................................................36 3-35 碳酸鈣沈積之矽奈米微粒TGA圖................................................................373-36 MS-Ca及MS-Ca-C的IR光譜圖...................................................................383-37 MS與MS-Ca-C之XRD與BET圖...............................................................393-38 MS-Ca-C與MS之TEM圖............................................................................403-39 MS-Ca-C之SEM圖........................................................................................403-40 碳酸鈣沈積之中孔洞氧化矽球材料BET圖與其孔洞半徑分佈圖............413-41 碳酸鈣沈積之中孔洞氧化矽球材料IR光譜圖............................................423-42 碳酸鈣沈積之中孔洞氧化矽球材料高角度XRD.........................................423-43 碳酸鈣沈積之中孔洞氧化矽球之熱重分析圖..............................................434-1 碳酸鈣沈積之材料應用於銅離子的吸附........................................................474-2 材料吸脫附銅離子及Cu2CO3(OH)2之高角度XRD......................................494-3 碳酸鈣沈積之中孔洞材料脫附銅離子後高角度XRD...................................504-4材料於乙二胺處理前後之XRD圖...................................................................50 4-5 脫附銅離子後之31P固態光譜及IR光譜圖...................................................51目錄2-1 以ATRP方式合成PEO-b-PMA聚合反應成果..............................................143-1 DPx(x = 45、65、90)物理性質.............................................................................213-2 含亞磷酸二乙酯之中孔洞材料在介尺度結構上的比較………………….…243-3 PAx-Ca之磷與鈣含量..............………………...................……………………253-4 CA90之物理性質.............................................................................................. 31表3-5 MS與MS-Ca-C的物理性質..............................................……………………393-6 碳酸鈣沈積之中孔洞氧化矽球材料的物理性質.……………………………413-7 材料之碳酸鈣含量.............................................................................................444-1 銅離子的吸附................................................................................................….464-2 以不同金屬離子鉗合劑處理材料後的殘餘銅含量.............…………………484-3乙二胺於不同pH值處理材料後之殘餘銅含量...............................................4915767938 bytesapplication/pdfen-USCaCO3 : 中孔洞mesoporousthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/187483/1/ntu-97-R95223085-1.pdf