【摘要】：介孔材料由于比表面積大、傳質(zhì)快、吸附容量高等特點,現(xiàn)已被廣泛應(yīng)用于吸附領(lǐng)域,特別是硅基介孔材料,因其表面負載豐富的硅醇基,為進一步功能化提供了便利。目前,基于介孔硅表面制備對目標(biāo)物具有靶向識別能力的表面印跡聚合物已成為當(dāng)下吸附領(lǐng)域研究的熱點。近幾年,大量的重金屬污染物隨工業(yè)廢水已被排放到環(huán)境中,對人體和生物體構(gòu)成了嚴(yán)重威脅。開發(fā)新型具有吸附容量大、選擇性強、再生性能優(yōu)良等特性的表面離子印跡聚合物,來去除水體中的重金屬污染物已迫在眉睫。本課題分別以不同結(jié)構(gòu)的介孔硅作為基質(zhì)材料,選擇Pb(II)、Cr(VI)、Cu(II)為模板離子,合成了三種新型表面離子印跡聚合物,并探討了其在重金屬離子選擇性分離中的應(yīng)用,其研究內(nèi)容和實驗所得結(jié)果如下:(1)分別以3-(γ-氨基乙氨基)-丙基-三甲氧基硅烷(AAPTS)和3-氨丙基三乙氧基硅烷(APTES)作為功能單體,制備了兩種對鉛離子具有高效選擇性的介孔硅吸附劑Pb(II)-IMS-NN和Pb(II)-IMS-N。制備的吸附劑通過傅里葉轉(zhuǎn)換紅外光譜(FT-IR)、X射線光電能譜儀(XPS)、透射電子顯微鏡(TEM)、掃描電子顯微鏡(SEM)、熱重分析(TGA)、N2吸附-脫附實驗等表征分析。數(shù)據(jù)表明Pb(II)-IMS具有高度有序的介孔結(jié)構(gòu)和良好的熱穩(wěn)定性。在一系列的靜態(tài)和動態(tài)吸附實驗中,Pb(II)-IMS-NN比Pb(II)-IMS-N呈現(xiàn)更高的飽和吸附容量,并隨后將其應(yīng)用于一系列不同條件下的固定床吸附實驗中。實驗結(jié)果顯示,固定床穿透時間隨著床高的增加而增加,但隨著流速和流入Pb(II)濃度的增加而降低,而且Thomas模型比Adams-Bohart模型更加適合描述動態(tài)吸附實驗數(shù)據(jù)。此外,Pb(II)-IMS-NN比Pb(II)-IMS-N對Pb(II)呈現(xiàn)更優(yōu)異的選擇性和更高的親和力。(2)以γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)修飾的SBA-15作為基質(zhì)材料,利用甲基丙烯酸(MAA)和4-乙烯基吡啶(4-VP)雙功能單體協(xié)同作用的預(yù)聚合體系,開發(fā)了一種新型的Cr(VI)陰離子表面印跡聚合物(Cr(VI)-IIP)。一系列的表征(FT-IR、EDS、SEM、TEM、小角XRD、N2吸附-脫附分析、TGA)表明表面Cr(VI)印跡聚合物被成功制備以及在印跡聚合后材料仍保持了較規(guī)整的介孔結(jié)構(gòu)。靜態(tài)吸附實驗表明,Cr(VI)-IIP在溶液pH=2.0,溫度為25 oC的條件下呈現(xiàn)最佳的吸附性能,其飽和吸附容量為96.32 mg g-1。動力學(xué)和熱力學(xué)分析表明,Cr(VI)-IIP對Cr(VI)的吸附分別符合準(zhǔn)二階動力學(xué)模型和Langmuir等溫吸附模型。在選擇性吸附實驗中,Cr(VI)-IIP對Cr(VI)陰離子較其他競爭離子(Cr(III)、Cu(II)、Cd(II)、Ni(II))呈現(xiàn)極強的選擇性識別能力。在固定床實驗中,Cr(VI)-IIP對Cr(VI)陰離子呈現(xiàn)理想的動態(tài)吸附性能以及高效的再生能力。(3)我們以一種磁性介孔硅納米微球(γ-Fe2O3@meso-SiO2)作為基質(zhì)材料,采用于核殼型納米顆粒表面引發(fā)RAFT聚合的方式,開發(fā)了一種新型的表面Cu(II)印跡聚合物,RAFT-IIP。由于RAFT聚合活性、可控的特點,RAFT-IIP比通過傳統(tǒng)自由基聚合制備的離子印跡聚合物(TP-IIP)呈現(xiàn)更規(guī)則的形貌、更好的單分散性和更強的磁響應(yīng)性。而且,在靜態(tài)飽和吸附實驗中,RAFT-IIP比TP-IIP呈現(xiàn)更高的吸附容量,分別為210.29 mg g-1和144.84 mg g-1。隨后,一系列的吸附實驗系統(tǒng)地研究了制備的RAFT-IIP的吸附性能。數(shù)據(jù)表明,RAFT-IIP具有較強的選擇性吸附能力、良好的重復(fù)利用性、理想的動態(tài)吸附性能,可以作為去除實際水樣中Cu(II)的理想的吸附劑。
[Abstract]:Mesoporous materials have been widely used in the adsorption field due to their large specific surface area, fast mass transfer and high adsorption capacity. Especially, silicon-based mesoporous materials have been widely used in the adsorption field because of their abundant silanol-based surface loadings, which provide convenience for further functionalization. In recent years, a large number of heavy metal pollutants have been discharged into the environment along with industrial wastewater, which poses a serious threat to human beings and organisms. Three novel surface ion imprinted polymers were synthesized by using different mesoporous silica substrates, Pb (II), Cr (VI) and Cu (II) as template ions, and their applications in the selective separation of heavy metal ions were discussed. The contents of the study and the experimental results were as follows: (1) Using 3-(2-) Two mesoporous silica adsorbents Pb(II)-IMS-NN and PB(II)-IMS-N with high selectivity for lead ions were prepared by using AAPTS and 3-aminopropyl triethoxysilane (APTES) as functional monomers. Electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), N2 adsorption-desorption experiments and other characterization analysis. Data show that Pb (II) -IMS has a highly ordered mesoporous structure and good thermal stability. In a series of static and dynamic adsorption experiments, Pb (II) -IMS-NN exhibits higher saturated adsorption capacity than Pb (II) -IMS-N and exhibits higher saturated adsorption capacity than Pb (II) -IMS-N. The experimental results show that the breakthrough time increases with the increase of bed height, but decreases with the increase of flow rate and Pb (II) concentration, and Thomas model is more suitable than Adams-Bohart model for describing dynamic adsorption experimental data. NN exhibits superior selectivity and higher affinity to Pb (II) than Pb (II) - IMS - N. (2) A novel Cr (VI) negative polymerization system was developed by using MBA-modified SBA-15 as matrix material and the synergistic effect of MAA and 4-vinylpyridine (4-VP) bifunctional monomers. A series of characterizations (FT-IR, EDS, SEM, TEM, XRD, N2 adsorption-desorption analysis, TGA) showed that the surface Cr (VI) imprinted polymer was successfully prepared and the material maintained a regular mesoporous structure after imprinting polymerization. Static adsorption experiments showed that Cr (VI) IIP was in the solution pH=2.0, the temperature was 25 oC. The adsorption capacity of Cr(VI)-IIP on Cr(VI) was 96.32 mg g-1. The kinetic and thermodynamic analysis showed that the adsorption of Cr(VI)-IIP on Cr(VI) conformed to quasi-second-order kinetic model and Langmuir isothermal adsorption model, respectively. Ni (II) exhibits strong selective recognition ability. Cr (VI) - IIP exhibits ideal dynamic adsorption and high regeneration ability for Cr (VI) anion in a fixed bed experiment. (3) A magnetic mesoporous silica nanosphere (gamma-Fe2O3 @meso-SiO2) was used as a matrix material to initiate RAFT polymerization on the surface of core-shell nanoparticles. A novel surface Cu(II) imprinted polymer, RAFT-IIP, has been developed. Due to its controllable and active RAFT polymerization, RAFT-IIP exhibits more regular morphology, better monodispersity and stronger magnetic responsiveness than TP-IIP prepared by conventional free radical polymerization. Moreover, in static saturated adsorption experiments, RAFT-IIP exhibits better monodispersity and stronger magnetic responsiveness. The adsorption capacity of RAFT-IIP was 210.29 mg-1 and 144.84 mg-1 respectively, higher than that of TP-IIP. Subsequently, a series of adsorption experiments were carried out to systematically study the adsorption properties of the prepared RAFT-IIP. The ideal adsorbent for Cu (II).
【學(xué)位授予單位】：江蘇科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O631;TB383.4

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相關(guān)碩士學(xué)位論文 前1條

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本文編號：2247731