發(fā)布時(shí)間：2018-06-21 12:36

  本文選題：凹凸棒土 + 八羧基酞菁鐵　； 參考：《東華大學(xué)》2017年博士論文

【摘要】：近年來(lái),隨著環(huán)境保護(hù)意識(shí)、可持續(xù)發(fā)展概念的不斷深入,水資源問(wèn)題的關(guān)注度日益提高。愈來(lái)愈多的研究開(kāi)始關(guān)注如何實(shí)現(xiàn)對(duì)污水進(jìn)行環(huán)境友好型處理,實(shí)現(xiàn)對(duì)水資源的保護(hù)及循環(huán)利用。近年來(lái)隨著研究的不斷深入,越來(lái)越多的新方法層出不窮。但與此同時(shí)對(duì)于污水處理的要求也不斷提高,因此仍需不斷完善、改進(jìn)污水處理方法。本文針對(duì)染料污水處理,利用超聲共沉淀法將四氧化三鐵負(fù)載到凹凸棒土表面,制備了一系列磁性凹凸棒土基功能復(fù)合材料。這種納米復(fù)合材料具有優(yōu)異的吸附性能并且可以利用磁分離技術(shù)解決凹凸棒土的回收再利用問(wèn)題。在此基礎(chǔ)上,本文引入具有光催化氧化性的金屬酞菁衍生物,制備了磁性凹凸棒土/金屬酞菁功能復(fù)合材料,探討了該納米復(fù)合材料對(duì)染料污水的光催化降解性能。基于滿(mǎn)足對(duì)污水處理材料智能化的要求,本文研究了將多重響應(yīng)智能水凝膠體系應(yīng)用于染料污水處理,通過(guò)智能水凝膠的不同響應(yīng)性實(shí)現(xiàn)了對(duì)處理過(guò)程的智能化控制。此外,本文還研究了表面分子印跡功能復(fù)合材料對(duì)重金屬污水中特定組分的選擇識(shí)別處理性能,主要研究?jī)?nèi)容如下:(1)利用超聲共沉淀法,制備了磁性凹凸棒土(AT/Fe3O4)納米復(fù)合材料,通過(guò)紅外光譜、X射線(xiàn)粉末衍射、場(chǎng)發(fā)射掃描電鏡、比表面積以及磁滯回線(xiàn)分析對(duì)其進(jìn)行了一系列的表征。結(jié)果表明Fe3O4納米粒子能均勻分散在AT表面,形成磁性納米復(fù)合粒子,在賦予其順磁性的同時(shí)依然保留著AT本身良好的吸附性能。染料吸附性能測(cè)試結(jié)果表明,AT/Fe3O4納米復(fù)合粒子對(duì)染料具有優(yōu)異的吸附去除效果,去除率在短時(shí)間內(nèi)即可達(dá)到90%以上,其吸附過(guò)程符合二級(jí)動(dòng)力學(xué)模型。隨著pH值的增大,對(duì)于陽(yáng)離子型染料的化學(xué)吸附作用顯著提高。通過(guò)磁分離技術(shù),實(shí)現(xiàn)了對(duì)AT/Fe3O4納米粒子在水相中的分離回收。經(jīng)四次循環(huán)再利用后,其對(duì)染料的去除率依然可達(dá)60%以上。通過(guò)模擬連續(xù)化動(dòng)態(tài)吸附過(guò)程,進(jìn)一步探討了AT/Fe3O4納米復(fù)合粒子在工業(yè)化連續(xù)處理染料污水應(yīng)用中的可行性。(2)利用具有光催化氧化性的八羧基金屬酞菁鐵(FeOCAP)與磁性凹凸棒土相復(fù)合,制備了AT/Fe3O4-FeOCAP納米復(fù)合粒子,通過(guò)紅外光譜、紫外可見(jiàn)光譜、x射線(xiàn)光電子能譜以及光催化降解實(shí)驗(yàn)等對(duì)其進(jìn)行了一系列的表征與測(cè)試。結(jié)果表明feocap結(jié)構(gòu)成功地引入到了這種納米復(fù)合粒子中。通過(guò)采用at/fe3o4作為載體材料,避免了feocap平面大環(huán)結(jié)構(gòu)的聚集,從而提高了光催化活性。根據(jù)帶隙能與費(fèi)米能級(jí)計(jì)算結(jié)果可知,隨著feocap含量的增加,這種納米粒子的光催化降解活性不斷增加。所制備的納米復(fù)合材料對(duì)rhb染料分子具有優(yōu)異的光催化降解作用,避免了傳統(tǒng)吸附材料的最大飽和吸附量以及復(fù)雜的再生過(guò)程,符合langmuir-hinshelwood動(dòng)力學(xué)模型。(3)利用具有溫度、ph值以及磁場(chǎng)響應(yīng)性的磁性凹凸棒土基聚乙二醇(pmoa-at/fe3o4)多重響應(yīng)智能凝膠體系,實(shí)現(xiàn)了對(duì)染料污水處理的智能化要求,通過(guò)染料吸附測(cè)試對(duì)其性能進(jìn)行了一系列的分析。結(jié)果表明pmoa-at/fe3o4多重響應(yīng)智能凝膠對(duì)染料具有良好的去除效果,符合準(zhǔn)二級(jí)吸附動(dòng)力學(xué)模型以及l(fā)angmuir等溫吸附模型,因而吸附過(guò)程傾向于復(fù)雜非均質(zhì)體系吸附。通過(guò)改變外界環(huán)境,使得智能凝膠結(jié)構(gòu)產(chǎn)生不同的響應(yīng),對(duì)染料污水表現(xiàn)出了不同的去除效果,實(shí)現(xiàn)對(duì)染料處理過(guò)程的智能化控制。進(jìn)一步利用凝膠的這種智能響應(yīng)性,可以通過(guò)簡(jiǎn)單操作實(shí)現(xiàn)對(duì)該凝膠吸附材料重復(fù)再生處理,重復(fù)循環(huán)再生4次之后,對(duì)染料污水仍具有較好的處理效果。(4)利用具有優(yōu)異光催化性能的at/fe3o4-feocap納米粒子,進(jìn)一步設(shè)計(jì)制備了具有光催化降解性的feocap/mat-pmoa多重響應(yīng)智能凝膠,通過(guò)紅外光譜等對(duì)其結(jié)構(gòu)進(jìn)行了表征。結(jié)果表明,該多重響應(yīng)智能凝膠體系中存在有氫鍵作用力,因此避免了at/fe3o4-feocap納米粒子在凝膠網(wǎng)絡(luò)中的相分離,提高了光催化活性。光催化降解性能測(cè)試結(jié)果表明,feocap/mat-pmoa多重響應(yīng)智能凝膠對(duì)染料污水的去除率接近100%,依然符合langmuir-hinshelwood動(dòng)力學(xué)模型。重復(fù)循環(huán)測(cè)試結(jié)果表明,水凝膠網(wǎng)絡(luò)結(jié)構(gòu)的引入,顯著增加了金屬酞菁的穩(wěn)定性,避免了其向溶液中的遷移,重復(fù)再生五次后,對(duì)染料的去除效率依然可以接近100%,且溶液呈無(wú)色狀,沒(méi)有任何金屬酞菁擴(kuò)散的痕跡。隨著外界環(huán)境的改變,feocap/mat-pmoa復(fù)合凝膠依舊能產(chǎn)生多種智能響應(yīng)性,表現(xiàn)出了不同的染料處理效果。(5)以磁性凹凸棒土為基體,cu2+為模板,利用表面分子印跡技術(shù),制備了具有ph值智能響應(yīng)性的cu(ii)分子印跡智能凝膠,應(yīng)用于對(duì)重金屬污水中特定離子的選擇識(shí)別處理。紅外光譜測(cè)試結(jié)果表明,通過(guò)1.0M HNO3溶液洗脫,可以成功地將印跡模板洗脫,留下印跡位點(diǎn)用于后續(xù)的選擇識(shí)別過(guò)程。該分子印跡凝膠對(duì)模板Cu2+具有優(yōu)異的選擇識(shí)別性能,整個(gè)吸附過(guò)程符合Freundlich等溫吸附模型。經(jīng)5次重復(fù)再生循環(huán)測(cè)試后,依然對(duì)Cu2+具有優(yōu)異的吸附性能,同時(shí)保留良好的選擇識(shí)別性能。隨pH值的變化,該印跡凝膠可以對(duì)Cu2+表現(xiàn)出不同的選擇識(shí)別性。
[Abstract]:In recent years, with the awareness of environmental protection and the continuous development of the concept of sustainable development, the attention of water resources is increasing. More and more studies have begun to pay attention to how to realize environmental friendly treatment of sewage and realize the protection and recycling of water resources. In recent years, more and more new methods have been developed with the deepening of research. But at the same time, the demand for sewage treatment is increasing, so it is still necessary to improve and improve the method of sewage treatment. In this paper, a series of magnetic attapulgite based functional composite materials are prepared by using the method of ultrasonic coprecipitation to prepare a series of magnetic attapulgite based functional composite. The material has excellent adsorption properties and can use magnetic separation technology to solve the recycling and reuse of attapulgite. On this basis, this paper introduces a metallic phthalocyanine derivative with photocatalytic oxidation, and the magnetic Palygorskite / metal phthalocyanine composite material is prepared, and the photocatalytic reaction of the nano composite to dye wastewater is discussed. Based on the requirements for the intellectualization of the sewage treatment materials, this paper studies the application of the multi response intelligent hydrogel system to the treatment of dyestuff wastewater, and realizes the intelligent control of the treatment process through the different responsiveness of the intelligent hydrogel. In addition, this paper also studied the heavy gold of the surface molecularly imprinted functional composite. The main research contents are as follows: (1) magnetic attapulgite (AT/Fe3O4) nanocomposites were prepared by ultrasonic co precipitation method, and a series of characterizations were carried out by infrared spectroscopy, X ray powder diffraction, field emission scanning electron microscopy, surface product and hysteresis loop analysis. It is shown that the Fe3O4 nanoparticles can be dispersed evenly on the surface of AT to form magnetic nanocomposite particles, which still retain the good adsorption properties of AT itself while giving it paramagnetic. The results of the dye adsorption performance test show that the AT/Fe3O4 nanocomposite particles have excellent adsorption and removal effect on the dye, and the removal rate can reach 9 in a short time. More than 0%, the adsorption process conforms to the two stage kinetic model. With the increase of pH value, the chemical adsorption of cationic dyes is significantly improved. The separation and recovery of AT/Fe3O4 nanoparticles in the aqueous phase is realized by magnetic separation technology. After four cycles, the removal rate of dyes can still be over 60%. The feasibility of continuous dynamic adsorption of AT/Fe3O4 nanocomposite particles in the industrial continuous treatment of dyestuff wastewater was further discussed. (2) the composite of eight carboxyl metal phthalocyanine (FeOCAP) with photocatalytic oxidation and magnetic attapulgite was prepared. The AT/ Fe3O4-FeOCAP nanocomposite particles were prepared by infrared spectroscopy and ultraviolet. The visible spectra, the X ray photoelectron spectroscopy and the photocatalytic degradation experiment have been characterized and tested. The results show that the feocap structure has been successfully introduced into the nanocomposite particles. By using at/fe3o4 as the carrier material, the aggregation of the large ring structure in the feocap plane is avoided and the photocatalytic activity is improved. According to the results of band gap energy and Fermi energy level calculation, with the increase of feocap content, the photocatalytic degradation activity of the nanoparticles is increasing. The prepared nanocomposites have excellent photocatalytic degradation of the RHB dye molecules, avoiding the maximum saturated adsorption capacity of the traditional adsorbents and the complex regeneration process. Langmuir-Hinshelwood dynamic model. (3) using the multi response intelligent gel system with magnetic palygorskite (pmoa-at/fe3o4) with temperature, pH and magnetic field responsiveness, the intelligent requirement for the treatment of dyestuff wastewater is realized. The performance of the dye adsorption test is analyzed by a series of dye adsorption tests. The results show that pmoa-at/ The Fe3O4 multi response intelligent gel has a good removal effect on the dye, which conforms to the quasi two stage adsorption kinetic model and the Langmuir isothermal adsorption model. Therefore, the adsorption process is inclined to the adsorption of complex heterogeneous systems. By changing the environment, the intelligent gel structure has a different response, and the dye sewage is different. The intelligent control of the dye treatment process is realized by removing the effect. Further using this intelligent responsiveness of the gel, the gel adsorption material can be regenerated by a simple operation. After repeated recycling for 4 times, the dye sewage still has a good treatment effect. (4) using at/fe3o with excellent photocatalytic performance. 4-feocap nanoparticles were further designed and prepared for the photocatalytic degradation of feocap/mat-pmoa multiple response intelligent gel. The structure was characterized by infrared spectroscopy. The results showed that the hydrogen bond force existed in the multi response intelligent gel system, thus avoiding the at/fe3o4-feocap nanoparticles in the gel network. The photocatalytic activity was enhanced by phase separation. The results of photocatalytic degradation test showed that the removal rate of feocap/mat-pmoa multiple response intelligent gel was close to 100% and still conformed to the Langmuir-Hinshelwood kinetic model. The results of repeated cycle test showed that the structure of hydrogel network increased the stability of metal phthalocyanine significantly. After five times of repeated regeneration, the removal efficiency of the dye can still be close to 100%, and the solution is colorless, and there is no trace of any metal phthalocyanine diffusion. With the change of the environment, the feocap/mat-pmoa composite gel can still produce many kinds of intelligent responsiveness, showing different dye treatment effects. (5) using magnetic palygorskite as the matrix and cu2+ as a template, the Cu (II) molecularly imprinted intelligent gel with pH value intelligent responsiveness is prepared by surface molecularly imprinted technique. It is applied to the selection recognition of specific ions in heavy metal sewage. The infrared spectrum test results show that the imprinting can be successfully carried out through 1.0M HNO3 solution elution. Template elution and left imprinting loci are used for the subsequent selection recognition process. The molecularly imprinted gel has excellent selection recognition performance for template Cu2+, and the whole adsorption process conforms to the Freundlich isothermal adsorption model. After 5 repeated recycling tests, the molecular imprinting gel still has excellent adsorption properties for Cu2+, while preserving good selection recognition With the change of pH value, the imprinted gel can show different selective recognition to Cu2+.
【學(xué)位授予單位】：東華大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TB33;X703

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