本文選題：金屬-有機(jī)骨架材料 + 染料�。� 參考：《哈爾濱工業(yè)大學(xué)》2017年碩士論文

【摘要】：隨著經(jīng)濟(jì)全球化和科技的飛速發(fā)展,由染料、酚類等有機(jī)污染物造成的水污染現(xiàn)象日趨嚴(yán)峻,如何高效的去除水中污染物是生物環(huán)境領(lǐng)域中的重要課題。吸附法具有操作簡單、經(jīng)濟(jì)和可回收利用等優(yōu)點(diǎn),是高效去除水中污染物的常見方法之一。但活性炭、沸石等傳統(tǒng)多孔吸附劑的選擇性和吸附量均不理想,因此開發(fā)具有高吸附性能的多孔材料具有重要意義。金屬-有機(jī)骨架材料(Metal-organic frameworks,MOFs)是一類由有機(jī)配體和金屬中心自組裝形成的多孔性結(jié)晶材料。MOFs具有比表面積大、孔隙率高、孔徑結(jié)構(gòu)可調(diào)和金屬活性位點(diǎn)等優(yōu)點(diǎn),因此具有良好的吸附性能。MOFs在吸附去除水體有機(jī)污染物領(lǐng)域具有良好的應(yīng)用前景,并引起了人們對MOFs材料的設(shè)計(jì)開發(fā)及應(yīng)用領(lǐng)域的廣泛關(guān)注。本文制備了兩種性能優(yōu)異的氨基MOFs材料,分別應(yīng)用于對水體污染物染料和酚類的吸附,探索其在吸附過程中可能存在的機(jī)理。主要研究內(nèi)容如下:(1)利用溶劑熱法制備了NH2-MIL-101(Fe),并通過FT-IR、XRD、SEM、N2吸附-脫附測試對制得的MOFs進(jìn)行表征。將其作為吸附劑對陰離子染料剛果紅和陽離子染料孔雀石綠的吸附動力學(xué)、等溫線和熱力學(xué)進(jìn)行了研究。動力學(xué)曲線符合偽二級動力學(xué)和顆粒內(nèi)擴(kuò)散模型,表明在吸附過程中物理吸附和化學(xué)吸附共存,膜擴(kuò)散和顆粒內(nèi)擴(kuò)散共同決定反應(yīng)速率。吸附等溫線符合Langmuir吸附模型,吸附劑對剛果紅和孔雀石綠的最大吸附量分別為1386.96 mg·g-1和1164.14 mg·g-1,遠(yuǎn)高于活性炭。靜電作用、氫鍵和π-π共軛在吸附過程中起著非常重要的作用。熱力學(xué)數(shù)據(jù)分析表明該吸附過程是自發(fā)的、放熱的、熵值減小的過程。(2)利用溶劑熱法制備了NH2-UiO-66(Zr),并通過FT-IR、XRD、SEM、N2吸附-脫附測試對制得的MOFs進(jìn)行表征。研究其對氯酚化合物的吸附行為并討論吸附機(jī)理。通過測定不同濃度下的動力學(xué)曲線,并進(jìn)行偽二級動力學(xué)和顆粒內(nèi)擴(kuò)散模型的擬合分析,表明吸附過程中物理吸附與化學(xué)吸附共存,疏水作用、氫鍵作用和π-π共軛是吸附過程中的主要機(jī)理,膜擴(kuò)散和顆粒內(nèi)擴(kuò)散共同決定反應(yīng)速率。吸附等溫線符合Freundlich吸附模型,為多分子層吸附,50℃下2-氯苯酚、2,4-二氯酚和2,4,6-三氯酚的吸附容量分別為248.27 mg·g-1、372.11 mg·g-1和517.62mg·g-1。熱力學(xué)數(shù)據(jù)分析表明該吸附過程是自發(fā)的、吸熱的、熵值增加的過程。
[Abstract]:With the rapid development of economic globalization and science and technology, water pollution caused by organic pollutants such as dyes and phenols is becoming more and more serious. How to efficiently remove pollutants in water is an important issue in the field of biological environment. Adsorption method has the advantages of simple operation, economy and recyclability. It is one of the common methods to remove pollutants in water efficiently. However, the selectivity and adsorption capacity of traditional porous adsorbents such as activated carbon and zeolite are not ideal, so it is of great significance to develop porous materials with high adsorption performance. Metal-organic frameworks (MOFs) are a kind of porous crystalline materials composed of organic ligands and metal centers. MOFs have the advantages of large specific surface area, high porosity, and the pore structure can be reconciled with the active sites of metals. Therefore, MOFs have a good application prospect in the field of adsorption and removal of organic pollutants in water body, and have attracted extensive attention to the design, development and application of MOFs materials. In this paper, two kinds of amino MOFs with excellent properties were prepared, which were used to adsorb dyes and phenols, respectively, and to explore the possible mechanism in the adsorption process. The main contents of this study are as follows: (1) NH2-MIL-101 Feon was prepared by solvothermal method and characterized by FT-IRN XRDX SEMN _ 2 adsorption-desorption test. The adsorption kinetics, isotherm and thermodynamics of anion dye Congo red and cationic dye malachite green were studied. The kinetic curves are in accordance with pseudo-second-order kinetics and intra-particle diffusion model. It is shown that physical adsorption and chemical adsorption coexist in the adsorption process and the reaction rate is determined by membrane diffusion and intraparticle diffusion. The adsorption isotherm was consistent with Langmuir adsorption model. The maximum adsorption capacity of Congo red and malachite green was 1386.96 mg g ~ (-1) and 1164.14 mg g ~ (-1), respectively, which was much higher than that of activated carbon. Electrostatic interaction, hydrogen bond and 蟺-蟺 conjugation play a very important role in the adsorption process. Thermodynamic data analysis showed that the adsorption process was spontaneous, exothermic, and entropy decreased. (2) NH _ 2-UiO-66 zirconium was prepared by solvothermal method, and the MOFs were characterized by FT-IRN XRDX SEMN _ 2 adsorption-desorption test. The adsorption behavior of chlorophenol compounds and its adsorption mechanism were studied. By measuring the kinetic curves at different concentrations and fitting the pseudo-second-order kinetics and the in-particle diffusion model, it is shown that physical adsorption and chemical adsorption coexist and hydrophobicity occurs during the adsorption process. Hydrogen bonding and 蟺-蟺 conjugation are the main mechanisms in the adsorption process. Film diffusion and intraparticle diffusion jointly determine the reaction rate. The adsorption isotherm accords with the Freundlich adsorption model. The adsorption capacities of 2-chlorophenol and 2-chlorophenol at 50 鈩，

本文編號：2037720