發(fā)布時(shí)間：2018-03-26 14:37

  本文選題：金屬-有機(jī)骨架材料　切入點(diǎn)：分子模擬　出處：《北京化工大學(xué)》2015年博士論文

【摘要】：最近,多孔材料如沸石和金屬-有機(jī)骨架(Metal-Organic Framework, MOF)材料在化學(xué)工程和材料科學(xué)領(lǐng)域取得了重要發(fā)展。特別地,MOF材料具有獨(dú)特的屬性(孔尺寸可控性、結(jié)構(gòu)可設(shè)計(jì)性及化學(xué)功能化),使其在吸附分離、膜分離、催化和生物醫(yī)藥等方面受到了廣泛的關(guān)注。另外,作為實(shí)驗(yàn)研究的補(bǔ)充,分子模擬在揭示MOF材料的微觀機(jī)理、建立材料結(jié)構(gòu)-性能(構(gòu)效)關(guān)系以及材料設(shè)計(jì)等方面表現(xiàn)出了極大的優(yōu)勢(shì)。本文利用實(shí)驗(yàn)與分子模擬相結(jié)合的方法,對(duì)MOF材料在水相中有機(jī)芳香分子吸附分離及氣相吸附/膜分離中的應(yīng)用進(jìn)行了研究,主要工作如下：1、以水穩(wěn)定的MIL-68(Al)材料為例,實(shí)驗(yàn)測(cè)定了水溶液中苯胺吸附等溫線并驗(yàn)證了計(jì)算模型。進(jìn)一步,系統(tǒng)地研究了水相中苯胺在32種MOF材料中的吸附行為,并分析了MOF材料吸附苯胺的構(gòu)效關(guān)系。結(jié)果表明,在低濃度下,苯胺吸附熱和材料自由體積對(duì)苯胺吸附同時(shí)起重要作用；在高濃度下,苯胺吸附量取決于材料的自由體積。另外,本工作提出了用于苯胺回收的最佳MOF材料的設(shè)計(jì)要求,并以此計(jì)算設(shè)計(jì)了一系列高性能材料。2、由于苯胺、苯酚具有相近的分子尺寸和沸點(diǎn),有效分離苯胺／苯酚體系存在技術(shù)挑戰(zhàn)。本工作結(jié)合實(shí)驗(yàn)與分子模擬方法,研究了廢水中苯胺／苯酚在柔性MIL-53(Al)材料中吸附分離行為。結(jié)果表明,在客體分子吸附過(guò)程中骨架柔性起了很重要的作用,因此能極大強(qiáng)化苯胺／苯酚的分離。與傳統(tǒng)吸附劑相比,MIL-53(A1)具有很高的苯胺吸附容量和苯胺／苯酚分離選擇性。因此,MIL-53(A1)可以作為這一體系分離的理想吸附劑。3、以變壓吸附工藝為例,采用分子模擬方法,研究了濕度條件下112種不同類型MOF材料用于天然氣凈化的構(gòu)效關(guān)系。本工作以吸附選擇性、目標(biāo)組分工作容量和再生性為評(píng)價(jià)標(biāo)準(zhǔn),提出了濕度條件下MOF材料設(shè)計(jì)的要求,并篩選了理想的應(yīng)用材料。4、采用了一種便宜且生物可兼容的MOF材料,MIL-88B(Fe),與Matrimid(?)5218聚合物摻雜制備了MIL-88B(Fe)/Matrimid混合基質(zhì)膜用于能源氣體(H2/CH4)凈化；測(cè)試了MIL-88B(Fe)/Matrimid膜的H2/CH4單組分和等摩爾混合組份的滲透分離性能。實(shí)驗(yàn)結(jié)果表明,由于分子篩效應(yīng),MIL-88B(Fe)摻雜能強(qiáng)化混合基質(zhì)膜中H2的通量但是會(huì)阻礙CH4的傳質(zhì),因此強(qiáng)化了H2/CH4分離性能。在298 K和3 bar下,與純聚合物膜相比,含10% MIL-88B(Fe)的混合基質(zhì)膜中H2的通量和H2/CH4分離因子分別提高了16%和66%。另外,升高操作溫度能強(qiáng)化MIL-88B(Fe)/Matrimid膜的H2/CH4分離性能。5、MOF膜后改性是提高其氣體分離性能的一種有效策略。然而,目前報(bào)道的改性方法需要MOF材料具備能參與反應(yīng)的功能團(tuán),因而限制了這種方法的應(yīng)用。為此,本工作提出了一種簡(jiǎn)單的膜改性方法用于C02捕集。仿生的聚多巴胺幾乎對(duì)任何材料都具有很強(qiáng)的黏附性。并且聚多巴胺含有大量的氨基和羥基,能對(duì)CO2形成強(qiáng)的吸附作用位點(diǎn)。作為概念驗(yàn)證試驗(yàn),本工作采用聚多巴胺對(duì)典型的ZIF-8膜進(jìn)行化學(xué)修飾。實(shí)驗(yàn)結(jié)果表明,在298 K和1 bar下,修飾后的ZIF-8膜表現(xiàn)出優(yōu)異的CO2分離性能,CH4/CO2和N2/C02選擇性分別為19.0,4.56和5.91,超過(guò)了對(duì)應(yīng)的努森選擇性(4.69,1.65和1.25)。為了說(shuō)明這一方法的通用性,本工作進(jìn)一步用聚多巴胺對(duì)氧化石墨烯GO進(jìn)行修飾,制備了具有C02選擇性的GO膜。這些工作表明,聚多巴胺可以作為膜后改性一個(gè)便捷和強(qiáng)大平臺(tái)。
[Abstract]:Recently, porous materials such as zeolites and metal organic frameworks (Metal-Organic Framework, MOF) materials have made important progress in the field of chemical engineering and materials science. In particular, the MOF material has unique properties (pore size controllability, structure design and function of the chemical), in adsorption separation, membrane separation. Catalysis and biomedicine have been widely concerned. In addition, as a supplement to the experimental study, molecular simulation on the micro mechanism of MOF materials, building material structure property relationship (QSAR) and materials design has shown great advantages. This method using a combination of experimental and molecular simulation of. MOF material / organic phase adsorption and gas adsorption and separation of aromatic molecules in the aqueous phase in the application of membrane separation were studied, the main work is as follows: 1, the water stable MIL-68 (Al) materials were measured in aqueous solution In the aniline adsorption isotherm and verify the calculation model. Further, systematically studied the adsorption behavior of aniline in aqueous phase of 32 kinds of MOF materials, and analyzes the structure-activity relationship of MOF adsorption of aniline. The results showed that under low concentration of aniline, adsorption heat and material free volume also plays an important role in the adsorption of aniline in; under high concentration, the free volume of aniline adsorption depends on the material. In addition, this work proposes the design requirements for the recovery of aniline best MOF material, and calculated and designed a series of high performance materials because of.2, aniline, phenol with molecular size and close boiling point, effective separation of aniline / phenol system are technical challenges this work combined with experiment and molecular simulation method of aniline in wastewater and phenol in flexible MIL-53 (Al) adsorption behavior of materials. The results show that the guest molecules in the adsorption process of bone The flexible frame plays a very important role, it can greatly strengthen the separation of aniline / phenol. Compared with the traditional adsorbent, MIL-53 (A1) has high adsorption capacity of aniline and aniline / phenol selectivity. Therefore, MIL-53 (A1) can be used as the ideal separation adsorbent.3 in transformer the adsorption process as an example, using molecular simulation method, 112 different types of MOF materials and humidity conditions for the structure-activity relationship of purification of natural gas was studied. The adsorption selectivity of target components, work capacity and regeneration as the evaluation criteria, the MOF material design of humidity conditions, and screening of application materials.4 ideal, a cheap and bio compatible materials MOF, MIL-88B (Fe), and Matrimid (?) MIL-88B prepared 5218 polymer doped (Fe) /Matrimid mixed matrix membranes for gas purification (H2/CH4); MIL-88B (test Fe)/Matrimid鑶滅殑H2/CH4鍗曠粍鍒嗗拰絳夋懇灝?dāng)尕滃悎缁勪唤鐨勬笚椋?

本文編號(hào)：1668271