金属—有机骨架材料MIL-101对典型挥发性有机物（VOCs）的吸附性能及机理
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摘要
苯系物、醛酮等典型挥发性有机物(VOCs)可以造成严重的环境污染,并对人体健康产生巨大危害。金属有机骨架材料MIL-101具有超高比表面积以及巨大的孔体积,在气体吸附方面具有很大的应用潜力。本文在合成具有超高表面积和孔体积的MIL-101及测定其对典型VOCs的吸附等温线的基础上,研究了MIL-101对VOCs的吸附性能机理及水蒸气和甲苯对苯的竞争吸附。研究结果为金属有机骨架材料MIL-101吸附净化VOCs提供理论依据和技术支持。论文取得了一些有价值的成果：
(1)MIL-101对丙酮及苯系物优秀的吸附性能,且丙酮及苯系物的饱和吸附体积与VOCs的分子横截面积之间存在负线性相关性。同时发现,MIL-101对进入其孔隙的VOCs分子的尺寸和形状具有选择性：丙酮、苯、甲苯、乙苯及对二甲苯以尺寸最小截面方式进入材料孔隙。间二甲苯和邻二甲苯以尺寸最大截面方式进入材料孔隙。二甲苯中甲基的排列方式及其空间位阻效应是决定它们进入MIL-101孔隙的重要因素。
(2)水蒸气与苯在MIL-101上发生竞争吸附,导致苯在MIL-101上的吸附量随着相对湿度的增加而减小。在90%高湿度时,MIL-101对苯的吸附量保持在655 mg/g,是其在零湿度时饱和吸附量的68.6%,表明MIL-101在高湿度下仍能有效吸附净化VOCs。
(3)苯与甲苯在MIL-101上发生竞争吸附,导致苯在MIL-101上的吸附量随着甲苯相对压力的增加而减小。二者的竞争吸附行为符合理想溶液吸附理论。在低相对压力时,苯和甲苯的互溶作用会影响理想溶液吸附理论拟合的准确度。
Volatile organic compounds (VOCs) existed in ambient environment may bring on serious environmental and health risks including photochemistry smog. Metal-organic frameworks (MOFs) MIL-101 with extremely large pore volume and high surface area, is a highly potential candidate as adsorbent on gas adsorption. Therefore, the excellent MIL-101 was hydrothermally synthesized in this paper to examine its adsorption performance for VOCs and the influences of molecular properties such as size and shape of VOCs. Meanwhile, the influences of competition adsorption of water vapor and toluene towards benzene on MIL-101 was also investigated. All studies in this paper was aimed to provide some theoretical basis and technical support for the sorption and removal of VOCs contamination. The main results are as follows:
1. MIL-101 shows superior adsorption capacity for acetone and BTEX. Adsorption of VOCs on MIL-101 is captured by a pore filling mechanism, showing the size and shape selectivity of VOC molecules into MIL-101 pores. These proves to be a negative linear relationship between the volume adsorption capacity of VOCs and their molecular cross-sectional area. Mostly, VOC molecules, such as acetone, benzene, toluene, ethylbenzene and p-xylene, enter into MIL-101 pores with the plane having the minimum diameter. However, m-xylene and o-xylene enter into the MIL-101pores with the plane having the maximum diameter because the two methyl groups, existing in o-xylene and m-xylene with an angle, blocked the pores with diameters smaller than their lengths.
2. Competition of benzene by water molecules was observed on the surface of MIL-101, which lead to the decreasing of benzene adsorption capacity on MIL-101 with the increasing of relative humidity. At a relative humidity of 90%, adsorption capacity of benzene on MIL-101 is of 655 mg/g (68.6% of the benzene adsorption capacity on MIL-101 without water molecules), which implies that MIL-101 is a excenlent adsorbent in the application of VOC removal at relatively high humidity.
3. Competition between benzene and toluene was also observed when they adsorbed onto MIL-101 simultaneously, showing that adsorption of benzene on MIL-101 decreased with the increasing of toluene concentrations. This competitive behavior can be well described by the ideal adsorption solution theory. In addition, mutually dissolved interaction between benzene and toluene both at relatively low concentrations may occur and result in the deviation of the prediction of the ideal adsorption solution theory from the experimental data.
(1)MIL-101对丙酮及苯系物优秀的吸附性能,且丙酮及苯系物的饱和吸附体积与VOCs的分子横截面积之间存在负线性相关性。同时发现,MIL-101对进入其孔隙的VOCs分子的尺寸和形状具有选择性：丙酮、苯、甲苯、乙苯及对二甲苯以尺寸最小截面方式进入材料孔隙。间二甲苯和邻二甲苯以尺寸最大截面方式进入材料孔隙。二甲苯中甲基的排列方式及其空间位阻效应是决定它们进入MIL-101孔隙的重要因素。
(2)水蒸气与苯在MIL-101上发生竞争吸附,导致苯在MIL-101上的吸附量随着相对湿度的增加而减小。在90%高湿度时,MIL-101对苯的吸附量保持在655 mg/g,是其在零湿度时饱和吸附量的68.6%,表明MIL-101在高湿度下仍能有效吸附净化VOCs。
(3)苯与甲苯在MIL-101上发生竞争吸附,导致苯在MIL-101上的吸附量随着甲苯相对压力的增加而减小。二者的竞争吸附行为符合理想溶液吸附理论。在低相对压力时,苯和甲苯的互溶作用会影响理想溶液吸附理论拟合的准确度。
Volatile organic compounds (VOCs) existed in ambient environment may bring on serious environmental and health risks including photochemistry smog. Metal-organic frameworks (MOFs) MIL-101 with extremely large pore volume and high surface area, is a highly potential candidate as adsorbent on gas adsorption. Therefore, the excellent MIL-101 was hydrothermally synthesized in this paper to examine its adsorption performance for VOCs and the influences of molecular properties such as size and shape of VOCs. Meanwhile, the influences of competition adsorption of water vapor and toluene towards benzene on MIL-101 was also investigated. All studies in this paper was aimed to provide some theoretical basis and technical support for the sorption and removal of VOCs contamination. The main results are as follows:
1. MIL-101 shows superior adsorption capacity for acetone and BTEX. Adsorption of VOCs on MIL-101 is captured by a pore filling mechanism, showing the size and shape selectivity of VOC molecules into MIL-101 pores. These proves to be a negative linear relationship between the volume adsorption capacity of VOCs and their molecular cross-sectional area. Mostly, VOC molecules, such as acetone, benzene, toluene, ethylbenzene and p-xylene, enter into MIL-101 pores with the plane having the minimum diameter. However, m-xylene and o-xylene enter into the MIL-101pores with the plane having the maximum diameter because the two methyl groups, existing in o-xylene and m-xylene with an angle, blocked the pores with diameters smaller than their lengths.
2. Competition of benzene by water molecules was observed on the surface of MIL-101, which lead to the decreasing of benzene adsorption capacity on MIL-101 with the increasing of relative humidity. At a relative humidity of 90%, adsorption capacity of benzene on MIL-101 is of 655 mg/g (68.6% of the benzene adsorption capacity on MIL-101 without water molecules), which implies that MIL-101 is a excenlent adsorbent in the application of VOC removal at relatively high humidity.
3. Competition between benzene and toluene was also observed when they adsorbed onto MIL-101 simultaneously, showing that adsorption of benzene on MIL-101 decreased with the increasing of toluene concentrations. This competitive behavior can be well described by the ideal adsorption solution theory. In addition, mutually dissolved interaction between benzene and toluene both at relatively low concentrations may occur and result in the deviation of the prediction of the ideal adsorption solution theory from the experimental data.
引文
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