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Cu-BTC@ZSM-5 复合材料的合成与应用作为在潮湿环境下去除甲苯气体的有效吸附剂:动力学、热力学和机理研究。

Synthesis and application of Cu-BTC@ZSM-5 composites as effective adsorbents for removal of toluene gas under moist ambience: kinetics, thermodynamics, and mechanism studies.

机构信息

College of Chemical Engineering, China University of Petroleum, Qingdao, 266580, People's Republic of China.

State Key Laboratory of Petroleum Pollution Control, Beijing, 102206, People's Republic of China.

出版信息

Environ Sci Pollut Res Int. 2020 Feb;27(6):6052-6065. doi: 10.1007/s11356-019-07293-2. Epub 2019 Dec 21.

Abstract

Metal organic frameworks (MOFs) are excellent adsorbents that provide abundant specific surface area, adjustable pore structure, and rich active sites. The purpose of this study was to prepare composites with hydrophobic and high microporous specific surface area and to adsorb toluene gas in moist ambience. An ethanol activation-assisted hydrothermal method was proposed to synthesize copper-benzene-1,3,5-tricarboxylic acid (Cu-BTC) metal-organic framework, Cu-BTC, and ZSM-5 molecular sieve composites (Cu-BTC@ZSM-5). The dynamic adsorption process of toluene on different adsorbents was investigated, and the results showed that the toluene adsorption capacity of Cu-BTC@ZSM-5 (158.6 mg/g) was 2.53 times higher than Cu-BTC (62.7 mg/g), when the ZSM-5 content is 5% and the humidity is 30%RH. Compared with other factors, the humidity inhibited the adsorption of toluene on Cu-BTC@ZSM-5. Langmuir model and the pseudo-second kinetics model can better describe the adsorption behavior of Cu-BTC@ZSM-5. The thermodynamic results showed the adsorption process was a spontaneous exothermic process at low temperature and mainly physical adsorption. The relative regenerability can still up to 80.4% after six cycles. The adsorption mechanisms of Cu-BTC@ZSM-5 were pore-filling adsorption, π-π interaction, cation-π bonding, and hydrophobic interactions. This study will help to design a systematic route to evaluate the adsorption performance of Cu-BTC@ZSM-5 for toluene.

摘要

金属有机骨架(MOFs)是一种出色的吸附剂,具有丰富的比表面积、可调节的孔结构和丰富的活性位点。本研究旨在制备具有疏水性和高微孔比表面积的复合材料,并吸附潮湿环境中的甲苯气体。提出了一种乙醇活化辅助水热法来合成铜-苯-1,3,5-三甲酸(Cu-BTC)金属有机骨架、Cu-BTC 和 ZSM-5 分子筛复合材料(Cu-BTC@ZSM-5)。研究了不同吸附剂对甲苯的动态吸附过程,结果表明,当 ZSM-5 含量为 5%且湿度为 30%RH 时,Cu-BTC@ZSM-5(158.6mg/g)对甲苯的吸附容量是 Cu-BTC(62.7mg/g)的 2.53 倍。与其他因素相比,湿度抑制了 Cu-BTC@ZSM-5 对甲苯的吸附。Langmuir 模型和准二级动力学模型可以更好地描述 Cu-BTC@ZSM-5 的吸附行为。热力学结果表明,该吸附过程在低温下是一个自发的放热过程,主要是物理吸附。经过六次循环后,相对再生率仍可达到 80.4%。Cu-BTC@ZSM-5 的吸附机制为孔填充吸附、π-π 相互作用、阳离子-π 键合和疏水性相互作用。本研究将有助于设计一种系统的路线来评估 Cu-BTC@ZSM-5 对甲苯的吸附性能。

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