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表面化学对含氧烃在活性炭上吸附的影响。

Influence of surface chemistry on the adsorption of oxygenated hydrocarbons on activated carbons.

机构信息

Institut de Science des Matériaux de Mulhouse, (CNRS LRC 7228), 15 rue Jean Starcky, 68057 Mulhouse, France.

出版信息

Langmuir. 2010 Dec 21;26(24):18824-33. doi: 10.1021/la103405j. Epub 2010 Nov 30.

DOI:10.1021/la103405j
PMID:21117633
Abstract

The objective of this work was to study the adsorption of different oxygenated hydrocarbons (methanol, ethanol, 1 and 2-butanol, methyl acetate) on activated carbons from organic mixtures with cyclohexane. Three activated carbons prepared by thermal and chemical treatments of a commercial carbon were employed for this purpose. Their textural properties were found to be similar, whereas their surface chemistries were modified, as shown by temperature-programmed desorption coupled to mass spectrometry (TPD-MS) and X-ray photoelectron spectroscopy (XPS). The adsorption isotherms were obtained by depletion method, and the analysis of adsorbed species was evaluated by TPD-MS to obtain new insight into the interactions between the different hydrocarbons and the carbon surface. Ethanol leads to a high-energy interaction between its hydroxyl function and the oxygenated surface groups and also to a lower energy interaction between the aliphatic part of the molecule and the carbon material. The desorption activation energy for this hydrophilic interaction is high (50 to 105 kJ/mol), and it is related to the nature of the carbon surface groups. The relative importance of these two interactions depend on the size of the alcohol/methanol is similar to ethanol, whereas butanols lead to more dispersive interactions. Methyl-acetate cannot undergo this kind of strong interaction and behaves like cyclohexane, having desorption activation energies ranging between 25 and 45 kJ/mol no matter the molecule and the carbon surface chemistry.

摘要

这项工作的目的是研究不同含氧烃(甲醇、乙醇、1-丁醇、2-丁醇、乙酸甲酯)在环己烷存在下从有机混合物中吸附到活性炭上的情况。为此,使用了通过商业碳的热和化学处理制备的三种活性炭。它们的结构性质相似,但表面化学性质不同,这通过程序升温脱附结合质谱(TPD-MS)和 X 射线光电子能谱(XPS)得到证实。通过消耗法获得吸附等温线,并通过 TPD-MS 分析吸附物种,以深入了解不同烃类与碳表面之间的相互作用。乙醇的羟基与含氧表面基团之间存在高能相互作用,分子的脂肪部分与碳材料之间也存在低能相互作用。这种亲水相互作用的解吸活化能很高(50 至 105 kJ/mol),与碳表面基团的性质有关。这两种相互作用的相对重要性取决于醇的大小;与乙醇类似,而丁醇则导致更分散的相互作用。乙酸甲酯不能发生这种强相互作用,其行为类似于环己烷,无论分子和碳表面化学如何,其解吸活化能都在 25 至 45 kJ/mol 之间。

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