Selective Adsorption of n-Alkanes from n-Octane on Metal-Organic Frameworks: Length Selectivity.

The liquid-phase adsorption of n-alkanes (from n-octane (C8) solvent) with different chain lengths was carried out over three metal-organic frameworks (MOFs), viz., metal-azolate framework-6 (MAF-6), copper-benzenetricarboxylate (Cu-BTC), and iron-benzenetricarboxylate (MIL-100(Fe)), and a conventional adsorbent activated carbon (AC). MAF-6 and Cu-BTC were found to have significant selectivity for the adsorption of n-dodecane (C12) and n-heptane (C7), respectively, from C8. Selectivity for C12 on MAF-6 was also observed in competitive adsorption from binary adsorbate systems. To understand the selective adsorption of C12 on MAF-6 more, the adsorption of C12 from C8 over MAF-6 was investigated in detail and compared with that over AC. The obtained selectivities over MAF-6 and Cu-BTC for C12 and C7, respectively, might be explained by the similarity between cavity size of adsorbents and molecular length of n-alkanes. In the case of AC and MIL-100(Fe), no specific adsorption selectivity was observed because the cavity sizes of the two adsorbents are larger than the size of the n-alkanes used in this study. The adsorption capacities (qt) of n-alkanes over AC and MIL-100(Fe) decreased and increased, respectively, as the polarity (or length) of the adsorbates increased, probably because of nonpolar and polar interactions between the adsorbents and n-alkanes. On the basis of the results obtained, it can be concluded that matching the cavity size (of adsorbents) with the molecular length (of n-alknaes) is more important parameter than the MOF's hydrophilicity/hydrophobicity for the selective adsorption/separation of alkanes.