Pure and mixed gas adsorption of CH4 and N2 on the metal–organic framework Basolite® A100 and a novel copper-based 1,2,4-triazolyl isophthalate MOF

Pure gas adsorption isotherms of CH4 and N2 and their binary mixtures were measured at 273 K, 298 K and 323 K and up to 2 MPa on two different microporous metal–organic frameworks (MOFs), i.e. the commercially available Basolite® A100 and the recently reported copper-based triazolyl benzoate MOF 3∞[Cu(Me-4py-trz-ia)] (1). The Tòth isotherm model and the vacancy solution model were used to describe the experimentally determined isotherms and proved to be well suited for this purpose. While 1 shows a more homogeneous surface with a nearly constant isosteric heat of adsorption of 18–18.5 kJ mol−1 for CH4 and 12–15 kJ mol−1 for N2, the isosteric heat of adsorption at zero coverage for Basolite® A100 is 19 kJ mol−1 for CH4 and 16.2 kJ mol−1 for N2, decreasing significantly with increasing loading. Binary adsorption isotherms were measured gravimetrically to determine the total adsorbed mass of CH4 and N2. The van Ness method was successfully applied to calculate partial loadings from gravimetrically measured binary adsorption isotherms. Further studies by volumetric–chromatographic experiments support the good correlation between experimental data and predictions by the vacancy solution model (VSM-Wilson) and the ideal adsorbed solution theory (IAST) from pure gas isotherms. The experimental selectivities were determined to be αCH4/N2 = 4.0–5.0 for 1, slightly higher than for Basolite® A100 with αCH4/N2 = 3.4–4.5. These values are in good agreement with predictions for ideal selectivities based on Henry's law constants. From the experimental selectivities the potential of both MOFs in gas separation of CH4 from N2 can be derived.