Enhancing CH4 Capture from Coalbed Methane through Tuning van der Waals Affinity within Isoreticular Al-Based Metal–Organic Frameworks

Efficient separation of the CH₄/N₂ mixture is of great significance for coalbed methane purification. It is an effective strategy to separate this mixture by tuning the van der Waals interaction due to the nonpolar properties of CH₄ and N₂ molecules. Herein, we prepared several isoreticular Al-based metal-organic frameworks (MOFs) with different ligand sizes and polarities because of their high structural stability and low cost/toxicity feature of Al metal. Adsorption experiments indicated that the CH₄ uptake, Q_st of CH₄, and CH₄/N₂ selectivity are in the order of Al-FUM-Me (27.19 cm³(STP) g^-1, 24.06 kJ mol^-1 and 8.6) > Al-FUM (20.44 cm³(STP) g^-1, 20.60 kJ mol^-1 and 5.1) > Al-BDC (15.98 cm³(STP) g^-1, 18.81 kJ mol^-1 and 3.4) > Al-NDC (10.86 cm³(STP) g^-1, 14.89 kJ mol^-1 and 3.1) > Al-BPDC (5.90 cm³(STP) g^-1, 11.75 kJ mol^-1 and 2.2), confirming the synergetic effects of pore sizes and pore surface polarities. Exhilaratingly, the ideal adsorbed solution theory selectivity of Al-FUM-Me is higher than those of all zeolites, carbon materials, and most water-stable MOF materials (except Al-CDC and Co₃(C₄O₄)₂(OH)₂), which is comparable to MIL-160. Breakthrough results demonstrate its excellent separation performance for the CH₄/N₂ mixture with good regenerability. The separation mechanism of Al-FUM-Me for the CH₄/N₂ mixture was elucidated by theoretical calculations, showing that the stronger affinity of CH₄ can be attributed to its relatively shorter interaction distance with adsorption binding sites. Therefore, this work not only offers a promising candidate for CH₄/N₂ separation but also provides valuable guidance for the design of high-performance adsorbents.