Efficient Ethane and Propane Separation from Natural Gas Using Heterometallic Metal-Organic Frameworks with Interpenetrated Structures.

The development of efficient technology for natural gas separation in industrial processes has become imperative. In this regard, the exploration of novel and effective adsorbents has gained significant attention. One promising approach is the metal regulation of metal-organic frameworks (MOFs), particularly heterometallic MOFs, which offer greater potential for gas separation due to their diverse composition. This study presents the synthesis of a series of iron- and vanadium-based heterometallic MOFs (MIL-126), featuring interpenetrated structures, and investigates their adsorption performance for methane (CH 4 ), ethane (C 2 H 6 ), and propane (C 3 H 8 ). Experimental results reveal that the choice of metal combinations within the MOF framework significantly influences the adsorption performance of MIL-126. Notably, heterometallic MIL-126(Fe/Ni) exhibits a stronger binding affinity for C 3 H 8 , with an impressive uptake of 177 cm 3 /g. The C 3 H 8 /CH 4 ideal adsorbed solution theory selectivity of MIL-126(Fe/Ni) surpasses that of MIL-126(Fe) by a factor of 7, reaching a value of 853, second only to the highest reported value. Furthermore, MIL-126(Fe/Ni) exhibits remarkable potential for the recovery of pure CH 4 from the equimolar C 3 H 8 /CH 4 mixture, with the amount of pure CH 4 approaching the maximum reported value for MOFs. Insights from isosteric heat at zero loading and Henry's coefficients indicate that the transformation of metal types leads to a change in the interaction energy between C 3 H 8 and the framework. Furthermore, breakthrough experiments validate the effective separation capability of MIL-126(Fe/Ni) for CH 4 /C 2 H 6 /C 3 H 8 mixtures. These findings underscore the remarkable potential of heterometallic MOFs in constructing a wide range of new MOFs with tailorable properties, thereby enhancing their gas separation performance.