Fabricating a Robust Ultramicroporous Metal‐Organic Framework for Purifying Natural Gas and Coal Mine Methane

Purifying methane (CH4) from natural gas and coal mine methane (CMM) is of great significance but challenging in the chemical industry. Herein, a robust ultramicroporous metal-organic framework (MOF) is reported, which can be synthesized on a gram scale by stirring under room temperature. Single-component adsorption isotherms of gases (CH4, ethane (C2H6), propane (C3H8), nitrogen (N2)) and breakthrough experiments indicate that the MOF can separate CH4 efficiently from CH4/C2H6/C3H8 ternary mixture, with super high purity-CH4 production of 154.7 cm3 g-1. Additionally, the MOF shows higher CH4 capacity than N2, resulting in excellent separation performance for the CH4/N2 mixture. Notably, the binding sites of gases can be precisely determined by single-crystal X-ray data, further confirmed by molecular simulation. It is found that there are multiple hydrogen bonds and C─H···π interactions between the gases and the framework. This work offers an excellent candidate material for CH4 purification with both high capacity and separation efficiency.