Defect Engineering in Metal–Organic Frameworks Towards Advanced Mixed Matrix Membranes for Efficient Propylene/Propane Separation

Abstract

Highly permselective and durable membrane materials have been sought for energy-efficient C₃ H₆ /C₃ H₈ separation. Mixed-matrix membranes (MMMs) comprising a polymer matrix and metal-organic frameworks (MOFs) are promising candidates for this application; however, rational matching of filler-matrix is challenging and their separation performances need to be further improved. Here, we propose a novel strategy of "defect engineering" in MOFs as an additional degree of freedom to design advanced MMMs. MMMs incorporated with defect-engineered MOFs exhibit exceptionally high C₃ H₆ permeability and maintained C₃ H₆ /C₃ H₈ selectivity, especially with enhanced stability under industrial mixed-gas conditions. The gas transport, sorption, and material characterizations reveal that the defect sites in MOFs provide the resulting MMMs with not only ultrafast diffusion pathways but also favorable C₃ H₆ sorption by forming complexation with unsaturated open metal sites, confirmed by in situ FT-IR studies. Most importantly, the concept is also valid for different polymer matrices and gas pairs, demonstrating its versatile potential in other fields.