Scalable Fabrication of MOF Glass Membranes for Gas Separation via Stepwise Phase Transition

ABSTRACT MOF glasses have emerged as promising membrane materials, yet the scalable fabrication of macroscopically continuous and crack‐free MOF glass membranes remains a critical bottleneck that hinders their industrial translation. Here, we report a stepwise phase transition strategy that enables the formation of large‐area MOF glass membranes. By constructing a crystalline‐amorphous composite precursor, this strategy mitigates electrostatic repulsion and leverage graded viscoelastic flow to promote early‐stage interparticle bonding. This approach effectively suppresses cracking and pinhole defect formation during large‐area processing, providing a viable pathway toward scalable glassy membrane manufacturing. Based on this method, a record‐breaking 100 cm 2 MOF glass membrane exhibiting a CH 4 permeance of ∼13,000 GPU and CH 4 /N 2 selectivity of ∼4.4, alongside a validated disc‐type module, has been successfully fabricated. This strategy establishes a scalable route for producing large‐area MOF glass membranes and advances their application in real‐world gas separation scenarios.