Step‐Nucleation In Situ Self‐Repair to Prepare Rollable Large‐Area Ultrathin MOF Membranes

Abstract Ultrathin membranes with ultrahigh permeance and good gas selectivity have the potential to greatly decrease separation process costs, but it requires the practical preparation of large area membranes for implementation. Metal–organic frameworks (MOFs) are very attractive for membrane gas separation applications. However, to date, the largest MOF membrane area reported in the literature is only about 100 cm². In the present study, a new step‐nucleation in situ self‐repair strategy is proposed that enables the preparation of large‐area (2400 cm²) ultrathin and rollable MOF membranes deposited on an inexpensive flexible polymer membrane support layer for the first time, combining a polyvinyl alcohol (PVA)‒metal‐ion layer and a pure metal‐ion layer. The main role of the pure metal‐ion layer is to act as the main nucleation sites for MOF membrane growth, while the PVA‒metal‐ion layer acts as a slow‐release metal‐ion source, which supplements MOF crystal nucleation to repair any defects occurring. Membrane modules are necessary components for membrane applications, and spiral‐wound modules are among the most common module formats that are widely applied in gas separation. A 4800 cm² spiral‐wound membrane module was successfully prepared, demonstrating the practical implementation of large‐area MOF membranes.