Boosting Hydrogen Transport in Mixed Matrix Membranes Through Continuous Spillover Via Pd‐Functionalized MOF Gel Networks

Abstract Membrane‐based gas separation offers notable energy efficiency benefits for hydrogen purification, yet it is often hindered by the inherent trade‐off between permeability and selectivity. To address this challenge, a novel mixed matrix membrane (MMM) design is presented to boost H₂ separation performance via continuous hydrogen spillover mechanisms for the first time. The MMM incorporates a palladium‐functionalized ZIF‐67 gel (Pd@ZIF‐67 gel) network into a polymer of intrinsic microporosity (PIM‐1) matrix. The ZIF‐67 gel network serves as a uniform dispersion medium for palladium nanoparticles (Pd NPs), thereby generating a multitude of active sites. These exposed sites, in conjunction with the microporous structure of ZIF‐67, facilitate hydrogen dissociation and establish a continuous hydrogen spillover pathway throughout the membrane. This synergistic MMM design leads to substantial improvements in both hydrogen transport and selectivity. At an optimal loading of 28 wt% Pd@ZIF‐67 gel, the MMMs exhibit a H₂ permeability of 3620 Barrer and a remarkable 417% enhancement in H₂/CH₄ selectivity (24.9), surpassing the 2008 upper bound. This approach paves the way for the development of advanced materials tailored for gas separation applications.