Palladium‐Percolated Networks Enabled by Low Loadings of Branched Nanorods for Enhanced H₂ Separations

Abstract Nanoparticles (NPs) at high loadings are often used in mixed matrix membranes (MMMs) to improve gas separation properties, but they can lead to defects and poor processability that impede membrane fabrication. Herein, it is demonstrated that branched nanorods (NRs) with controlled aspect ratios can significantly reduce the required loading to achieve superior gas separation properties while maintaining excellent processability, as demonstrated by the dispersion of palladium (Pd) NRs in polybenzimidazole for H₂/CO₂ separation. Increasing the aspect ratio from 1 for NPs to 40 for NRs decreases the percolation threshold volume fraction by a factor of 30, from 0.35 to 0.011. An MMM with percolated networks formed by Pd NRs at a volume fraction of 0.039 exhibits H₂ permeability of 110 Barrer and H₂/CO₂ selectivity of 31 when challenged with simulated syngas at 200 °C, surpassing Robeson's upper bound. This work highlights the advantage of NRs over NPs and nanowires and shows that right‐sizing nanofillers in MMMs is critical to construct highly sieving pathways at minimal loadings. This work paves the way for this general feature to be applied across materials systems for a variety of chemical separations.