Carbonic Anhydrase-Mimicking Supramolecular Nanoassemblies for Developing Carbon Capture Membranes

As a ubiquitous family of enzymes with high performance in converting carbon dioxide (CO₂) into bicarbonate, carbonic anhydrases (CAs) sparked enormous attention for carbon capture. Nevertheless, the high cost and operational instability of CAs hamper their practical relevance, and the utility of CAs is mainly limited to aqueous applications where CO₂-to-bicarbonate conversion is possible. Taking advantage of the chemical motif that endows CA-like active sites (metal-coordinated histidine), here we introduce a new line of high-performance gas separation membranes with CO₂-philic behavior. We first self-assembled a histidine-based bolaamphiphile (His-Bola) molecule in the aqueous phase and coordinated the resulting entities with divalent zinc. Optimizing the supramolecular synthesis conditions ensured that the resultant nanoparticles (His-NPs) exhibit high CO₂ affinity and catalytic activity. We then exploited the His-NPs as nanofillers to enhance the separation performance of Pebax MH 1657. The hydrogen-bonding interactions allowed the dispersion of His-NPs within the polymer matrix uniformly, as confirmed by microscopic, spectroscopic, and thermal analyses. The imidazole and amine functionalities of His-NPs enhanced the solubility of CO₂ molecules in the polymer matrix. The CA-mimic active sites of His-NPs nanozymes, on the other hand, catalyzed the reversible hydration of CO₂ molecules in humid conditions, facilitating their transport across the membranes. The resulting nanocomposite membranes displayed excellent CO₂ separation performance, with a high level of stability. At a filling ratio as low as 3 wt %, we achieved a CO₂ permeability of >145 Barrer and a CO₂/N₂ selectivity of >95 with retained performance under humid continuous gas feeds. The bio-inspired approach presented in this work offers a promising platform for designing durable and highly selective CO₂ capture membranes.