The development of catalytic materials capable of operating under mild conditions while maintaining high activity and stability is central to sustainable carbon management strategies. Bio-hybrid systems that combine enzymes with porous inorganic frameworks are emerging as promising candidates for low-energy CO₂ capture and conversion, yet their integration into scalable catalytic platforms remains limited by enzyme instability and transport constraints. Here, we present a hybrid catalytic architecture that combines metal–organic frameworks (MOFs), polyelectrolyte functional layers and membrane reactors into a single catalytic material platform designed for intensified CO₂ hydration reactions.

Carbonic anhydrase was selected as a model catalyst due to its exceptional intrinsic turnover for CO₂ hydration but well-known sensitivity to temperature, pH and industrial process conditions. To overcome these limitations, the enzyme was encapsulated within a zeolitic imidazolate framework (ZIF-8) and integrated onto polymeric membrane supports through polydopamine-assisted assembly and polyelectrolyte multilayers. This approach enables simultaneous control of enzyme microenvironment, catalytic accessibility and mass transport within a continuous-flow catalytic material. The resulting system can be described as a bio-hybrid catalytic membrane where the MOF provides structural and thermal protection, while the membrane reactor architecture enhances substrate delivery and product removal.

The individual contributions of each material component were first evaluated independently. Enzyme immobilization on functionalized membranes led to a substantial increase in apparent catalytic activity compared to the free enzyme, indicating that local microenvironment effects and convective transport can enhance catalytic performance. Encapsulation of the enzyme in ZIF-8 significantly improved thermal stability, preserving most of the initial activity after prolonged exposure to elevated temperatures, demonstrating the protective role of the porous framework. Integration of both strategies into a dual catalytic platform yielded the highest overall performance, combining improved activity with enhanced stability and sustained permeability.

The hybrid catalytic membrane exhibited biocatalytic activities exceeding those of conventional immobilization approaches while maintaining relevant permeate fluxes, demonstrating that the incorporation of porous framework materials can enhance both catalytic robustness and transport properties. The results highlight how interfacial engineering using MOFs, polyelectrolytes and membrane supports can create synergistic catalytic environments where enzyme stability, local pH conditions and substrate availability are simultaneously optimized. Importantly, the system operates under mild aqueous conditions and does not rely on energy-intensive regeneration steps typical of conventional solvent-based CO₂ capture processes.

From a materials perspective, this work illustrates the potential of combining crystalline porous materials with soft catalytic components to generate multifunctional catalytic interfaces. Such hybrid architectures open opportunities for designing next-generation catalytic membranes for carbon capture, biocatalytic transformations and low-energy separations. More broadly, the study demonstrates how bio-derived catalysts can be integrated into engineered material platforms to bridge the gap between molecular catalysis and scalable process technologies.

The presented approach aligns with current efforts in sustainable materials and catalytic process intensification by demonstrating a pathway toward robust, low-energy CO₂ conversion systems based on hybrid catalytic materials. These findings provide a foundation for further development of MOF-based bio-hybrid catalysts and membrane-integrated catalytic reactors for environmental and energy applications.