Self‐Assembled Hybrid Cell‐Enzyme Materials for Gas‐Powered Biocatalysis

The integration of biological energy conversion into functional materials represents a key challenge in the development of advanced catalytic systems. Here, we introduce self-assembled cell-enzyme hybrid materials that integrate cellular metabolism with programmable enzyme networks for gas-powered biocatalysis. By harnessing the native formate hydrogenlyase machinery of Escherichia coli, H$_2$ and CO$_2$ are converted into formate, which serves as a transient electron carrier for enzymatic NADH regeneration by a highly stable formate dehydrogenase. Integration of a transhydrogenase further provides access to NADPH-dependent pathways, establishing a modular redox platform that can be coupled to diverse downstream biocatalysts. The catalytic system is translated into ready-to-use material formats through cryogenic fabrication of lyophilized carrier-free hybrid beads and their subsequent encapsulation into alginate composites, enabling simple “count-and-add” operation, catalyst recycling, and robust performance under challenging reaction conditions. By exploiting H$_2$ as the reducing substrate while recycling CO$_2$ within the formate-mediated regeneration cycle, the system avoids sacrificial organic reduction equivalents and associated by-products, resulting in high atom economy. ... mehrThe integration of metabolic energy conversion, programmable self-assembly, and materials engineering thus provides a general strategy for gas-powered redox biocatalysis.