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

Abstract

ABSTRACT 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. The integration of metabolic energy conversion, programmable self‐assembly, and materials engineering thus provides a general strategy for gas‐powered redox biocatalysis.