Artificial Photosynthetic Hydrogel Microspheres as a Versatile Platform for Programmable CO2 Valorization

Carbon-negative biomanufacturing is essential for global sustainability. Artificial photosynthesis based on material-microbe hybrid systems holds promise but suffers from inefficient energy supply, phototoxicity, abiotic–biotic incompatibility, and limited product spectrum. Here, we present artificial photosynthetic hydrogel microspheres (APHM) as a versatile platform for efficient and programmable CO 2 valorization. Within an alginate/carboxymethyl cellulose hydrogel matrix, spatial compartmentalization integrated a COF/Pt/Cr 2 O 3 photocatalyst (for in situ hydrogen evolution) and a light-shielded acetogen ( Acetobacterium woodii ) in a tailored bifunctional medium, enabling CO 2 -to-acetate conversion. The system operated stably under high-intensity illumination (60 mW cm –2 ), achieving a near-stoichiometric H 2 -to-acetate coupling efficiency of 88.85%. The resulting acetate served as a well-defined carbon hub, enabling seamless interface with engineered yeast for programmable synthesis of diverse products, including glucose (316 mg L –1 ), myo -inositol (64 mg L –1 ), glucosamine (24 mg L –1 ), sucrose (609 mg L –1 ), and starch (256 mg L –1 ). Overall, this work presents a universal, efficient route to versatile solar-to-chemical synthesis.