Photocatalytic CO2‐to‐Syngas Evolution with Molecular Catalyst Metal‐Organic Framework Nanozymes

Syngas, a mixture of CO and H₂ , is a high-priority intermediate for producing several commodity chemicals, e.g., ammonia, methanol, and synthetic hydrocarbon fuels. Accordingly, parallel sunlight-driven catalytic conversion of CO₂ and protons to syngas is a key step toward a sustainable energy cycle. State-of-the-art catalytic systems and materials often fall short as application-oriented concurrent CO and H₂ evolution requires challenging reaction conditions which can hamper stability, selectivity, and efficiency. Here a light-harvesting metal-organic framework hosting two molecular catalysts is engineered to yield colloidal, water-stable, versatile nanoreactors for photocatalytic syngas generation with highly controllable product ratios. In-depth fluorescence, X-ray, and microscopic studies paired with kinetic analysis show that the host delivers energy efficiently to active sites, conceptually yielding nanozymes. This unlocked sustained CO₂ reduction and H₂ evolution with benchmark turnover numbers and record incident photon conversions up to 36%, showcasing a highly active and durable all-in-one material toward application in solar energy-driven syngas generation.