Anchoring Co^II Ions into a Thiol-Laced Metal–Organic Framework for Efficient Visible-Light-Driven Conversion of CO₂ into CO

Using solar energy to convert CO₂ into valuable fuels or chemicals offers a powerful solution to urgent energy and environmental problems. However, the development of efficient and selective catalysts remains a considerable scientific challenge. To address this, catalytically active Co^II centers can be anchored into the porous matrix of metal–organic frameworks (MOFs) by utilizing a robust Zr-based MOF (Zr-DMBD) functionalized with freestanding thiol groups to enable efficient post-synthetic metal insertion. The thus-prepared Zr-DMBD−Co MOF solids are modified by well-defined Co–thiolate units and have the capability of photocatalytically converting CO₂ into CO with high efficiency and selectivity under visible-light irradiation in a water-containing system. The turnover number and CO selectivity reach as high as 97 941 and 98 %, respectively.