Ultrasmall Copper Nanoclusters in Zirconium Metal‐Organic Frameworks for the Photoreduction of CO2

Encapsulating ultrasmall Cu nanoparticles inside Zr‐MOFs to form core–shell architecture is very challenging but of interest for CO2 reduction. We report for the first time the incorporation of ultrasmall Cu NCs into a series of benchmark Zr‐MOFs, without Cu NCs aggregation, via a scalable room temperature fabrication approach. The Cu NCs@MOFs core–shell composites show much enhanced reactivity in comparison to the Cu NCs confined in the pore of MOFs, regardless of their very similar intrinsic properties at the atomic level. Moreover, introducing polar groups on the MOF structure can further improve both the catalytic reactivity and selectivity. Mechanistic investigation reveals that the CuI sites located at the interface between Cu NCs and support serve as the active sites and efficiently catalyze CO2 photoreduction. This synergetic effect may pave the way for the design of low‐cost and efficient catalysts for CO2 photoreduction into high‐value chemical feedstock. A room‐temperature synthetic strategy is reported for incorporation of ultrasmall Cu nanoclusters into a series of robust Zr‐metal–organic frameworks. The resultant core–shell composites mediate CO2 photoreduction selectively and outperform similar composites even with variable Cu spatial distribution.