Ultrasmall Copper Nanoclusters in Zirconium Metal‐Organic Frameworks for the Photoreduction of CO(2)

Encapsulating ultrasmall Cu nanoparticles inside Zr‐MOFs to form core–shell architecture is very challenging but of interest for CO(2) 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 Cu(I) sites located at the interface between Cu NCs and support serve as the active sites and efficiently catalyze CO(2) photoreduction. This synergetic effect may pave the way for the design of low‐cost and efficient catalysts for CO(2) photoreduction into high‐value chemical feedstock.