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 CO2 reduction. We report the first time incorporation NCs into a series benchmark Zr-MOFs, without aggregation, via scalable room temperature fabrication approach. The NCs@MOFs composites show much enhanced reactivity in comparison confined pore MOFs, regardless their similar intrinsic properties at atomic level. Moreover, introducing polar groups on MOF structure can further improve both catalytic and selectivity. Mechanistic investigation reveals that CuI sites located interface between support serve as active efficiently catalyze photoreduction. This synergetic effect may pave way design low-cost efficient catalysts photoreduction high-value chemical feedstock.