Controlling nanocluster growth through nanoconfinement: the effect of the number and nature of metal–organic framework functionalities

Controlled nanocluster growth via nanoconfinement is an attractive approach as it allows for geometry control and potential surface-chemistry modification simultaneously. However, it is still not a straight-forward method and much of its success depends on the nature and possibly concentration of functionalities on the cavity walls that surround the clusters. To independently probe the effect of the nature and number of functional groups on the controlled Pd nanocluster growth within the pores of the metal-organic frameworks, Pd-laden UiO-66 analogues with mono- and bi-functionalised linkers of amino and methyl groups were successfully prepared and studied in a combined experimental-computational approach. The nature of the functional groups determines the strength of host-guest interactions, while the number of functional groups affects the extent of Pd loading. The interplay of these two effects means that for a successful Pd embedding, mono-functionalised host matrices are more favourable. Interestingly, in the context of the present and previous research, we find that host frameworks with functional groups displaying higher Lewis basicity are more successful at controlled Pd NC growth via nanoconfinement in MOFs.Synthesis of active nanoclusters through confinement in pores of functional frameworks is an attractive approach as it allows for geometry control and potential surface-chemistry modification simultaneously.