Incorporation of clusters within inorganic materials through their addition during nucleation steps

Nanomaterials are known to display chemical and physical behaviours that are different from those of their bulk counterparts, but assembly processes in the sub-nanometre region are difficult to control. The early growth of nanomaterials is typically thought to involve two separate steps: nucleation and the growth stage, as described by the LaMer model. Control of the shape and size of the final structure is typically determined during the growth stage by interactions between the nuclei and surrounding monomers. Here, we show that clusters with well-defined structures, such as polyoxometalates, can intervene at the nucleation stage of nickel oxysulfide and nickel–cobalt hydroxide by co-assembling with nuclei to produce uniform binary assemblies. Those can, in turn, incorporate a third, or also a fourth, type of nanocluster to form ternary or quaternary assemblies, respectively. Both binary and ternary assemblies are shown to serve as efficient atomic-site catalysts for room-temperature gasoline desulfurization and stereoselective catalytic reactions. During the synthesis of inorganic materials nickel oxysulfide and nickel–cobalt hydroxide, clusters with well-defined structures—such as polyoxometalates—can co-assemble with nuclei to produce uniform binary assemblies. The resulting materials can, in turn, incorporate a third, and fourth, type of nanocluster deposited on their surface to form ternary and quaternary assemblies, respectively.