Architected Metal Selenides via Sequential Cation and Anion Exchange on Self-Organizing Nanocomposites

Shape-preserving conversion reactions have the potential to unlock new routes for self-organization of complex three-dimensional (3D) nanomaterials with advanced functionalities. Specifically, developing such conversion routes toward shape-controlled metal selenides is of interest due to their photocatalytic properties and because these metal selenides can undergo further conversion reactions toward a wide range of other functional chemical compositions. Here, we present a strategy toward metal selenides with controllable 3D architectures using a two-step self-organization/conversion approach. First, we steer the coprecipitation of barium carbonate nanocrystals and silica into nanocomposites with controllable 3D shapes. Second, using a sequential exchange of cations and anions, we completely convert the chemical composition of the nanocrystals into cadmium selenide (CdSe) while preserving the initial shape of the nanocomposites. These architected CdSe structures can undergo further conversion reactions toward other metal selenides, which we demonstrate by developing a shape-preserving cation exchange toward silver selenide. Moreover, our conversion strategy can readily be extended to convert calcium carbonate biominerals into metal selenide semiconductors. Hence, the here-presented self-assembly/conversion strategy opens exciting possibilities toward customizable metal selenides with complex user-defined 3D shapes.