One-pot synthesis of an inorganic heterostructure: uniform occlusion of magnetite nanoparticles within calcite single crystals†
A facile one-pot method is described for the formation of novel heterostructures in which inorganic nanoparticles are homogeneously distributed throughout an inorganic single crystal matrix. Our strategy uses nanoparticles functionalised with a poly(sodium 4-styrenesulphonate)-poly(methacrylic acid) [PNaStS-PMAA] diblock copolymer as a soluble crystal growth additive. This copolymer plays a number of essential roles. The PMAA anchor block is physically adsorbed onto the inorganic nanoparticles, while the PNaStS block acts as an electrosteric stabiliser and ensures that the nanoparticles retain their colloidal stability in the crystal growth solution. In addition, this strong acid block promotes binding to both the nanoparticles and the host crystal, which controls nanoparticle incorporation within the host crystal lattice. We show that this approach can be used to achieve encapsulation loadings of at least 12 wt% copolymer-coated magnetite particles within calcite single crystals. Transmission electron microscopy shows that these nanoparticles are uniformly distributed throughout the calcite, and that the crystal lattice retains its continuity around the embedded magnetite particles. Characterisation of these calcite/magnetite nanocomposites confirmed their magnetic properties. This new experimental approach is expected to be quite general, such that a small family of block copolymers could be used to drive the incorporation of a wide range of pre-prepared nanoparticles into host crystals, giving intimate mixing of phases with contrasting properties, while limiting nanoparticle aggregation and migration.