Efficient Occlusion of Nanoparticles within Inorganic Single Crystals

In principle, the incorporation of guest nanoparticles within host crystals should provide a straightforward and versatile route to a wide range of nanocomposite materials. However, crystallization normally involves expelling impurities, so nanoparticle occlusion is both counter-intuitive and technically challenging. Clearly, the nanoparticles should have a strong interaction with the growing crystalline lattice, but quantifying such an affinity has been challenging; the basic principles that govern efficient nanoparticle occlusion within inorganic single crystals are rather poorly understood. In the past few years, we have focused on the elucidation of robust design rules for such systems; our progress is summarized in this article.Polymerization-induced self-assembly (PISA) is widely recognized as a powerful platform technology for the preparation of a broad range of model organic nanoparticles. Herein, PISA was exploited to prepare sterically stabilized diblock copolymer nano-objects (e.g., spheres, worms, or vesicles) of varying size using steric stabilizers of well-defined chain length, variable anionic charge density, tunable surface density, and adjustable chemical functionality (e.g., carboxylic acid, phosphate, sulfate or sulfonate groups). Thus, we were able to systematically investigate how such structural parameters influence nanoparticle occlusion. Given its commercial importance for many industrial sectors, calcium carbonate was selected as the model host crystal for nanoparticle occlusion studies. Perhaps surprisingly, the extent of nanoparticle occlusion is not particularly sensitive to nanoparticle size or morphology. However, the steric stabilizer chain length can play a key role: relatively short chains lead to surface-confined occlusion, while sufficiently long chains enable uniform nanoparticle occlusion to be achieved throughout the crystal lattice (albeit sometimes inducing a significant change in crystal morphology). Optimizing the anionic charge density and surface density of the stabilizer chains is required to maximize the extent of nanoparticle occlusion, while steric stabilizer chains comprising anionic carboxylate groups led to greater occlusion compared to those composed of phosphate, sulfate, or sulfonate groups when examining a model vesicle system.Subsequently, our occlusion studies were extended to include functional hybrid nanocomposite crystals. For example, the spatially controlled occlusion of poly(glycerol monomethacrylate)-stabilized gold nanoparticles was achieved within semiconductive ZnO crystals by either controlling the nanoparticle concentration or by delaying their addition to the reaction mixture. Moreover, oil droplets of up to 500 nm have been incorporated into calcite crystals at up to 11% by mass, despite the large mismatch in surface energy between the hydrophobic oil droplets and the ionic crystal lattice. We have also explored a "Trojan horse" strategy, whereby cargos comprising nanoparticles or soluble dye molecules are first encapsulated within anionic block copolymer vesicles prior to their incorporation within calcite crystals. This approach offers a generic and efficient strategy for the occlusion of many types of guest species into single crystals. In summary, we have established important guidelines for efficient nanoparticle occlusion within crystals, which opens up new avenues for the synthesis of next-generation hybrid materials.