In principle, nanoparticle occlusion within crystals provides a straightforward and efficient route to make new nanocomposite materials. However, developing a deeper understanding of the design rules underpinning this strategy is highly desirable. In particular, controlling the spatial distribution of the guest nanoparticles within the host crystalline matrix remains a formidable challenge. Herein, we show that the surface chemistry of the guest nanoparticles and the [Ca2+ ] concentration play critical roles in determining the precise spatial location of the nanoparticles within calcite crystals. Moreover, in situ studies provide important mechanistic insights regarding surface-confined nanoparticle occlusion. Overall, this study not only provides useful guidelines for efficient nanoparticle occlusion, but also enables the rational design of patterned calcite crystals using model anionic block copolymer vesicles.
Keywords: block copolymer vesicles; calcite (CaCO3); patterned structures; polymerization-induced self-assembly (PISA); spatially controlled occlusion.
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