ABSTRACT
Biominerals can exhibit exceptional mechanical properties owing to their hierarchically-ordered organic/inorganic nanocomposite structure. However, synthetic routes to oriented artificial biominerals of comparable complexity remain a formidable technical challenge. Herein we design a series of soft, deformable nanogels that are employed as particulate additives to prepare nanogel@calcite nanocomposite crystals. Remarkably, such nanogels undergo a significant morphological change-from spherical to pseudo-hemispherical-depending on their degree of cross-linking. This deformation occurs normal to the growth direction of the (104) face of the calcite and the underlying occlusion mechanism is revealed by in situ atomic force microscopy studies. This model system provides new mechanistic insights regarding the formation of oriented structures during biomineralization and offers new avenues for the design of synthetic nanocomposites comprising aligned anisotropic nanoparticles.
ABSTRACT
The direct incorporation of guest crystals into another type of host crystals during the formation of the latter is technically challenging due to the large difference in surface energy for different crystalline components. Nevertheless, we herein demonstrate that metal-organic frameworks (MOFs, UiO-66-NH2 as a model guest crystal) after postsynthetic modification with poly(methacrylic acid) can be efficiently incorporated into calcite single crystals, forming a unique composite structure where the MOF crystals are uniformly distributed throughout the whole calcite host crystals. Remarkably, such MOF@calcite composite crystals exhibit superior performance in fluoride removal compared with the MOF or calcite alone. Moreover, this incorporation strategy is general as it can be extended to other guest particles. In principle, this study opens up a versatile avenue for the rational design and preparation of a wide range of hybrid functional materials with controllable compositions and enhanced physicochemical properties.
