Double Epitaxy as a Paradigm for Templated Growth of Highly Ordered Three-Dimensional Mesophase Crystals

Molecular templating and self-assembly are fundamental mechanisms for controlling the morphology of biominerals, while in synthetic two-dimensional layered materials similar levels of control over materials structure can be achieved through the epitaxial relationship with the substrate. In this study these two concepts are combined to provide an approach for the nucleation and growth of three-dimensional ordered mesophases on solid surfaces. A combined experimental and theoretical study revealed how atomic ordering of the substrate controls the structure of surfactant template and the orientation and morphology of the epitaxially grown inorganic material. This dual epitaxial relationship between the substrate, surfactant template, and inorganic mesophase gives rise to a highly ordered porous mesophase with a well-defined cubic lattice of pores. The level of control over the material's three-dimensional architecture achieved in this one-step synthesis is reminiscent of that in biomineralization.