Porous compositions and methods of making and using same. The compositions may be one or more layer(s) of mesoporous inorganic materials. The mesoporous inorganic material(s) may be a plurality of inorganic nanocages, which may be microporous. A composition may include homostacks of layers of the same inorganic mesoporous materials. A composition may include heterostacks of layers of inorganic mesoporous materials, where at least two of the layers are different. The compositions may be surface functionalized. The compositions may be formed in a reaction mixture including one or more precursor(s), one or more surfactant(s), water, and one or more organic solvent(s). The compositions may be formed at the liquid-liquid interface between the water and the one or more organic solvent(s). A composition may be used as a catalyst, in a catalytic method, as a separation medium, in a separation method, in nanomedicine applications, or the like.