This article reviews different methodologies for the fabrication of monolithic ceramic components possessing multiscale porosity, i.e., with pores ranging from a few nanometers to several hundred microns. Two main strategies have been discussed: (a) the assembling of micro/ mesoporous materials into components possessing also macropores; (b) the addition of micro/mesoporosity to macroporous, cellular monoliths. Both routes include onepot and multi-step processing routes, and yield components with different properties in terms, for instance, of specific surface area values, mechanical strength, and permeability to fluids. The wide range of processing approaches available enable the fabrication of components with very varied morphology, suitable for a variety of industrial applications

One-pot self-assembled hybrid films were synthesized by the cohydrolysis of methyltriethoxysilane and tetraethoxysilane and deposited via dip-coating. The films show a high "defect-free" mesophase organization that extends throughout the film thickness and for domains of a micrometer scale, as shown by scanning transmission electron microscopy. We have defined these films defect-free to describe the high degree of order that is achieved without defects in the pore organization, such as dislocations of pores or stacking faults. A novel mesophase, which is tetragonal I4/mmm (space group), is observed in the films. This phase evolves but retains the same symmetry throughout a wide range of temperatures of calcination. The thermal stability and the structural changes as a function of the calcination temperature have been studied by small-angle X-ray scattering, scanning transmission electron microscopy, and Fourier transform infrared spectroscopy. In situ Fourier transform infrared spectroscopy employing synchrotron radiation has been used to study the kinetics of film formation during the deposition. The experiments have shown that the slower kinetics of silica species can explain the high degree of organization of the mesostructure.

The knowledge of the physics and the chemistry behind the evaporation of solvents is very important for the development of several technologies, especially in the fabrication of thin films from liquid phase and the organization of nanostructures by evaporation-induced self-assembly. Ethanol, in particular, is one of the most common solvents in sol-gel and evaporation-induced self-assembly processing of thin films, and a detailed understanding of its role during these processes is of fundamental importance. Rapid scan time-resolved infrared spectroscopy has been applied to study in situ the evaporation of ethanol and ethanol-water droplets on a ZnSe substrate. Whereas the evaporation rate of ethanol remains constant during the process, water is adsorbed by the ethanol droplet from the external environment and evaporates in three stages that are characterized by different evaporation rates. The adsorption and evaporation process of water in an ethanol droplet has been observed to follow a complex behavior: due to this reason, it has been analyzed by two-dimensional infrared correlation. Three different components in the water bending band have been resolved.

Dynamic spatial control of MOF position is obtained by incorporating carbon‐coated cobalt nanoparticles within metal organic framework (MOF)‐5 crystals. The cobalt framework composite obtained responds efficiently to magnetic stimuli. A luminescent functionality is added, showing that multifunctional MOF devices can be prepared. This new generation of adaptive material is tested as a position‐controlled molecular sensor.