Surfactant-Assisted Synthesis of Mesoporous Metal Phosphonates to Control Surface Properties Including an Opportunity to Organize a Bulky Biphenyl Linker.

Abstract

A wide variety of properties by the presence of functional organic groups have so far been investigated by using periodic mesoporous organosilica (PMO)-type materials but not yet discussed with surface properties that are controlled through the success in synthesizing analogous non-silica-based hybrid mesoporous materials and subsequent evaluation and/or comparison of their properties. Here, we demonstrated the advance in synthesizing biphenyl group (-Ph-Ph-, also expressed as -2Ph)-containing mesoporous metal phosphonates with a rational understanding of surface properties. Ordered mesoporous films of aluminum and titanium ones (AOP-2Ph and TiOP-2Ph) were fabricated by spin-coating and their powders were recovered by spray-drying with the confined assembly of spherical mesopores. As in the case of PMO-type materials, the possibility to organize a -Ph-Ph- linker at the molecular scale was found in the powder samples of AOP-2Ph and TiOP-2Ph because thick frameworks would give an opportunity to organize the bulky -Ph-Ph- linker as the small-sized domains even around spherical mesopores. Surface properties of AOP-2Ph and TiOP-2Ph were evaluated by using the data of water (H2O) adsorption isotherms and compared with those containing different organic groups. The unique hydrophilicity starting from the hydration of AlO4 units was drastically reduced by the presence of -Ph-Ph- groups with a disappearance of the capillary condensation by the presence of mesopores. In addition, a partial replacement of TiO6 units with AlO4 and/or its hydrated AlO6 species was proposed for decreasing the strong hydrophobicity of TiOP-2Ph. The contact angle over the spin-coated films was also measured by using a droplet of H2O, indicating that the surface of the films, especially TiOP-2Ph, was extremely hydrophilic. Although surface properties at the molecular scale can be evaluated by using molecular H2O vapor during the measurement of H2O adsorption isotherms, the interaction of the H2O cluster (droplet) with the bulk surface seems to be predominated by inorganic moieties.