This review covers comprehensively the 2D layered and 3D porous materials that have been reported in the past 5 years where combined solid-state NMR, FT-IR and computational methods have been employed for their characterization.

Detailed spectroscopic measurements have been used to elucidate the nature of Ti(IV)-centred active sites that were anchored to a mesoporous silica surface (MCM41) by two distinct routes from titanocene precursors. The catalyst prepared in dry argon (Ti-MCM41 [Ar]) is more active than that prepared in air (in the presence of water vapour) in its activity in the epoxidation of cyclohexene with tert-butylhydroperoxide (TBHP). The degree of loading of the titanium onto the silica support also influences the precise nature of the active sites. In Ti-MCM41 [Ar] samples containing less that 2 wt.% of Ti, the most abundant species are tetrahedrally bonded Ti(IV) active sites which absorb at 210–230 nm in diffuse reflectance (DR) UV–Vis spectra and exhibit an emission at 430 and 490 nm when excited with a 250 nm light. Samples of catalyst with greater than 4 wt.% loading are shown to contain TiO₂-like microclusters. These species absorb at λ250 nm in the DR UV–Vis and emit very weakly in the 500–600 nm region. In the case of Ti-MCM41 [air] catalysts, which were prepared in the presence of atmospheric water at the MCM41 surface, even at the lowest Ti loading (e.g. ⩽0.5%) an incipient formation of oligomers occurs. It is proposed that dimers or very small oligomers which absorb at around 250 nm in the DR spectra are responsible for a very strong emission at around 500 nm in the photoluminescence spectra. The abundant presence of these species might well explain the lower catalytic performance of Ti-MCM41 [air] in comparison with that of Ti-MCM41 [Ar]. The anchoring of the Ti species at the surface silanol groups of MCM41 was in all cases followed by FTIR spectroscopy.

The synthesis and characterization of amino‐functionalized mesoporous silica nanoparticles are presented following two different synthetic methods: co‐condensation and post‐synthesis grafting of 3‐aminopropyltriethoxysilane. The amino groups’ distribution on the mesoporous silica nanoparticles was evaluated considering the aggregation state of a grafted photosensitizer (Verteporfin) by using spectroscopic techniques. The homogeneous distribution of amino groups within the silica network is a key factor to avoid aggregation during further organic functionalization and to optimize the performance of functionalized silica nanoparticles in biomedical applications. In addition, the formation of a protein corona on the external surface of both bare and amino‐functionalized mesoporous silica was also investigated by adsorbing Bovine Serum Albumin (BSA) as a model protein. The adsorption of BSA was found to be favorable, reducing the aggregation phenomena for both bare and amino‐modified nanoparticles. Nevertheless, the dispersant effect of BSA was much more evident in the case of amino‐modified nanoparticles, which reached monodispersion after adsorption of the protein, thus suggesting that amino‐modified nanoparticles can benefit from protein corona formation for preventing severe aggregation in biological media.