Various aspects of the constraints imposed on the photochemistry of systems in porous silica.
This manuscript briefly reviews the photochemistry of organic molecules on porous silica (or SiO2). To gain an understanding of the chemistry on silica, data are displayed and discussed with respect to studies in homogeneous solution. In particular, the exact dimensionality of kinetic processes on porous SiO2 is a matter for debate. Hence, units of concentration of an adsorbate on the surface are expressed as moles per nanometer squared and as moles per liter, in order to compare with solution. Many studies show that organic molecules adsorb to SiO2 via the surface silanol (or surface hydroxyl OH) groups. The adsorption is heterogeneous, due to various clusters of silanol groups and to charge transfer (CT) sites. Photophysical studies clearly show these effects. The photo-induced reactions on SiO2 may be described by 'fractal' approaches, but a 'Gaussian' approach is often more useful to the photochemist. Photo-induced reactions occur via movement of the reactants on the surface, as in the case of the Langmuir-Hinshelwood (LH) mechanism or, as in the case of the Eley-Rideal (ER) mechanism, by bombardment of a surface bound excited state by a gaseous reactant, such as O2. Quenching of excited singlet states by O2 produces excited triplet states, which in turn are quenched to give singlet molecular oxygen. At room temperature the O2 quenching process on silica occurs by both mechanisms to approximately the same extent. However, the LH mechanism is dominant at lower temperatures and the ER mechanism is dominant at higher temperatures. Some quenchers, including carbon tetrachloride and tetranitromethane only quench by the LH mechanism giving rise to static quenching and chloro or nitro derivatives of the excited state. Photo-induced electron transfer between excited arenes and amines occurs readily, but the ionic products are short-lived compared to solution. This is due to the limited diffusion of the products on the surface, which in turn promotes back-electron transfer. Photoionization of arenes occurs on SiO2 via a two-photon process and gives very long-lived ions compared to solution. This is due to trapping of the photo-produced electrons by the SiO2 itself. Finally, the effects of co-adsorbants, including solvents, surfactants, and polymers, in photoreactions at the SiO2 surface are considered. The review ends with suggestions for future studies.