Mechanistic and adsorption studies of relevance to photocatalysts on titanium grafted mesoporous silicalites

Ti-SBA-15 and Ti-MCM-41 were synthesized and evaluated as possible photocatalysts for the reduction of CO₂, and for the photo-Kolbe decomposition of acetic acid. UV-Raman was used to study the adsorption of carbon dioxide, water, formic acid, and acetic acid over Ti-MCM-41 by monitoring the UV enhanced resonance peak of the totally symmetric stretching band of the grafted Ti species at 1,085 cm^-1. Acetic and formic acid dissociate on Ti-SBA-15 and Ti-MCM-41 to form acetate and formate, respectively. The conjugate bases subsequently interact strongly with Ti sites. Water interacts with the Ti sites, while no change in the amplitude of the 1,085 cm^-1 band is observed in the presence of CO₂. Photocatalysis experiments indicate that these mesoporous silicalites are active in the photo-Kolbe decomposition of acetic acid. CO₂ is formed by reaction of a hole with the acetate carboxylate groups. The methyl radical co-products react with a surface proton and an electron to form methane. No products resulting from the dimerization of methyl radicals are observed, presumably because of the highly dispersed active sites.