Selective oxidation with nanoporous silica supported sensitizers: An environment friendly process using air and visible light

Highlights: ► Photo-sensitizers were covalently grafted on silica matrices. ► Grafted powdered silica was characterized by diffuse reflectance and emission spectroscopy. ► Selective solvent-free photo-oxygenation was carried out with air under visible light. ► Singlet generation and reactivity at the gas–solid interface was demonstrated. - Abstract: Transparent and porous silica xerogels containing various grafted photosensitizers (PSs) such as anthraquinone derivatives, Neutral Red, Acridine Yellow and a laboratory-made dicyano aromatics (DBTP) were prepared. In most cases, the xerogels were shown to be mainly microporous by porosimetry. The PSs were characterized in the powdered monoliths (form, aggregation, concentration) by electronic spectroscopy which also proved to be a useful tool for monitoring the material evolution after irradiation. These nanoporous xerogels were used as microreactors for gas/solid solvent-free photo-oxygenation of dimethylsulfide (DMS) using visible light and air as the sole reactant. All these PSs containing monoliths were efficient for gas–solid DMS oxidation, leading to sulfoxide and sulfone in varying ratios. As these polar oxidation products remained strongly adsorbed on the silica matrix, the gaseous flow at the outlet of the reactor was totally free of sulfide and odorless. The best results in term of yield and initial rate of degradation of DMS were obtained with DBTP containing xerogels. Moreover, as these materials were reusable without loss of efficiency and sensitizer photobleaching after a washing regeneration step, the concept of recyclable sensitizing materials was approved, opening the way to green process.