Optical sensing of triethylamine using CdSe aerogels

The photoluminescence (PL) response of highly porous CdSe aerogels to triethylamine (TEA) is investigated and compared to results from prior studies on single crystals and nanoparticle-polymer composites. As-prepared CdSe aerogels show significant and reversible enhancement of luminescence intensity upon exposure to TEA relative to the intensity in pure argon carrier gas. The enhancement in the PL response is dependent on the concentration and linear over the range of TEA concentration studied (4.7 x 103-75 x 103 ppm). The sensing response of previously tested samples exhibits saturation behavior that is modeled using Langmuir adsorption isotherms, yielding adsorption equilibrium constants in the range 300-380 atm-1. The response is sensitively affected by the surface characteristics of the aerogel; when the wet gels are treated with pyridine prior to aerogel formation, the response to TEA is diminished, and when as-prepared aerogels are heated in a vacuum, no subsequent response is observed. Deactivation is attributed to an increase in surface oxide (SeO2) and decrease in surface Cd2+ Lewis acid sites. Sensing runs of approximately one hour have little impact on the morphology or crystallinity of the aerogels, but do result in partial removal of residual thiolate ligands left over from the gelation process.