Investigation on photogenerated radicals of some carboxylates in solution and in aqueous dispersions of AgBr

The photogenerated free radicals from formate, oxalate and acetate in aqueous solutions without and with dispered AgBr grains under illuminations of 355 nm laser light, natural light and monochromatic red, green or blue light were detected by electron spin resonance with spin-trap DMPO. The results showed that: (a) ·CO₂^- radicals were produced in the formate solution by all of these illuminations; (b) the signals of ·CO₂^- radicals were greatly intensified when an AgBr dispersion was present in the formate solution; (c) the signals of ·CO₂^- radicals in the oxalate solution were also detected and intensified when an AgBr dispersion was present, but only after illumination by the 355 nm laser; (d) ·CH₃ radicals, instead of ·CO₂^-, were weakly detected in the acetate solution, but only in the presence of AgBr under illumination by the 355 nm laser. The photochemical behaviour of these carboxylates, particularly formate and oxalate, perhaps implies their capability for trapping photogenerated holes and their potential for acting as a hole converter to an effective electron carrier.