Photoinduced redox reactions between colloidal manganese dioxide and some organic compounds of environmental importance

Numerous organic compounds of environmental importance, i.e., phenol, citric, tartaric, and oxalic acids, proved to promote or accelerate reductive dissolution of colloidal manganese dioxide upon irradiation. This is accounted for the formation of surface-located charge-transfer complexes between the MnO₂ particulates and the organic electron donors. From the dependences of the rate of the photoassisted and thermal dissolution on the concentration of the organic compounds, the equilibrium constants for the formation of these complexes have been determined in the case of phenol, resorcinol, citrate, and tartaric acid. The quantum yields for these photoinduced reactions (at λ _ir = 365 nm), however, do not show any correlation with the values of the corresponding equilibrium constants, although adsorption is prerequisite for the efficient reductive dissolution of MnO₂. The changes in pH markedly affect the rate of this process, indicating that protonation of both the electron donors and the surface of the MnO₂ particulates may play significant roles in these systems. The results of experiments carried out in manganese dioxide excess suggest that total mineralization of organic electron donors is strongly hindered by the disadvantageous adsorption properties of the primary redox products. Dedicated to Professor Janos H. Fendler on the occasion of his 70th birthday.