Acid Strength Effects on Dimerization during Metal-Free Catalytic Dioxygen Reduction

Development of earth-abundant catalysts for the reduction of dioxygen (ORR) is essential for the development of alternative industrial processes and energy sources. Here, we report a transition metal-free dicationic organocatalyst (PhPhen) for the ORR. The ORR performance of this compound was studied in acetonitrile solution under both electrochemical conditions and spectrochemical conditions, using halogenated acetic acid derivatives spanning a pK_a range of 12.65 to 20.3. Interestingly, it was found that under electrochemical conditions, a kinetically relevant peroxo dimer species forms with all acids. However, under spectrochemical conditions, strong acids diminish the kinetic contribution of this dimer to the observed rate due to lower catalyst concentrations, whereas weaker acids were still rate-limited by the dimer equilibrium. Together, these results provide insight into the mechanisms of ORR by organic-based, metal-free catalysts, suggesting that balancing redox activity and unsaturated character of these molecules with respect to the pK_a of intermediates can enable reaction tuning analogous to transition metal-based systems.