TEMPO‐Modified Polymethacrylates as Mediators in Electrosynthesis – Redox Behavior and Electrocatalytic Activity toward Alcohol Substrates

Homogeneous catalysts (“mediators”) are useful for tuning selectivity in organic electrosynthesis. However, they can have a negative impact on the overall mass and energy balance if used only once or recycled inefficiently. In previous work, we introduced polymediator concept, which soluble redox-active polymers catalyze electrochemical reaction, allowing recovery by dialysis pressure-driven membrane filtration. Using anodic alcohol oxidation as test case, it was shown that TEMPO-modified polymethacrylates (TPMA) serve efficient reusable mediators. present study, properties of TPMA sample with well-defined molecular weight distribution were studied using cyclic voltammetry compared to low-molecular TEMPO species. The non-catalytic profiles shaped diffusive adsorptive processes, whereby latter become pronounced at low mediator concentrations high scan rates. Electrocatalytic studies suggest under applied conditions, TPMA-catalyzed is predominantly homogeneous process. kinetics determined rather potential than steric influences polymer backbone.