{Reference Type}: Journal Article
{Title}: Mechanistic Study of the Activation and the Electrocatalytic Reduction of Hydrogen Peroxide by Cu-tmpa in Neutral Aqueous Solution.
{Author}: Langerman M;Hetterscheid DGH;
{Journal}: ChemElectroChem
{Volume}: 8
{Issue}: 15
{Year}: Aug 2021 2
{Factor}: 4.782
{DOI}: 10.1002/celc.202100436
{Abstract}: Hydrogen peroxide plays an important role as an intermediate and product in the reduction of dioxygen by copper enzymes and mononuclear copper complexes. The copper(II) tris(2-pyridylmethyl)amine complex (Cu-tmpa) has been shown to produce H2O2 as an intermediate during the electrochemical 4-electron reduction of O2. We investigated the electrochemical hydrogen peroxide reduction reaction (HPRR) by Cu-tmpa in a neutral aqueous solution. The catalytic rate constant of the reaction was shown to be one order of magnitude lower than the reduction of dioxygen. A significant solvent kinetic isotope effect (KIE) of 1.4 to 1.7 was determined for the reduction of H2O2, pointing to a Fenton-like reaction pathway as the likely catalytic mechanism, involving a single copper site that produces an intermediate copper(II) hydroxo species and a free hydroxyl radical anion in the process.