Electron Paramagnetic Resonance for the Detection of Electrochemically Generated Hydroxyl Radicals: Issues Associated with Electrochemical Oxidation of the Spin Trap

[Image: see text] For the detection of electrochemically produced hydroxyl radicals (HO(·)) from the oxidation of water on a boron-doped diamond (BDD) electrode, electron paramagnetic resonance spectroscopy (EPR) in combination with spin trap labels is a popular technique. Here, we show that quantification of the concentration of HO(·) from water oxidation via spin trap electrochemical (EC)-EPR is problematic. This is primarily due to the spin trap oxidizing at potentials less positive than water, resulting in the same spin trap-OH(·) adduct as formed from the solution reaction of OH(·) with the spin trap. We illustrate this through consideration of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap for OH(·). DMPO oxidation on a BDD electrode in an acidic aqueous solution occurs at a peak current potential of +1.90 V vs SCE; the current for water oxidation starts to rise rapidly at ca. +2.3 V vs SCE. EC-EPR spectra show signatures due to the spin trap adduct (DMPO-OH(·)) at potentials lower than that predicted thermodynamically (for water/HO(·)) and in the region for DMPO oxidation. Increasing the potential into the water oxidation region, surprisingly, shows a lower DMPO-OH(·) concentration than when the potential is in the DMPO oxidation region. This behavior is attributed to further oxidation of DMPO-OH(·), production of fouling products on the electrode surface, and bubble formation. Radical scavengers (ethanol) and other spin traps, here N-tert-butyl-α-phenylnitrone, α-(4-pyridyl N-oxide)-N-tert-butylnitrone, and 2-methyl-2-nitrosopropane dimer, also show electrochemical oxidation signals less positive than that of water on a BDD electrode. Such behavior also complicates their use for the intended application.