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

Emily Braxton; David J Fox; Ben G Breeze; Joshua J Tully; Katherine J Levey; Mark E Newton; Julie V Macpherson

doi:10.1021/acsmeasuresciau.2c00049

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

ACS Meas Sci Au. 2022 Sep 26;3(1):21-31. doi: 10.1021/acsmeasuresciau.2c00049. eCollection 2023 Feb 15.

Authors

Emily Braxton^{1

2}, David J Fox¹, Ben G Breeze³, Joshua J Tully¹, Katherine J Levey^{1

4}, Mark E Newton³, Julie V Macpherson¹

Affiliations

¹ Department of Chemistry, University of Warwick, CoventryCV4 7AL, U.K.
² Molecular Analytical Science Centre for Doctoral Training, University of Warwick, CoventryCV4 7AL, U.K.
³ Department of Physics, University of Warwick, CoventryCV4 7AL, U.K.
⁴ Centre for Doctoral Training in Diamond Science and Technology, University of Warwick, CoventryCV4 7AL, U.K.

Abstract

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.