Detection of Free Oxygen Reduction Reaction Intermediates Generated at Pt Nanoparticles By Electron Paramagnetic Resonance Spectroscopy

Abstract

In the search for clean energy conversion systems, PEM fuel cells have attracted a lot of attention over the last decades. Nanostructured electrocatalysts such as porous platinum nanoparticles (NPs) are considered one of the most promising advances to lower the cost of these fuel cells and make them more commercially attractive. The efficiency of these catalysts is limited by their activity towards the oxygen reduction reaction (ORR), and most research is thus focused on understanding reaction mechanisms and improving the activity. The mechanism is well understood for alkaline conditions, but there is still some debate for that under acidic conditions. It has been shown indirectly[1],[2] that radical intermediates formed during the reaction can desorb from the catalyst surface, but direct proof is still absent. More importantly, these free radicals are suspected to be responsible for the degradation of the carbon support, leading to the deactivation of the electrocatalyst NPs[3]. We propose an approach to detect and identify the free radicals produced during the ORR using electron paramagnetic resonance (EPR) spectroscopy. EPR spectroscopy combined with spin trapping has been shown to be useful for detecting radicals produced in electrochemical reactions[4],[5]. This method relies on binding the free oxygen radicals to the spin trap DMPO, forming the stable radical complex DMPO-OH•. The DMPO-OH complex can be detected using an EPR spectrometer. Custom-made glassy carbon RDE’s with a large geometrical surface area have been designed and were loaded with Pt nanoparticles via double pulse electrodeposition. The large surface area is necessary in order to produce sufficiently large amounts of free radicals to be detectable in the EPR spectrometer. A DMPO-OH• signal is formed and increases in strength for the duration of the ORR experiments. Furthermore, we observe a direct correlation between the charge produced during the experiment and the strength of the DMPO-OH• signal. This approach, capable of detecting the free oxygen radicals produced during the ORR, is employed to shed light on the ORR mechanism at carbon electrodes loaded with Pt NPs in acidic conditions.