Mass spectrometric snapshots for electrochemical reactions†
A hybrid ultramicroelectrode containing one micro-carbon electrode and one empty micro-channel was employed to be a micro-electrochemical cell and a mass spectrometric nanospray emitter. This setup can combine MS with an electrode directly and provide in situ information about an electrochemical reaction. The mechanisms proposed by Bard et al. for a Ru(bpy)32+ (bpy = 2,2′-bipyridine) electrochemiluminescence (ECL) system were confirmed by the MS detection of key intermediates. The short-lived diimine intermediate of electrochemical oxidation of uric acid was also detected, which affirms that the novel technique is able to catch fleeting intermediates. These experimental results demonstrate that this new method is simple, easy to implement and can be coupled with many commercial mass spectrometric instruments to provide very useful information about electrochemical reactions.