Hot electron generation in aqueous solution at oxide-covered tantalum electrodes. Reduction of methylpyridinium and electrogenerated chemiluminescence of Ru(bpy)(3)(2+)

We describe the injection of hot electrons into an aqueous solution by use of a Ta/Ta2O5 electrode. Evidence for this process was obtained by studying the chemically irreversible reduction of N-methylpyridinium ion (NMP+, E d egrees = -1.37 V vs SHE). The reduction of NMP+ gives rise to a radical whi ch undergoes rapid dimerization to produce a water-insoluble species, 1,1 - tetrahydrobipyridine (TBP), that deposits on the electrode surface. The dep osit was analyzed by AFM, XPS, IR-reflectance, and TOF/SIMS to provide evid ence of TBP formation. We also investigated the electrochemical reduction o f Ru(bpy)(3)(2+) to confirm the generation of hot electrons on a Ta/Ta2O5 e lectrode in water. The electrochemical and spectroelectrochemical results p resent a well-defined reduction wave at high overpotential on Ta/Ta2O5 whic h is not observed on Pt or Au electrodes. Reduction of Ru(bpy)(3)(3+) at a Ta/Ta2O5 electrode produces emission (electrogenerated chemiluminescence) a nd provides additional evidence of hot electron injection.