Catalysis of the Water Oxidation Reaction in the Presence of Iron and a Copper Foil.

The oxygen evolution reaction (OER) can provide electrons for reducing water, carbon dioxide, and ammonia. On the other hand, copper compounds are among the most interesting OER catalysts. In this study, water oxidation of a Cu foil in the presence of K2FeO4, a soluble Fe source, under alkaline conditions (pH ≈ 13) is investigated using electrochemical methods, X-ray diffraction, X-ray photoelectron spectroscopy, in situ visible spectroelectrochemistry, Raman spectroscopy, and scanning electron microscopy. After the reaction of the Fe salt with the Cu foil, a remarkable improvement for OER is recorded, which indicates that either the Fe ions on the copper foil directly participate in OER or these ions are critical for activating copper ions on the surface toward OER. Indeed, a remarkable decrease (130 mV) in the overpotential is recorded for the Cu foil in the presence of [FeO4]2-. Tafel slopes for the Cu foil in the absence and presence of K2FeO4 are 113.2 and 46.4 mV/decade, respectively. X-ray photoelectron spectroscopy shows that there is a strong interaction between Cu(II) and Fe(III) on the surface of the Cu foil. During OER in the presence of Cu(II) (hydr)oxide, Cu(III) is detected. In situ visible spectroelectrochemistry shows that Cu and Fe ions are dynamically active and precipitate on the surface of the counter electrode during cyclic voltammetry (CV). The isotopic experimental data using H218O based on Raman spectroscopy show that there is no change in the lattice oxygen. All of these experiments adopt a new perspective on the role of Fe in OER in the presence of a Cu foil under alkaline conditions.