An Acetate Bound Cobalt Oxide Catalyst for Water Oxidation: Role of Monovalent Anions and Cations In Lowering Overpotential

Abstract: Co(II) dissolved in acetate buffer at pH 7 is found to be a good water oxidation catalyst (WOC) showing electrocatalytic water oxidation current significantly greater than Co(II) in phosphate buffer under the same conditions owing to the higher solubility of the former. When electrodeposited on ITO/FTO electrodes it forms acetate bound cobalt(II)oxide based material (Co-Ac-WOC) showing catalytic water oxidation current density of 0.1 mA/cm$^{2}$ at 830 mV and 1 mA/cm$^{2}$ at 1 V in a pH 7 buffer solution. The morphology of Co-Ac-OEC is investigated with AFM, HR-TEM and SEM (at different times and electrodeposition potentials). The chemical composition of Co-Ac-OEC is investigated using XPS, EDX, combustion analysis and ATR-FTIR which indicates that this material has a CoO core with chloride and acetate anions bound to the Co center. Sodium is found to be integrated in the Co-Ac-WOC. The presence of the sodium ions and the chloride ions lowers the onset potential for oxygen evolution reaction (OER) by 240 mV relative to the classic Co-Pi at pH 7. The lower onset potential and higher OER current lowers the exchange current density to 10$^{-6.7}$ in Co-Ac-WOC relative to 10$^{-8}$-10$^{-10}$ in Co-Pi and its derivatives.