(320c) Direct Electrochemical Oxidation of Methane to Methanol on Transition Metal Oxide Electrodes

Electrochemical partial oxidation of methane to methanol is a promising approach to the transformation of stranded methane resources into a high-value, easy-to-transport fuel or chemical. Transition metal oxides are potential electrocatalysts for this transformation. However, a comprehensive and systematic study of the dependence of methane activation rates and methanol selectivity on catalyst morphology and experimental operating parameters has not been realized. Here, we describe an electrochemical method for the deposition of a family of thin-film transition metal (oxy)hydroxides as catalysts for the partial oxidation of methane. CoO_x, NiO_x, MnO_x, and CuO_x are discovered to be active for the partial oxidation of methane to methanol. Taking CoO_x and MnO_x as prototypical methane partial oxidation electrocatalysts, we systematically study the dependence of activity and methanol selectivity on catalyst film thickness, overpotential, temperature, and electrochemical cell hydrodynamics. Optimal conditions of low catalyst film thickness, intermediate overpotentials, intermediate temperatures, and fast methanol transport are identified to favor methanol selectivity. Through a combination of control experiments and DFT calculations, we show that the oxidized form of the as-deposited (oxy)hydroxide catalyst films are active for the thermal oxidation of methane to methanol even without the application of bias potential, demonstrating that high valence transition metal oxides are intrinsically active for the activation and oxidation of methane to methanol at ambient temperatures. Calculations uncover that electrocatalytic oxidation enables reaching an optimum potential window in which methane activation forming methanol and methanol desorption are both thermodynamically favorable, methanol desorption being favored by competitive adsorption with hydroxide anion.