Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO₂ catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm^-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.