Abstract
Developing robust nonprecious electrocatalysts towards hydrogen/oxygen evolution reactions is crucial for widespread use of electrochemical water splitting in hydrogen production. Here, we report that intermetallic Co(3)Mo spontaneously separated from hierarchical nanoporous copper skeleton shows genuine potential as highly efficient electrocatalysts for alkaline hydrogen/oxygen evolution reactions in virtue of in-situ hydroxylation and electro-oxidation, respectively. The hydroxylated intermetallic Co(3)Mo has an optimal hydrogen-binding energy to facilitate adsorption/desorption of hydrogen intermediates for hydrogen molecules. Associated with high electron/ion transport of bicontinuous nanoporous skeleton, nanoporous copper supported Co(3)Mo electrodes exhibit impressive hydrogen evolution reaction catalysis, with negligible onset overpotential and low Tafel slope (~40 mV dec(-1)) in 1 M KOH, realizing current density of -400 mA cm(-2) at overpotential of as low as 96 mV. When coupled to its electro-oxidized derivative that mediates efficiently oxygen evolution reaction, their alkaline electrolyzer operates with a superior overall water-splitting output, outperforming the one assembled with noble-metal-based catalysts.