Unusual Activity of Rationally Designed Cobalt Phosphide/Oxide Heterostructure Composite for Hydrogen Production in Alkaline Medium

[Image: see text] Design and development of an efficient, nonprecious catalyst with structural features and functionality necessary for driving the hydrogen evolution reaction (HER) in an alkaline medium remain a formidable challenge. At the root of the functional limitation is the inability to tune the active catalytic sites while overcoming the poor reaction kinetics observed under basic conditions. Herein, we report a facile approach to enable the selective design of an electrochemically efficient cobalt phosphide oxide composite catalyst on carbon cloth (CoP-Co(x)O(y)/CC), with good activity and durability toward HER in alkaline medium (η(10) = −43 mV). Theoretical studies revealed that the redistribution of electrons at laterally dispersed Co phosphide/oxide interfaces gives rise to a synergistic effect in the heterostructured composite, by which various Co oxide phases initiate the dissociation of the alkaline water molecule. Meanwhile, the highly active CoP further facilitates the adsorption–desorption process of water electrolysis, leading to extremely high HER activity.