Electro-synthesized Co(OH)₂@CoSe with Co-OH active sites for overall water splitting electrocatalysis

Constructing noble metal-free electrocatalytically active sites for the simultaneous hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution is key to realizing electricity-driven water splitting in practical applications. Here, we rationally designed Co(OH)₂@CoSe nanorods (NRs) as an excellent bifunctional electrocatalyst by an in situ electrochemical transformation strategy, where the Co-based nanorod template was converted into Co(OH)₂@CoSe at the cathode. The obtained electrode exhibits superior electrocatalytic activity for both the HER (overpotential of 208 mV at 20 mA cm^-2) and the OER (268 mV at 20 mA cm^-2) at high current density in a 1 M KOH solution. The theoretical calculations and experimental evidence indicate that the chemical coupling Co-OH active site between Co(OH)₂ and CoSe regulates the hydrogen adsorption and desorption energy and fast electron transfer capability, which is responsible for the improved HER. Moreover, the Co(OH)₂@CoSe NRs can be further converted into CoOOH nanosheets which serve as OER active sites. Toward practical electrolytic cell applications, the Co(OH)₂@CoSe nanorods as both the cathode and anode achieved a current density of 100 mA cm^-2 at 1.94 V for overall water splitting, better than that of noble metal-based electrocatalysts.