F and rare V⁴⁺ doped cobalt hydroxide hybrid nanostructures: excellent OER activity with ultralow overpotential

Highly efficient and stable Earth abundant transition metal electrocatalysts are in great demand for the oxygen evolution reaction (OER), a bottleneck process involved in the water splitting reaction and metal-air batteries. Herein, we have demonstrated a single step direct fabrication of cobalt hydroxide (Co(OH)₂) nanowires doped with vanadium(V) in a less stable +4 oxidation state and fluoride (F) ions (V-Co(OH)₂) on a carbon cloth electrode that showed highly enhanced OER activity under alkaline conditions. V-Co(OH)₂ nanowires synthesized under the optimized conditions produced excellent OER activity with an ultralow overpotential of 136 mV at 10 mA cm^-2 (scan rate 1 mV s^-1), a small Tafel slope (51.6 mV dec^-1) and good stability over 72 h. To the best of our knowledge, this is the lowest overpotential reported for cobalt-based electrocatalysts to achieve a geometric current density of 10 mA cm^-2. The controlled synthesis and HR-TEM studies revealed the formation of hybrid nanostructures (nanowires along with spherical assembly of nanoparticles) and codoping of V and F ions played an important role in enhancing the OER activity. The detailed chemical composition and oxidation state analysis by X-ray photoelectron spectroscopy (XPS) confirmed the doping of V⁴⁺ and ionic F in V-Co(OH)₂ with mixed valence states of Co²⁺/Co³⁺ and a higher Co²⁺ ratio. The outstanding OER activity of V-Co(OH)₂ is attributed to the formation of a spherical assembly of nanoparticles with nanowires, which provided a high number of catalytically active sites with enhanced charge transport, and doping of higher valence V⁴⁺ and strongly electronegative F in V-Co(OH)₂ with a higher ratio of Co²⁺/Co³⁺ promoted OOH* intermediate generation and significantly boosted the OER activity. Overall, the present work highlights the possibility of achieving highly active Earth abundant OER electrocatalysts by controlling the mixed oxidation state of Co with a judicious choice of dopants along with maintaining optimal nanostructure morphologies.