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[References: 50 tit.]

Developing non-noble metal catalysts with superior catalytic activity and excellent durability is critically essential to promote electrochemical water splitting for hydrogen production. Morphology control as a promising and effective strategy is widely implemented to change the surface atomic coordination and thus enhance the intrinsic catalytic performance of current electrocatalysts. Herein, a series of cobalt phosphide (CoP) electrocatalysts with tunable morphologies of nanosheets, nanowires, nanorods, and nanoblocks have been prepared for the enhanced hydrogen evolution reaction (HER) by only adjusting the amount of ammonium fluoride (NH4F) in the hydrothermal process. Benefiting from the large active area, high surface activity, and favorable ion and gas diffusion channels, the clustered CoP nanorods obtained at a concentration of 0.15 M NH4F show the best HER performance with only an overpotential of 71 mV at a current density of 10 mA cm-2 and a low Tafel slope of 60.75 mV dec-1 in 1 M KOH. After 3000 CV cycles and 24 h durability tests, there is only a very slight degradation of performance owing to its outstanding stability and robust substrate adhesion.