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Developing cost-effective and highly efficient bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of great interest for overall water splitting but still remains a challenging issue. Herein, a self-template route is employed to fabricate a unique hybrid composite constructed by encapsulating cobalt nitride (Co5.47N) nanoparticles within three-dimensional (3D) N-doped porous carbon (Co5.47N NP@N-PC) polyhedra, which can be served as a highly active bifunctional electrocatalyst. To afford a current density of 10 mA cm-2, the as-fabricated Co5.47N NP@N-PC only requires overpotentials as low as 149 and 248 mV for HER and OER, respectively. Moreover, an electrolyzer with Co5.47N NP@N-PC electrodes as both the cathode and anode catalyst in alkaline solutions can drive a current density of 10 mA cm-2 at a cell voltage of only 1.62 V, superior to that of the Pt/IrO2 couple. The excellent electrocatalytic activity of Co5.47N NP@N-PC can be mainly ascribed to the high inherent conductivity and rich nitrogen vacancies of the Co5.47N lattice, the electronic modulation of the N-doped carbon toward Co5.47N, and the hierarchically porous structure design.
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