We developed a method to engineer well-distributed dicobalt phosphide (Co2P) nanoparticles encapsulated in N,P-doped graphene (Co2P@NPG) as electrocatalysts for hydrogen evolution reaction (HER). We fabricated such nanostructure by the absorption of initiator and functional monomers, including acrylamide and phytic acid on graphene oxides, followed by UV-initiated polymerization, then by adsorption of cobalt ions and finally calcination to form N,P-doped graphene structures. Our experimental results show significantly enhanced performance for such engineered nanostructures due to the synergistic effect from nanoparticles encapsulation and nitrogen and phosphorus doping on graphene structures. The obtained Co2P@NPG modified cathode exhibits small overpotentials of only -45 mV at 1 mA cm(-2), respectively, with a low Tafel slope of 58 mV dec(-1) and high exchange current density of 0.21 mA cm(-2) in 0.5 M H2SO4. In addition, encapsulation by N,P-doped graphene effectively prevent nanoparticle from corrosion, exhibiting nearly unfading catalytic performance after 30 h testing. This versatile method also opens a door for unprecedented design and fabrication of novel low-cost metal phosphide electrocatalysts encapsulated by graphene.

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