▎ 摘　　要

Low-cost electrocatalysts play an important role in the hydrogen evolution reaction (HER). Particularly, transition metal phosphides (TMPs) are widely applied in the development of HER electrocatalysts. To improve the poor electrochemical reaction kinetics of HER, we introduce a facile way to synthesize carbon core-shell materials containing cobalt phosphide nanoparticles embedded in different graphene aerogels (GAs) (CoP@C-NPs/GA-x (x = 5, 10 and 20)) using seaweed biomass as precursors. The synthesized CoP@C-NPs/GA-5 exhibits efficient catalytic activity with small overpotentials of 120 and 225 mV at current densities of 10 mA cm(-2), along with the low Tafel slopes of 57 and 66 mV dec(-1), for HER in acidic and alkaline electrolytes, respectively. Compared with carbon aerogel (CA) containing cobalt phosphide nanoparticles (CoP-NPs@CA), the stability of CoP@C-NPs/GA-5 coated with carbon-shells (approximate to 0.8 nm) was significantly improved in acidic electrolytes. We also prepared carbon core-shell materials containing nickel phosphide nanoparticles embedded in GA (Ni2P@C-NPs/GA) to further expand this synthetic route. The graphene-Ni2P@C aerogel shows a similar morphology and better catalytic activity for HER in acidic and alkaline electrolytes. In this work, the robust three-dimensional (3D) GA matrix with abundant open pores and large surface area provides unblocked channels for electrolyte contact and electronic transfer and enables very close contact between the catalyst and electrolyte. The MxP@C core-shell structure prevents the inactivation of MxP NPs during HER processes, and the thin graphene oxide (GO) layers and 3D CA together build up a 3D conductive matrix, which not only adjusts the volume expansion of MxP NPs as well as preventing their aggregation, but also provides a 3D conductive pathway for rapid charge transfer processes. The present synthetic strategy for phosphides via in situ phosphorization with 3D GA can be extended to other novel high-performance catalysts. The simple synthesis and efficient catalytic activity of MXP@C-NPs/GA indicate good application prospects in HER.