New vesicular carbon-based rhenium phosphides with all-pH range electrocatalytic hydrogen evolution activity.

• The novel Re 3 P 4 @NPVC and Re 2 P@NPVC catalysts were designed by a novel strategy. • Coupling metal Re and P is able to promote the HER pathway. • The electronic coupling of NPVC layer and nanoparticles efficiently promotes the electron-transfer process for HER. • The Re 3 P 4 @NPVC exhibit remarkable catalytic activity for HER at all pH, which rivals the commercial Pt/C. Considering the great application prospect of noble metal rhenium (Re) in the catalytic field derived from its intrinsic properties, exploring more novel and highly effective Re-based catalysts becomes an important topic. Herein, for the first time, we design a novel strategy for fabrication of Re 2 P and Re 3 P 4 nanoparticles anchored in N, P doped vesicular carbon (NPVC) via pyrolyzing ammonium perrhenate (NH 4 ReO 4), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and melamine on the surface of SiO 2 spheres. Choosing hydrogen evolution as a probe reaction, Re 3 P 4 @NPVC heterostructure exhibits highly efficient catalytic activity compared with as-synthesized samples, which rivals the commercial Pt/C. Concretely, the Tafel slope is 38, 77 and 62 mV dec−1, and overpotential is 40, 70 and 61 mV at 10 mA cm−2 in 0.5 M H 2 SO 4 , 1 M phosphate buffer solution and 1 M KOH, respectively. Both experiment and DFT calculation unambiguously validate that Coupling metal Re and P is able to promote the HER pathway by tuning the ΔG H* value close to the optimum, balancing adsorption and desorption of hydrogen. Besides, the electronic coupling of NPVC layer and NPs synergistically enhances the proton adsorption and reduction kinetics. [ABSTRACT FROM AUTHOR]