Single-Step Synthesis of W₂C Nanoparticle-Dispersed Carbon Electrocatalysts for Hydrogen Evolution Reactions Utilizing Phosphate Groups on Carbon Edge Sites

A novel, one-step protocol for the selective synthesis of W₂C nanoparticles from phosphotungstic acid (H₃PW₁₂O₄₀), a low-cost and commercially available tungsten compound, was developed. The nanoparticles had diameters of 1–50 nm and were dispersed on a carbon substrate. The W₂C nanoparticles were prepared by a simple operation sequence, involving impregnation of carbon black with H₃PW₁₂O₄₀ followed by calcination at 1000 °C. X-ray diffraction study revealed the selective formation of the W₂C phase in the samples prepared, whereas the tungsten carbide (WC) phase was present in the control prepared from H₂WO₄. Stable W₂C nanoparticles were obtained using this method owing to the presence of phosphate at the interfaces between the W₂C nanoparticles and the carbon substrates, which inhibited the diffusion of carbon atoms from the carbon substrates to the W₂C nanoparticles, leading to the formation of WC. The W₂C nanoparticles prepared showed an excellent catalytic activity for the hydrogen evolution reaction (HER), with low Tafel slopes of ∼50 mV/decade. The HER catalytic activity was notably high, being comparable to that of MoS₂, which is a promising alternative to Pt. The present method can potentially be applied to produce highly effective, low-cost, Pt-free electrocatalysts for the HER