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Earlier research has been primarily focused on WC as one of the most promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER), whereas the other compound in this carbide family—W 2 C—has received far less attention. Our theoretical calculations suggest that such a focus is misplaced and W 2 C is potentially more HER-active than WC. Nevertheless, the preparation of phase pure and sintering-free W 2 C nanostructures represents a formidable challenge. Here we develop an improved carburization method and successfully prepare ultrasmall and phase-pure W 2 C nanoparticles. When evaluated for HER electrocatalysis, W 2 C nanoparticles exhibit a small onset overpotential of 50 mV, a Tafel slope of 45 mV dec −1  and outstanding long-term cycling stability, which are dramatically improved over all existing WC-based materials. In addition, the integration of W 2 C nanoparticles with p-type Si nanowires enables highly active and sustainable solar-driven hydrogen production. Our results highlight the great potential of this traditionally non-popular material in HER electrocatalysis.

Ultrasmall and phase-pure W2C nanoparticles for efficient electrocatalytic and photoelectrochemical hydrogen evolution