Noble metal-free ternary cobalt-nickel phosphides for enhanced photocatalytic dye-sensitized hydrogen evolution and catalytic mechanism investigation

Transition metal phosphides have emerged as compelling alternatives to noble metal catalysts for photocatalytic hydrogen evolution, owing to their high efficiency, stability, ease of preparation, and low-cost-effectiveness. This study investigates a series of binary and ternary phosphides predominantly composed of cobalt and nickel employed for photocatalytic dye-sensitized hydrogen evolution. Under the optimal dye-to-catalyst mass ratio, CoNiP exhibited the highest hydrogen evolution activity (12.96 mmol g⁻¹ h⁻¹), demonstrating more significant and satisfactory performance than a variety of other reported materials. This can be attributed to the high conductivity and low hydrogen evolution overpotential of phosphides, which result from their metallic characteristics and the presence of free electrons, which promote efficient electron transfer between the catalyst and sensitizer. Density functional theory calculations revealed that the cobalt incorporation into the binary phosphides causes a negative shift in the average d-band center for CoNiP, weakening the adsorption affinity of the catalyst towards H₂ molecules, thus effectively improving the hydrogen evolution rate compared to the pure binary phosphides. This work provides valuable insights for the development of low-cost and high-performance ternary phosphide photocatalysts.