Achieving advanced hydrogen evolution under large current density using an amorphous/crystalline core–shell electrocatalyst of a-NiCoP/Co2P†

Non-precious transition metal-based electrocatalysts with high activities are promising candidates for substituting Pt- or Ru-based electrocatalysts in hydrogen evolution. In this study, we propose core–shell engineering to combine the amorphous NiCoP and crystalline Co₂P (a-NiCoP/Co₂P@NF), which requires an ultra-low overpotential of only 26 mV to achieve the benchmark current density of 10 mA cm⁻². Furthermore, it achieves an industrial-level hydrogen evolution current density of 500 mA cm⁻² with excellent stability. The superior catalytic performance and stability can be attributed to the hierarchical amorphous/crystalline interface and the electron-rich interfacial Co sites. The amorphous NiCoP shell can not only protect the internal Co₂P from corrosion, but also provide a larger electrochemically active area. Together, the Co₂P core provides fast electron transport and promotes H₂ emission from the interfacial electron-rich Co sites. This work provides inspiration to the rational design of an advanced core–shell structure between amorphous and crystalline states.