Active nonprecious metal-based hydrogen evolution reaction (HER) electrocatalysts are critical for the clean and sustainable generation of hydrogen. Here, we synthesized multishelled FeCo@FeCoP@C hollow spheres by the carbonization and phosphorization of the FeCo-MIL-88 metal-organic framework. Owing to both composition (FeCo mixed phosphide) and morphology (multishelled morphology) effects, the as-obtained FeCo@FeCoP@C exhibits excellent HER performance with a low overpotential of 65 mV to achieve an HER current density of 10 mA cm–2 and high stability in acidic solution. Density functional theory calculations show that the FeCoP have the optimal hydrogen absorption energy than that of FeP and CoP. The carbon shell prevents the oxidation of the phosphides, and the FeCo core provides better conductivity. Our work provides a new method to synthesize multishelled structure catalysts, which has potential applications in the further hydrogen production.
Designing readily available and highly active electrocatalysts for water splitting is essential for renewable energy technologies. Here we present the construction of FeCo-FeCoP@C hollow nanocubes encapsulated in nitrogen-doped carbon nanocages (FeCo-FeCoP@C@NCCs) through controlled carbonization and subsequent phosphorization of a Prussian blue analogue. With stronger electronic interaction and hollow structure, the as-obtained FeCo-FeCoP@C@NCCs material requires small overpotentials of 91 mV and 280 mV to deliver 10 mA cm −2 in 1 M KOH toward hydrogen and oxygen evolution, respectively. More importantly, applying this material for overall water splitting, it only requires 1.64 V to afford 10 mA cm −2 and exhibits impressively durability over 40 h without obvious performance decay. The present approach inspires potentials for the controllable synthesis of multi-component catalysts for practical applications.