Fast site-to-site electron transfer of high-entropy alloy nanocatalyst driving redox electrocatalysis

Designing electrocatalysts with high-performance for both reduction and oxidation reactions faces severe challenges. Here, the uniform and ultrasmall (~3.4 nm) high-entropy alloys (HEAs) Pt₁₈Ni₂₆Fe₁₅Co₁₄Cu₂₇ nanoparticles are synthesized by a simple low-temperature oil phase strategy at atmospheric pressure. The Pt₁₈Ni₂₆Fe₁₅Co₁₄Cu₂₇/C catalyst exhibits excellent electrocatalytic performance for hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR). The catalyst shows ultrasmall overpotential of 11 mV at the current density of 10 mA cm⁻², excellent activity (10.96 A mg⁻¹Pt at -0.07 V vs. reversible hydrogen electrode) and stability in the alkaline medium. Furthermore, it is also the efficient catalyst (15.04 A mg⁻¹Pt) ever reported for MOR in alkaline solution. Periodic DFT calculations confirm the multi-active sites for both HER and MOR on the HEA surface as the key factor for both proton and intermediate transformation. Meanwhile, the construction of HEA surfaces supplies the fast site-to-site electron transfer for both reduction and oxidation processes.