2D MOF‐assisted Pyrolysis‐displacement‐alloying Synthesis of High‐entropy Alloy Nanoparticles Library for Efficient Electrocatalytic Hydrogen Oxidation

Abstract Multimetallic alloy nanoparticles (NPs) have received considerable attention in various applications due to their compositional variability and exceptional properties. However, the complexity of both the general synthesis and structure–activity relationships remain the long‐standing challenges in this field. Herein, we report a versatile 2D MOF‐assisted pyrolysis‐displacement‐alloying route to successfully synthesize a series of binary, ternary and even high‐entropy NPs that are uniformly dispersed on porous nitrogen‐doped carbon nanosheets (PNC NSs). As a proof of utility, the obtained Co 0.2 Ru 0.7 Pt 0.1 /PNC NSs exhibits apparent hydrogen oxidation activity and durability with a record‐high mass specific kinetic current of 1.84 A mg −1 at the overpotential of 50 mV, which is approximately 11.5 times higher than that of the Pt benchmark. Both experimental and theoretical studies reveal that the addition of Pt engenders a phase transition in CoRu alloys from hexagonal close‐packed ( hcp ) to face‐centered cubic ( fcc ) structure. The elevated reactivity of the resulted ternary alloy can be attributed to the optimized adsorption of hydrogen intermediate and the decreased reaction barrier for water formation. This study opens a new avenue for the development of highly efficient alloy NPs with various compositions and functions.