Lattice Strained B‐Doped Ni Nanoparticles for Efficient Electrochemical H2O2 Synthesis

Abstract Surface strains are necessary to optimize the oxygen adsorption energy during the oxygen reduction reaction (ORR) in the four‐electron process, but the surface strains regulation for ORR in the two‐electron process to produce hydrogen peroxide (H 2 O 2 ) is rarely studied. Herein, it is reported that the tensile strained B‐doped Ni nanoparticles on carbon support (Ni‐B@BNC) could enhance the adsorption of O 2 , stabilize OO bond, and boost the electrocatalytic ORR to H 2 O 2 . Moreover, the Ni‐B@BNC catalysts exhibit volcano‐type activity for electrocatalytic ORR to H 2 O 2 as a function of the strain intensity, which is controlled by B content. Among them, Ni 4 ‐B 1 @BNC exhibits the highest H 2 O 2 selectivity of over 86%, H 2 O 2 yield of 128.5 mmol h –1 g –1 , and Faraday efficiency of 94.9% at 0.6 V vs reversible hydrogen electrode as well as durable stability after successive cycling, being one of the state‐of‐the‐art electrocatalysts for two‐electron ORR. The density functional theory calculations reveal that tensile strain introduced by doping B into Ni nanoparticles could decrease the state density of Ni‐3d orbital and optimize the binding energy of OOH* during ORR. A new direction is provided here for the design of highly active and stable catalysts for potential H 2 O 2 production and beyond.