Tensile Strain and Interatomic Orbital Hybridization Effects Boost the Electrocatalytic Performance of Intermetallic Pd3Pb Nanowires for Ethanol Electrooxidation†

Comprehensive Summary We present a strategy that effectively modulate the d‐band electronic structure of the active center by strain effect and interatomic orbital hybridization. This strategy efficiently promotes the kinetic process of the ethanol oxidation reaction (EOR) in alkaline media. In the intermetallic Pd 3 Pb nanowires, the introduction of Pb not only causes the lattice expansion of Pd but also achieves the interatomic orbital hybridization bonding with Pd. Such interatomic orbital hybridization effect and tensile strain effect can effectively achieve a co‐regulation of the d‐band electronic structure of Pd, which directly affects the adsorption behavior of intermediate on Pd for EOR. Hence, the intermetallic Pd 3 Pb nanowires demonstrate enhanced EOR activity and anti‐poisoning ability against CO ads . Theoretical calculations show that the enhanced OH* adsorption ability and the low energy barrier for the oxidative dehydrogenation of ethanol are the keys to high EOR activity and stability of the intermetallic Pd 3 Pb nanowires.