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Owing to multiple structural and compositional merits, resultant PdB alloy NWs synergistically expose more electrocatalytically active sites and also kinetically accelerate the removal of CO-related poisons, remarkably improving electrocatalytic EOR activity and stability compared to their counterpart catalysts. Besides, wavy PdB alloy NWs are also electrochemically more active for electrocatalytic oxidation of other alcohols (methanol, glycerol, and glucose). The findings reported here thus shed a bright light on rational design of the