摘要：In this work,we have performed density functional theory(DFT)calculations to investigate the methanol electro‐oxidation reaction(MOR)catalyzed by the Pt,PtCu alloy and *** complex reaction networks,including the intermediate dehydrogenation,water dissociation and anti‐poison reaction steps,are systematically investigated to explore the *** the standard condition of pH=0 and zero potential,for Cu,most dehydrogenation steps along the favorable pathway are endergonic,making it less active in *** the Pt and PtCu alloy,their dehydrogenation steps are mainly exergonic,but the formed CO intermediate binds too tightly on Pt,that can accumulate on active sites to poison the electro‐*** CO can be consumed by the thermodynamic reaction with OH*,which comes from water *** calculation shows alloying the Pt with Cu could not only reduce the free energy barrier for binding between CO*and OH*,but also assist the water dissociation to produce more OH*for that anti‐poison *** makes the PtCu alloy more active than the pure Pt electrode in *** results reveal the importance of anti‐poison reaction and water dissociation in MOR,which could be applied to the rational design of more active alloy electro‐catalysts in future.

摘要：Surface tailoring of Pt-based nanocatalysts is an effective pathway to promote their electrocatalytic performance and ***,we report two kinds of one-dimensional(1D)ultrafine PtCu nanowires(smooth surface&rugged surface)synthesized via a wet chemical method and their distinct catalytic performances in electro-oxidation of *** alloyed PtCu nanowires having rough surfaces with atomic steps exhibit superior catalytic activity toward multiple electrochemical reactions compared with the smooth *** functional theory simulations show the excellent reactivity of rugged PtCu na-nowires and attribute it to the surface synergetic Pt-Cu site which accounts for the promotion of water dissociation and the dehydrogenation of the carboxyl *** current study provides an insight into reasonable design of alloy nanocatalysts in energy-related electrocatalytic systems.