Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully int...Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen‐adsorption strength to improve its interfacial H_(2)‐evolution rate via the Pd‐Cu alloying effect.Herein,the ultrasmall Pd_(100−x)Cu_(x) alloy nanodots(2−5 nm)as a novel H_(2)‐evolution cocatalyst were integrated with the TiO_(2) through a simple NaH_(2)PO_(2)‐mediated co‐deposition route.The resulting Pd_(100−x)Cu_(x)/TiO_(2) sample shows the significantly enhanced photocatalytic H_(2)‐generation performance(269.2μmol h^(−1)),which is much higher than the bare TiO2.Based on in situ irradiated X‐ray photoelectron spectroscopy(ISI‐XPS)and density functional theory(DFT)results,the as‐formed Pd_(100−x)Cu_(x) alloy nanodots can effectively promote the separation of photo‐generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen‐desorption process on Pd_(75)Cu_(25) alloy,thus leading to high photocatalytic H_(2)‐evolution activity.Herein,the weakened H adsorption of Pd_(75)Cu_(25) cocatalyst can be ascribed to the formation of electron‐rich Pd after the introduction of weak electronegativity Cu.The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.展开更多
文摘Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen‐adsorption strength to improve its interfacial H_(2)‐evolution rate via the Pd‐Cu alloying effect.Herein,the ultrasmall Pd_(100−x)Cu_(x) alloy nanodots(2−5 nm)as a novel H_(2)‐evolution cocatalyst were integrated with the TiO_(2) through a simple NaH_(2)PO_(2)‐mediated co‐deposition route.The resulting Pd_(100−x)Cu_(x)/TiO_(2) sample shows the significantly enhanced photocatalytic H_(2)‐generation performance(269.2μmol h^(−1)),which is much higher than the bare TiO2.Based on in situ irradiated X‐ray photoelectron spectroscopy(ISI‐XPS)and density functional theory(DFT)results,the as‐formed Pd_(100−x)Cu_(x) alloy nanodots can effectively promote the separation of photo‐generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen‐desorption process on Pd_(75)Cu_(25) alloy,thus leading to high photocatalytic H_(2)‐evolution activity.Herein,the weakened H adsorption of Pd_(75)Cu_(25) cocatalyst can be ascribed to the formation of electron‐rich Pd after the introduction of weak electronegativity Cu.The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.
