Aromatic amines(AAs)are widely used in manufacturing industries,where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds.Understanding their reactivity is a ...Aromatic amines(AAs)are widely used in manufacturing industries,where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds.Understanding their reactivity is a prerequisite for their use in various fields.Given their chemical diversity and significance,the behavior of AAs on surfaces is of considerable interest for potential applications.Herein,we combined scanning tunneling microscopy(STM)and X-ray photoelectron spectroscopy(XPS)to explore the reactivity of AAs on silver(Ag)and gold(Au)surfaces using a gas-mediated reaction strategy.Our results revealed that oxidative dehydrogenation was readily achieved after O_(2)-mediated treatment on Ag surfaces,leading to the formation of organometallic nanopores,while AAs remained unperturbed on Au(111),indicating a substrate-dependent behavior.Density functional theory(DFT)calculations corroborate the experimental observations,by simulated core-level shifts and microscopy images,and demonstrate how the choice of substrate dictates the thermodynamics of the overall reactions.These findings emphasize the importance of substrate selection in modulating the surface chemistry of AAs,paving the way for more efficient catalytic processes and material design.展开更多
基金This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(grant nos.U24A20496 and 22402139)the Natural Science Foundation of Jiangsu Province,China(grant no.BK20240765)the German Research Foundation via the Excellence Cluster e-conversion.
文摘Aromatic amines(AAs)are widely used in manufacturing industries,where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds.Understanding their reactivity is a prerequisite for their use in various fields.Given their chemical diversity and significance,the behavior of AAs on surfaces is of considerable interest for potential applications.Herein,we combined scanning tunneling microscopy(STM)and X-ray photoelectron spectroscopy(XPS)to explore the reactivity of AAs on silver(Ag)and gold(Au)surfaces using a gas-mediated reaction strategy.Our results revealed that oxidative dehydrogenation was readily achieved after O_(2)-mediated treatment on Ag surfaces,leading to the formation of organometallic nanopores,while AAs remained unperturbed on Au(111),indicating a substrate-dependent behavior.Density functional theory(DFT)calculations corroborate the experimental observations,by simulated core-level shifts and microscopy images,and demonstrate how the choice of substrate dictates the thermodynamics of the overall reactions.These findings emphasize the importance of substrate selection in modulating the surface chemistry of AAs,paving the way for more efficient catalytic processes and material design.
