As an excellent clean medium for hydrogen storage and fuel cell applications,the photolysis of ammonia via localized surface plasmon could be invoked as a promising route towards significantly reducing the temperature...As an excellent clean medium for hydrogen storage and fuel cell applications,the photolysis of ammonia via localized surface plasmon could be invoked as a promising route towards significantly reducing the temperature for conventional thermolysis.Here,we explore the underlying microscopic mechanism of ultrafast carrier dynamics in plasmon-mediated NH3 photodecomposition at the single-molecular level using real-time time-dependent density functional theory.The NH_(3)molecule adsorbed on the tip of archetypal magic metal clusters represented by tetrahedral Ag_(2)0 and icosahedral Ag147,splits within a hundred femtoseconds upon laser pulse illumination.We found that the splitting of the first N-H bond is dominated by the intramolecular charge transfer driven by localized surface plasmon.Surprisingly,the phase of laser pulse could modulate the dynamics of charge transfer and thus affect the plasmon-induced bond breaking.These findings offer a new avenue for NH3 decomposition and provide in-depth insights in designing highly efficient plasmon-mediated photocatalysts.展开更多
基金We acknowledge financial support from MOST,the National Key Research and Development Project(No.2021YFA1400200)the National Natural Science Foundation of China(NSFC)(Nos.12025407,11774396,91850120,11934003,and 11674289)CAS(XDB330301).
文摘As an excellent clean medium for hydrogen storage and fuel cell applications,the photolysis of ammonia via localized surface plasmon could be invoked as a promising route towards significantly reducing the temperature for conventional thermolysis.Here,we explore the underlying microscopic mechanism of ultrafast carrier dynamics in plasmon-mediated NH3 photodecomposition at the single-molecular level using real-time time-dependent density functional theory.The NH_(3)molecule adsorbed on the tip of archetypal magic metal clusters represented by tetrahedral Ag_(2)0 and icosahedral Ag147,splits within a hundred femtoseconds upon laser pulse illumination.We found that the splitting of the first N-H bond is dominated by the intramolecular charge transfer driven by localized surface plasmon.Surprisingly,the phase of laser pulse could modulate the dynamics of charge transfer and thus affect the plasmon-induced bond breaking.These findings offer a new avenue for NH3 decomposition and provide in-depth insights in designing highly efficient plasmon-mediated photocatalysts.
