In Situ Raman Probing of Hot‐Electron Transfer at Gold–Graphene Interfaces with Atomic Layer Accuracy

• Published in: Angewandte Chemie International Edition Vol. 61; no. 5; pp. e202112749 - n/a
• Main Authors: Yang, Jing‐Liang, Wang, Hong‐Jia, Zhu, Zhenwei, Yue, Mu‐Fei, Yang, Wei‐Min, Zhang, Xia‐Guang, Ruan, Xiangyu, Guan, Zhiqiang, Yang, Zhi‐Lin, Cai, Weiwei, Wu, Yuan‐Fei, Fan, Feng‐Ru, Dong, Jin‐Chao, Zhang, Hua, Xu, Hongxing, Tian, Zhong‐Qun, Li, Jian‐Feng
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 26.01.2022
• Edition: International ed. in English
• Subjects: Chemical reactions; Density functional theory; Electric fields; Electrochemistry; Electron transfer; Gold; gold nanoparticles; Graphene; Graphical user interface; Heavy metals; Hot electrons; Interfaces; Nanoparticles; Photoexcitation; plasmon-induced photocatalysis; Plasmonics; Raman spectroscopy; surface-enhanced Raman spectroscopy; Transportation; Two dimensional materials; hot electrons; plasmon-induced photocatalysis; gold nanoparticles; graphene; surface-enhanced Raman spectroscopy
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202112749

Plasmonic metals under photoexcitation can generate energetic hot electrons to directly induce chemical reactions. However, the capability and fundamental insights of the transportation of these hot electrons at plasmonic metal‐2D material interfaces remain unclear. Herein, hot‐electron transfer at Au‐graphene interfaces has been in situ studied using surface‐enhanced Raman spectroscopy (SERS) with atomic layer accuracy. Combining in situ SERS studies with density functional theory calculations, it is proved that hot electrons can be injected from plasmonic Au nanoparticles to graphene and directly penetrate graphene to trigger photocatalytic reactions. With increasing graphene layers, the transportation of hot electrons decays rapidly and would be completely blocked after five layers of graphene. Moreover, the transfer of hot electrons can be modulated by applying an external electric field, and the hot‐electron transfer efficiency under electrochemical conditions is improved by over three times in the presence of a monolayer of graphene. Hot‐electron transfer at Au–graphene interfaces has been investigated in situ with atomic layer accuracy, and it is shown that hot electrons can be injected from plasmonic Au nanoparticles to graphene and penetrate up to four layers of graphene.