Open AccessIndirect to Direct Charge Transfer Transition in Plasmon‐Enabled CO 2 Photoreduction
Author(s) -
Zhang Yimin,
Yan Lei,
Guan Mengxue,
Chen Daqiang,
Xu Zhe,
Guo Haizhong,
Hu Shiqi,
Zhang Shengjie,
Liu Xinbao,
Guo Zhengxiao,
Li Shunfang,
Meng Sheng
Publication year - 2022
Publication title -
advanced science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.388
H-Index - 100
ISSN - 2198-3844
DOI - 10.1002/advs.202102978
Subject(s) - plasmon , nanoclusters , photocatalysis , chemical physics , density functional theory , nanomaterials , materials science , photochemistry , excited state , electron transfer , surface plasmon , surface plasmon resonance , nanotechnology , chemistry , optoelectronics , nanoparticle , atomic physics , catalysis , computational chemistry , physics , biochemistry
Understanding hot carrier dynamics between plasmonic nanomaterials and its adsorbate is of great importance for plasmon‐enhanced photoelectronic processes such as photocatalysis, optical sensing and spectroscopic analysis. However, it is often challenging to identify specific dominant mechanisms for a given process because of the complex pathways and ultrafast interactive dynamics of the photoelectrons. Here, using CO 2 reduction as an example, the underlying mechanisms of plasmon‐driven catalysis at the single‐molecule level using time‐dependent density functional theory calculations is clearly probed. The CO 2 molecule adsorbed on two typical nanoclusters, Ag 20 and Ag 147 , is photoreduced by optically excited plasmon, accompanied by the excitation of asymmetric stretching and bending modes of CO 2 . A nonlinear relationship has been identified between laser intensity and reaction rate, demonstrating a synergic interplay and transition from indirect hot‐electron transfer to direct charge transfer, enacted by strong localized surface plasmons. These findings offer new insights for CO 2 photoreduction and for the design of effective pathways toward highly efficient plasmon‐mediated photocatalysis.