4.8 Article

Synergistic Effect between CO2 Chemisorption Using Amino-Modified Carbon Nitride and Epoxide Activation by High-Energy Electrons for Plasmon-Assisted Synthesis of Cyclic Carbonates

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 14, Issue 45, Pages 51029-51040

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.2c16382

Keywords

surface plasmon resonance; plasmon-assisted CO2 cycloaddition reaction; high-energy electrons; activation of propylene oxide; single-particle photoluminescence study

Funding

  1. National Natural Science Foundation of China [22072072, 22102087]
  2. Shandong University multidisciplinary research and innovation team of young scholars [2020QNQT11]
  3. Natural Science Foundation of Shandong Province [ZR2021JQ06, ZR2021QB040]
  4. National Key Research and Development Program of China [2020YFA0710301]
  5. China Postdoctoral Science Foundation [2021M691901]
  6. Qilu Young Scholars and Outstanding Young Scholars Projects of Shandong University

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This study introduces g-C3N4/Ag hybrids as a promising catalyst for CO2 cycloaddition. The coupling of a semiconductor into the plasmonic system enhances the activity of the reaction. The mechanism involves CO2 chemisorption by ACN and the activation of propylene oxide by photo-generated electrons from ACN transferring to Ag. Experimental evidence confirms the importance of plasmon excitation.
Photocatalytic CO2 cycloaddition is a promising approach for CO2 value-added processes. However, the efficiency of plasmon-assisted CO2 cycloaddition still needs to be improved and the reaction mechanism is unclear. Herein, g-C3N4/Ag (ACN-Ag) hybrids exhibited superior activity of CO2 cycloaddition by coupling a semiconductor into the plasmonic system, in which the ACN grafting amino group by the formation of carbon vacancies can enhance CO2 chemisorption; meanwhile, photo-generated electrons from ACN transfer to Ag to form high-energy electrons, which can activate propylene oxide, accelerating the ring-opening step. Importantly, photo-generated electron injection from ACN to Ag and the interaction between Ag nanoparticles and ACN were confirmed by single-particle photoluminescence spectroscopy. The wavelength-dependent activity demonstrated that the plasmon excitation is crucial for the reaction. Moreover, in situ single-particle PL quenching caused by propylene oxide and in situ electron paramagnetic resonance verified the activation of propylene oxide by ACN-Ag. This work is conducive to an in-depth understanding of the mechanism of CO2 cycloaddition at the single-particle level and provides guidance for the organic synthesis.

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