Au nanoparticles-anchored defective metal–organic frameworks for photocatalytic transformation of amines to imines under visible light

Au nanoparticles-anchored defective DUT-67(Zr) MOF was fabricated for photocatalytic transformation of amines to imines and the synergetic mechanism combining the plasmon with the molecular activation was illustrated. [Display omitted] Designing efficient metal organic frameworks (MOF)-based photoca...

Full description

Saved in:
Bibliographic Details
Published in:Journal of colloid and interface science 2023-02, Vol.631, p.154-163
Main Authors: Liu, Cheng, Liu, Yanyang, Shi, Yingzhang, Wang, Zhiwen, Guo, Wei, Bi, Jinhong, Wu, Ling
Format: Article
Language:English
Subjects:
Active site
benzylamines
deprotonation
DUT-67(Zr)
Fourier transform infrared spectroscopy
imines
light
Molecular activation
nanogold
oxidation
oxygen
Oxygen vacancy
Photocatalysis
photocatalysts
Plasmon
species
superoxide anion
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Au nanoparticles-anchored defective DUT-67(Zr) MOF was fabricated for photocatalytic transformation of amines to imines and the synergetic mechanism combining the plasmon with the molecular activation was illustrated. [Display omitted] Designing efficient metal organic frameworks (MOF)-based photocatalysts has recently attracted wide attention. In this work, Au nanoparticles(NPs)-decorated defective DUT-67(Zr) (Au@DUT-67(Zr)) with enlarged channels was successfully fabricated and achieved 7.5 times higher conversion than Au NPs-decorated UiO-66(Zr) (Au@UiO-66(Zr)) for photocatalytic selective oxidation of amines to imines driven by visible light. Au NPs are more effectively fixed on DUT-67(Zr) due to its partially hollow structure. Au@DUT-67(Zr) possesses more active sites including unsaturated Zr atoms and oxygen vacancies (VO) than Au@UiO-66(Zr). In situ Fourier transform infrared (FTIR) spectrum reveals that benzylamine is activated on unsaturated Zr sites via HN…Zr species, facilitating deprotonation of –CH2 in benzylamine. VO can not only adsorb and activate oxygen (O2) but also capture plasmonic hot electrons, enhancing the forming of superoxide radical (O2−). Plasmonic hot holes assisted with O2− effectively achieve the selective oxidation of benzylamine. Finally, a possible synergetic mechanism combining the plasmon with the molecular activation is presented to illustrate the photocatalytic pathway at the molecular level.
ISSN:0021-9797
1095-7103
DOI:10.1016/j.jcis.2022.11.042