Composite Si-O-metal network catalysts with uneven electron distribution: Enhanced activity and electron transfer for catalytic ozonation of carbamazepine

[Display omitted] •The Co-Ce-MCM-48/O3 could mineralize carbamazepine efficiently.•The Si-O-Metal shell was fitted by X-ray absorption fine structure analysis.•The electron distribution of catalysts with improved redox behavior was uneven.•The interaction between ozone and catalysts was enhanced due...

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Bibliographic Details
Published in:Applied catalysis. B, Environmental Environmental, 2020-04, Vol.263, p.118311, Article 118311
Main Authors: Li, Shangyi, Wang, Jing, Ye, Yiyun, Tang, Yiming, Li, Xukai, Gu, Fenglong, Li, Laisheng
Format: Article
Language:English
Subjects:
Bonding bridge
Carbamazepine
Catalysts
Catalytic ozonation
Composite materials
Density functional theory
Electron distribution
Electron transfer
Electrons
Energy gap
Immobilization
Intermediates
MCM-48
Metal bonding
Mineralization
Molecular sieves
NMR
Nuclear magnetic resonance
Ozonation
Ozone
Reactive oxygen species
Synergistic effect
X ray absorption
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Summary:[Display omitted] •The Co-Ce-MCM-48/O3 could mineralize carbamazepine efficiently.•The Si-O-Metal shell was fitted by X-ray absorption fine structure analysis.•The electron distribution of catalysts with improved redox behavior was uneven.•The interaction between ozone and catalysts was enhanced due to Co-Ce doping.•Co-O-Si-O-Si-O-Ce units showed the lowest HOMO-LUMO energy gap. Electron-rich center and electron-poor center were formed around Si and metal atom linked via Si-O-metal bonding bridge in the Co-Ce doping mesoporous molecular sieves MCM-48 for catalytic ozonation of carbamazepine (CBZ). The density functional theory (DFT) calculations of Co-Ce-MCM-48 concluded that unique Co-O-Si-O-Si-O-Ce had a much lower energy gap than those of Si-O-Si-O-Si-O-Si, Co-O-Si-O-Si-O-Ce and Co-O-Si-O-Si-O-Ce. The successful immobilization of Co-Ce was verified by X-ray absorption fine-structure (XAFS), Raman and 29Si MAS-NMR spectrum. Co-Ce-MCM-48/O3 process achieved 75.6% mineralization of CBZ at 60 min by generation of reactive oxygen species (ROSs) and enhanced redox behaviors of Ce(Ⅲ)/Ce(Ⅳ) and Co(Ⅱ)/Co(Ⅲ). Two new intermediates (P13 and P14) of CBZ in Co-Ce-MCM-48/O3 were observed by DFT and LCMS/MS results. This study opened a new insight by employing an integration of theoretical and experimental techniques to elucidate the synergistic effect of uneven electrons distribution at Co-O-Si-O-Si-O-Ce and catalytic reaction pathway of CBZ.
ISSN:0926-3373
1873-3883
DOI:10.1016/j.apcatb.2019.118311