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Title: Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO 2 Composites

Abstract

The integration of metal organic frameworks (MOFs) with semiconductors has attracted mounting attention for photocatalytic applications. However, more efforts are needed to unravel the interface structure in MOF/semiconductor composites and its role in charge transfer. In this paper, a MIL-100(Fe)/TiO 2 composite was synthesized as a prototypical photocatalyst and studied systematically to explore the interface structure and unravel the charge transfer pathways during the photocatalytic processes. The composite was fabricated by growing MIL-100(Fe) crystals on TiO 2 using surface-coated FeOOH as the precursor. The as-prepared MIL-100(Fe)/TiO 2 exhibited significantly improved photocatalytic performance over pristine TiO 2, which was mainly because of the enhanced charge separation as confirmed by transient absorption spectroscopy analysis. This enhancement partially arose from the special chemical structure at the interface, where the Fe-O-Ti bond was formed. As verified by the density functional theory calculation, this distinct structure would create defect energy levels adjacent to the valence band maximum of TiO 2. During the photocatalytic processes, the defect energy levels serve as sinks to capture excited charge carriers and retard the recombination, which subsequently leads to the increased charge density and promoted photocatalytic efficiency. Meanwhile, the intimate interactions between MIL-100(Fe) and TiO 2 would also help tomore » improve the charge separation by transferring photo-induced holes through the ligands to Fe-O clusters. Lastly, these findings would advance the fundamental understanding of the interface structure and the charge transfer pathways in MOF/semiconductor composite photocatalysts.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Virginia Commonwealth Univ., Richmond, VA (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1546061
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 13; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; charge transfer; defect energy level; metal-organic framework; photocatalysis; transient absorption spectroscopy

Citation Formats

He, Xiang, Fang, Hong, Gosztola, David J., Jiang, Zhang, Jena, Puru, and Wang, Wei-Ning. Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO2 Composites. United States: N. p., 2019. Web. doi:10.1021/acsami.9b00223.
He, Xiang, Fang, Hong, Gosztola, David J., Jiang, Zhang, Jena, Puru, & Wang, Wei-Ning. Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO2 Composites. United States. doi:10.1021/acsami.9b00223.
He, Xiang, Fang, Hong, Gosztola, David J., Jiang, Zhang, Jena, Puru, and Wang, Wei-Ning. Wed . "Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO2 Composites". United States. doi:10.1021/acsami.9b00223.
@article{osti_1546061,
title = {Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO2 Composites},
author = {He, Xiang and Fang, Hong and Gosztola, David J. and Jiang, Zhang and Jena, Puru and Wang, Wei-Ning},
abstractNote = {The integration of metal organic frameworks (MOFs) with semiconductors has attracted mounting attention for photocatalytic applications. However, more efforts are needed to unravel the interface structure in MOF/semiconductor composites and its role in charge transfer. In this paper, a MIL-100(Fe)/TiO2 composite was synthesized as a prototypical photocatalyst and studied systematically to explore the interface structure and unravel the charge transfer pathways during the photocatalytic processes. The composite was fabricated by growing MIL-100(Fe) crystals on TiO2 using surface-coated FeOOH as the precursor. The as-prepared MIL-100(Fe)/TiO2 exhibited significantly improved photocatalytic performance over pristine TiO2, which was mainly because of the enhanced charge separation as confirmed by transient absorption spectroscopy analysis. This enhancement partially arose from the special chemical structure at the interface, where the Fe-O-Ti bond was formed. As verified by the density functional theory calculation, this distinct structure would create defect energy levels adjacent to the valence band maximum of TiO2. During the photocatalytic processes, the defect energy levels serve as sinks to capture excited charge carriers and retard the recombination, which subsequently leads to the increased charge density and promoted photocatalytic efficiency. Meanwhile, the intimate interactions between MIL-100(Fe) and TiO2 would also help to improve the charge separation by transferring photo-induced holes through the ligands to Fe-O clusters. Lastly, these findings would advance the fundamental understanding of the interface structure and the charge transfer pathways in MOF/semiconductor composite photocatalysts.},
doi = {10.1021/acsami.9b00223},
journal = {ACS Applied Materials and Interfaces},
number = 13,
volume = 11,
place = {United States},
year = {2019},
month = {3}
}

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