Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO2 Composites

He, Xiang; Fang, Hong; Gosztola, David J.; Jiang, Zhang; Jena, Puru; Wang, Wei-Ning

doi:10.1021/acsami.9b00223

Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO₂ Composites

Journal Article · Wed Mar 13 00:00:00 EDT 2019 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.9b00223· OSTI ID:1546061

He, Xiang ^[1]; ^[1]; ^[2]; Jiang, Zhang ^[2]; ^[1]; ^[1]

Virginia Commonwealth Univ., Richmond, VA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Lemont, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1546061

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 13 Vol. 11; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Computational Studies of Photocatalysis with Metal–Organic Frameworks Wu, Xin‐Ping; Choudhuri, Indrani; Truhlar, Donald G. ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 4 https://doi.org/10.1002/eem2.12051	journal	September 2019
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TiO ₂ nanocrystals with the {001} and {101} facets co-exposed with MIL-100(Fe): an egg-like composite nanomaterial for efficient visible light-driven photocatalysis Wu, Wan; Zhu, Jie; Deng, Yue Hong RSC Advances, Vol. 9, Issue 54 https://doi.org/10.1039/c9ra06359e	journal	January 2019

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge transfer
defect energy level
metal-organic framework
photocatalysis
transient absorption spectroscopy