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The interfacial contact between TiO 2 and graphitic carbon in a hybrid composite plays a critical role in electron transfer behavior, and in turn, its photocatalytic efficiency. Herein, we report a new approach for improving the interfacial contact and delaying charge carrier recombination in the hybrid by wrapping short single-wall carbon nanotubes (SWCNTs) on TiO 2 particles (100 nm) via a hydration-condensation technique. Short SWCNTs with an average length of 125 ± 90 nm were obtained from an ultrasonication-assisted cutting process of pristine SWCNTs (1–3 μm in length). In comparison to conventional TiO 2 –SWCNT composites synthesized from long SWCNTs (1.2 ± 0.7 μm), TiO 2 wrapped with short SWCNTs showed longer lifetimes of photogenerated electrons and holes, as well as a superior photocatalytic activity in the gas-phase degradation of acetaldehyde. In addition, upon comparison with a TiO 2 –nanographene “quasi-core–shell” structure, TiO 2 -short SWCNT structures offer better electron-capturing efficiency and slightly higher photocatalytic performance, revealing the impact of the dimensions of graphitic structures on the interfacial transfer of electrons and light penetration to TiO 2 . The engineering of the TiO 2 –SWCNT structure is expected to benefit photocatalytic degradation of other volatile organic compounds, and provide alternative pathways to further improve the efficiency of other carbon-based photocatalysts.
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Electron shuttle in the MOF derived TiO 2 /CuO heterojunction boosts light driven hydrogen evolution
Metal organic frameworks (MOFs) have emerged as a novel template to develop porous photocatalytic materials for solar fuel conversion. In this work, we report the synthesis, charge separation dynamics, and photocatalytic performance of the TiO 2 /CuO heterostructure derived from mixed-phase MOFs based on Ti and Cu metal nodes, which demonstrates significantly enhanced catalytic activity for the hydrogen evolution reaction (HER) compared to metal oxides derived from single node MOFs. More importantly, using transient absorption spectroscopy, we identified the specific role each component in the heterostructure plays and unravelled the key intermediate species that is responsible for the exceptional photocatalytic activity of the heterostructure. We found that the HER is initiated with ultrafast electron transfer (<150 fs) from the molecular photosensitizer to the conduction band of TiO 2 , where TiO 2 acts as an electron mediator and shuttles the electron to the CuO cocatalyst, facilitating charge separation and ultimately boosting the HER efficiency. These results not only demonstrate the great potential of using mixed-phase MOFs as templates to synthesize mesoporous heterostructure photocatalysts but also provide important insight into the HER mechanism.
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- Award ID(s):
- 1706971
- PAR ID:
- 10303780
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 9
- Issue:
- 10
- ISSN:
- 2050-7488
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0TA12220C
