Cooperative α-C–H activation enabled quantitative and partial photooxidation of biomass-derived 5-hydroxymethylfurfural
Photocatalytic activation of C–H bonds is versatile but challenging for undergoing oriented conversion processes. Herein, a spatially site-isolated heterojunction (ZS-Vs/ZIS) of ZnIn2S4 with strong Lewis acidity (ZIS) and ZnS with S-vacancy (ZS-Vs) is constructed for activating α-C‒H bond and formin...
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| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
KeAi Communications Co., Ltd.
2025-05-01
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| Series: | Green Energy & Environment |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2468025724003182 |
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| Summary: | Photocatalytic activation of C–H bonds is versatile but challenging for undergoing oriented conversion processes. Herein, a spatially site-isolated heterojunction (ZS-Vs/ZIS) of ZnIn2S4 with strong Lewis acidity (ZIS) and ZnS with S-vacancy (ZS-Vs) is constructed for activating α-C‒H bond and forming ·O2− to cleave the C–H bond, respectively. ZS-Vs/ZIS displays outstanding performance in visible-light partial photooxidation of bio-based 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) in an unprecedented yield of 95.7% at 25 °C. In-situ experiments and calculations reveal that Zn sites of ZIS serve as hole enrichment to adsorb HMF for α-C‒H activation via ligand-to-metal charge transfer. Shallow trap states introduced by S-vacancy in ZS-Vs act as an electron pool to realize directed O2 activation into ·O2− for breaking pre-activated α-C‒H bond in HMF to exclusively give DFF. Moreover, ZS-Vs/ZIS has good recyclability and universality in the photooxidation of various alcohols to carbonyls (86.4–95.6% yields). The synergistic C–H activation/breaking strategy exhibits high potential in targeted photocatalytic transformations. |
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| ISSN: | 2468-0257 |