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Selective removal of oxygen from biomass-derived polyols is critical toward bridging the gap between biomass feedstocks and the production of commodity chemicals. In this work, we show that earth-abundant molybdenum oxide based heterogeneous catalysts are active, selective, and stable for the cleavage of vicinal C–O bonds in biomass-derived polyols. Catalyst characterization (Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)) shows that partially reduced MoOx centers are responsible for C–O bond cleavage and are generated in situ by hydrogen dissociated atoms over palladium (Pd) nanoparticles. We find that the support, TiO2, facilitates communication between the hydrogen dissociating metal and dispersed MoOx sites through hydrogen spillover. Reactivity studies using a biomass-derived model substrate (1,4-anhydroerythritol) show the effective removal of vicinal hydroxyls over MoOx-Pd/TiO2 producing tetrahydrofuran with >98% selectivity at 29% conversion. Catalyst stability is demonstrated upon cycling. These studies are critical toward the development of low-cost heterogeneous catalysts for sustainable hydrodeoxygenation of biobased polyols to platform chemicals.
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Selective C−O Bond Cleavage of Bio‐Based Organic Acids over Palladium Promoted MoO x /TiO 2
Abstract Hydrodeoxygenation chemistries play a key role in the upgrading of biomass‐derived feedstocks. Among these, the removal of targeted hydroxyl groups through selective C−O bond cleavage from molecules containing multiple functionalities over heterogeneous catalysts has shown to be a challenge. Herein, we report a highly selective and stable heterogeneous catalyst for hydrodeoxygenation of tartaric acid to succinic acid. The catalyst consists of reduced Mo5+centers promoted by palladium, which facilitate selective C−O bond cleavage, while leaving intact carboxylic acid end groups. Stable catalytic performance over multiple cycles is demonstrated. This catalytic system opens up opportunities for selective processing of biomass‐derived sugar acids with a high degree of chemical functionality.
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- PAR ID:
- 10256759
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemCatChem
- Volume:
- 13
- Issue:
- 5
- ISSN:
- 1867-3880
- Page Range / eLocation ID:
- p. 1294-1298
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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