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Phosphorylated carbons have been reported to be effective catalysts in dehydration reactions for biomass valorization. The amount and the nature of P groups are a key parameter affecting the catalytic performances of functionalized materials. Herein, we investigate the role of structural and surface properties of carbon-based materials, specifically carbon nanofibers, in determining the amount of P-functionalities. In order to incorporate P groups on carbon surfaces, various carbon nanofibers (CNFs) with different graphitization degrees have been functionalized through treatment with a H3PO4-HNO3 mixture at 150 °C. The pristine materials, as well as the functionalization protocol, were properly selected to achieve an effective functionalization without drastically altering the morphology of the samples. Surface and structural properties of the synthesized functionalized materials have been investigated by means of transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The catalytic behavior of phosphorylated carbon nanofibers has been evaluated in the selective dehydration of fructose to hydroxymethylfurfural (HMF) to elucidate structure-activity relationships.

Controlling the Incorporation of Phosphorus Functionalities on Carbon Nanofibers: Effects on the Catalytic Performance of Fructose Dehydration