Exploiting an Efficient and Stable Catalyst for the Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by Incorporating Vanadium in the Framework of Hydroxyapatite

Abstract

Hydroxyapatite displays immense potential in catalysis because of its properties to form doped single and multiphasic systems. In the present study, vanadium-incorporated hydroxyapatite was investigated for aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran. The amount of vanadium precursor and the pH in catalyst synthesis were significant factors in defining the catalytic properties of V-HAP. The morphologies and structures of the catalysts were well studied. Field emission scanning electron microscopy revealed different morphologies of the catalyst with varying amounts of vanadium and pH, suggesting that both these factors play a critical role in determining the catalytic properties. Through X-ray diffraction spectra, the incorporation of vanadium ions into the HAP framework by replacing phosphate ions was confirmed by the augmentation of lattice parameters and unit cell volume. The vanadium amount corresponding to x = 3 and pH 11 for the synthesis of the catalyst displayed good catalytic efficiency for HMF conversion. To further enhance the performance of the synthesized catalyst, the reaction parameters such as the temperature of reaction and catalyst loading were optimized. Under optimum reaction conditions, 78% HMF conversion with 63 and 81% DFF yield and selectivity, respectively, was observed. V-HAP (x = 3) was highly stable in nature and did not show a decrease in activity during experimental cycles, thereby showing that the incorporated vanadium did not leach out and that the catalyst was recyclable, which was also confirmed by energy-dispersive X-ray spectroscopy results. V-HAP (x = 3) was also compared with V2O5-HAP and was found to have superior catalytic properties as compared to the latter. This study contributes to the development of green and stable catalysts for biomass conversion.

Recent Progress in Metal‐Catalyzed Selective Oxidation of 5‐Hydroxymethylfurfural into Furan‐Based Value‐Added Chemicals

“…Except the above‐mentioned noble metals, V has also been widely utilized in this transformation. In general, various V species with chemical valences of V 5+ or V 4+ have been loaded to different carriers, such as H‐Beta, [39] metal oxides, [40] activated carbon, [41] carbon nanotubes, [42] carbon spheres, [43] ceramic powders, [44] hydroxyapatite (HAP) [45] and zeolites, [46] etc (as listed in Table 2).…”

Investigation of CoNi/Hydroxyapatite for Catalytic Deoxygenation of Biorenewable Platform Molecules under Solvent-Free Conditions

“…Our research group has effectively combined earth-abundant transition metals with natural clay and a SiO 2 –Al 2 O 3 support system for excellent selectivity of biodiesel and bio jet fuel. ,, Researchers have investigated the catalytic role of HAP, a biomineral that is a major component of bones and teeth (50% by volume and 70% by weight) . The hydroxyapatite (HAP) support catalyst also exhibits several outstanding qualities, including higher surface area, superior thermal stability, and acid–base properties . The naturally abundant, minerals-loaded HAP catalyst was explored in catalytic reactions .…”

Pd/HAP Catalyzed Synthesis of Adipic Acid from 1,6‐Hexanediol under Aerial Base‐free Conditions

“…[40] In a similar direction, Zhao et al reported selective oxidation of 5hydroxymethylfurfural to 2,5-diformylfuran using vanadium incorporated HAP at 150 °C in DMSO and 15 mL/min O 2 with 78 % conversion and 63 % yield. [41] Very recently, Hau et al used Pd/HAP catalyst for oxidation of glycerol to glyceric acid under aqueous basic conditions and 10 bar O 2 at 80 °C and achieved 59 % conversion with 90 % selectivity for glyceric acid. [42] Though the catalytic activities of hydroxyapatite-supported catalysts have been explored for various oxidation reactions, additive-free aerial oxidation of HDO and related diols is rarely investigated.…”

“…In a similar direction, Zhao et al . reported selective oxidation of 5‐hydroxymethylfurfural to 2,5‐diformylfuran using vanadium incorporated HAP at 150 °C in DMSO and 15 mL/min O 2 with 78 % conversion and 63 % yield [41] . Very recently, Hau et al .…”