H x Zr 3‐x PW 12 O 40 as an Insoluble and Reusable Heteropolyacid for Highly Selective Dehydration of Fructose to 5‐Hydroxymethyl Fufural in DMSO System

Dehydration of fructose is a way to produce an important platform chemical such as 5‐hydroxymethylfurfural (HMF) which is widely used to synthesize variety of renewable chemicals and fuel. Heteropoly acid, H 3 PW 12 O 40 is highly soluble strong acidic catalyst with well‐defined structure. This study reports the modification of soluble heteropoly acid to insoluble and reusable heteropolyacid (H x Zr 3‐x PW 12 O 40 ) by exchanging with Zr and investigation of its catalytic performance in selective transformation of renewable fructose to 5‐HMF in Dimethyl sulfoxide (DMSO) system. The physico‐chemical properties of H x Zr 3‐x PW 12 O 40 were derived from Powder‐XRD, NH 3 ‐TPAD and FT‐IR technique. The characterization of H x Zr 3‐x PW 12 O 40 revealed that the Keggin structure of HPA remained intact as proton replaced by Zr. The partial exchange of Zr in H 2 Zr 1 PW 12 O 40 catalyst resulted in an increase in acidity, however further increase of Zr above 1, acidity was found to be decreased. At optimized reaction condition, 5‐HMF yield of 85% with 100% selectivity was achieved with H 1 Zr 2 PW 12 O 40 catalyst at much lower reaction time of 10 min than reported. The catalyst was observed to be recoverable, reusable as compared to parent H 3 PW 12 O 40 .