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Dehydration of Glucose to 5‐Hydroxymethylfurfural Using Nb‐doped Tungstite
Author(s) -
Yue Chaochao,
Li Guanna,
Pidko Evgeny A.,
Wiesfeld Jan J.,
Rigutto Marcello,
Hensen Emiel J. M.
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201600649
Subject(s) - chemistry , dehydration , isomerization , lewis acids and bases , catalysis , yield (engineering) , hydrolysis , fructose , hydroxymethylfurfural , brønsted–lowry acid–base theory , dehydration reaction , deprotonation , heterogeneous catalysis , organic chemistry , inorganic chemistry , ion , biochemistry , materials science , furfural , metallurgy
Dehydration of glucose to 5‐hydroxymethylfurfural (HMF) remains a significant problem in the context of the valorization of lignocellulosic biomass. Hydrolysis of WCl 6 and NbCl 5 leads to precipitation of Nb‐containing tungstite (WO 3 ⋅H 2 O) at low Nb content and mixtures of tungstite and niobic acid at higher Nb content. Tungstite is a promising catalyst for the dehydration of glucose to HMF. Compared with Nb 2 O 5 , fewer by‐products are formed because of the low Brønsted acidity of the (mixed) oxides. In water, an optimum yield of HMF was obtained for Nb–W oxides with low Nb content owing to balanced Lewis and Brønsted acidity. In THF/water, the strong Lewis acidity and weak Brønsted acidity caused the reaction to proceed through isomerization to fructose and dehydration of fructose to a partially dehydrated intermediate, which was identified by LC‐ESI‐MS. The addition of HCl to the reaction mixture resulted in rapid dehydration of this intermediate to HMF. The HMF yield obtained in this way was approximately 56 % for all tungstite catalysts. Density functional theory calculations show that the Lewis acid centers on the tungstite surface can isomerize glucose into fructose. Substitution of W by Nb lowers the overall activation barrier for glucose isomerization by stabilizing the deprotonated glucose adsorbate.