Abstract
Periodic density functional theory (DFT) calculations were carried out to investigate the mechanism of glucose to fructose isomerization over tungstite (WO3·H2O). The isomerization reaction is catalyzed by undercoordinated W6+ sites. The reaction mechanism proceeds through an H-shift from C2 to C1 and involves a cooperative action of Lewis acidic tungsten sites with neighboring proton donors, which form a hydrogen-bonding surface network. Dopants of group IV-VI transition metals stabilize the preactivated complex, which is the deprotonated open form of glucose adsorbed to the surface. In particular, calculations reveal that doping the tungstite structure with Nb5+ and Ti4+ ions is effective in lowering the overall barrier for glucose isomerization.
Original language | English |
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Pages (from-to) | 4162-4169 |
Number of pages | 8 |
Journal | ACS Catalysis |
Volume | 6 |
Issue number | 7 |
DOIs | |
Publication status | Published - 23 May 2016 |
Externally published | Yes |
Keywords
- aldose-ketose isomerization
- biomass conversion
- cooperative catalysis
- heterogeneous catalysis
- hydrogen bonding
- lignocellulose
- surface doping
- tungstite