Selective Metal-Organic Framework Catalysis of Glucose to 5-Hydroxymethylfurfural Using Phosphate-Modified NU-1000

Mizuho Yabushita, Peng Li, Timur Islamoglu, Hirokazu Kobayashi, Atsushi Fukuoka, Omar K. Farha, Alexander Katz

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73 Citations (Scopus)


This manuscript demonstrates the synthesis of selective Lewis-acid sites in a metal-organic framework (MOF) for glucose transformation to 5-hydroxymethylfurfural (HMF). These sites are synthesized via partial phosphate modification of zirconia-cluster nodes in MOF NU-1000, which titrates strong Lewis-acid sites that would lead to undesired side reactions. Our mechanistic study using isotope tracer analysis and kinetic isotope effect measurements reveals that an isomerization-dehydration mechanism mainly occurs on the MOF catalyst, where fructose is an intermediate. This mechanism suggests that dilute concentrations are favorable in order to suppress undesired intermolecular condensation of glucose/fructose/HMF and maximize HMF yield. We demonstrate both high yield and selectivity of HMF formation of 64% with the MOF catalyst, at an initial glucose concentration of 1 mM in water/2-propanol. In stark contrast, similar partial phosphate modification of a bulk zirconia yields a catalyst that exhibits poor HMF selectivity, while possessing nearly identical Brønsted acidity to the selective NU-1000-based catalyst.

Original languageEnglish
Pages (from-to)7141-7148
Number of pages8
JournalIndustrial and Engineering Chemistry Research
Issue number25
Publication statusPublished - 2017 Jun 28
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering


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