Mechanistic role of protonated polar additives in ethanol for selective transformation of biomass-related compounds

Haixin Guo, Alif Duereh, Yaqiong Su, Emiel J.M. Hensen, Xinhua Qi, Richard Lee Smith

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

We report on a combined experimental, spectroscopic and theoretical study of acid catalysed dehydration-etherification of fructose in ethanol for understanding the mechanistic role of polar solvent additives and product selectivity. Herein, we show that polar solvent additives (e.g. tetrahydrofuran, acetone, acetonitrile, gamma-valerolactone, dimethyl sulfoxide) protonated with a common solid acid catalyst in ethanol allow transformation of biomass-related compounds into desired dehydration or etherification products. Fructose in ethanol with DMSO additive is selectively transformed into 5-hydroxymethylfurfural with negligible formation of 5-ethoxymethylfurfural due to preferential DMSO protonation according to its polarity. Spectroscopic methods and density functional theory show that additives having higher polarity than ethanol are readily protonated and act as the key catalytic protonation species and as the key stabilization species for reaction intermediates. Understanding the mechanism of protonated polar additives in reaction systems allows one to tailor selectivity in acid-catalyzed dehydration-etherification schemes and to develop sustainable chemistry for biomass resources.

Original languageEnglish
Article number118509
JournalApplied Catalysis B: Environmental
Volume264
DOIs
Publication statusPublished - 2020 May 5

Keywords

  • Acid-catalyzed protonation mechanism
  • Product selectivity
  • Proton transfer
  • Stabilization
  • Sustainable chemistry

ASJC Scopus subject areas

  • Catalysis
  • Environmental Science(all)
  • Process Chemistry and Technology

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