Heteropolyacid catalysts for Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to renewable p-xylene

Yanuar Philip Wijaya, Haryo Pandu Winoto, Young Kwon Park, Dong Jin Suh, Hyunjoo Lee, Jeong Myeong Ha, Jungho Jae

Research output: Contribution to journalArticlepeer-review

47 Scopus citations


The Diels-Alder cycloaddition of biomass-derived furans and subsequent dehydration are promising routes for the sustainable production of commodity chemicals such as p-xylene (PX). In this paper, we have investigated the catalytic performances of a range of phosphotungstic acid (HPW) and silicotungstic acid (HSiW) catalysts supported on various oxides, i.e., SiO2, Al2O3, TiO2 and ZrO2 and their structure-activity correlation in the conversion of 2,5-dimethylfuran (DMF) and ethylene to PX. The characterization studies of the catalysts using XRD, BET, Raman and 31P MAS-NMR spectroscopy reveal that all of the supported heteropolyacid (HPA) catalysts (except HPW/ZrO2) retain their Keggin structure on the surface of oxide supports. Results from ammonia- and n-propylamine-TPD studies show that all of the supported HPA catalysts possess well-defined Brønsted acid sites with the total acidity decreasing in the following order: HPA/SiO2 > HPA/Al2O3 > HPA/ZrO2 > HPA/TiO2. The conversion of DMF and the initial rate of PX production generally increase with an increase in the total acidity, with HPA/SiO2 being the most active catalyst. The turnover frequency of PX production for HPA/SiO2 is also considerably greater than those for the HPAs supported on Al2O3, ZrO2, and TiO2, which suggests that the higher activity of HPA/SiO2 is at least partly due to the enhanced strength of Brønsted acid sites. Both the silica-supported HSiW and HPW catalysts demonstrate remarkably high PX selectivity (82–85%) at high DMF conversion (91–94%) at 250 °C after 6 h reaction. The effects of reaction conditions such as acid loading, reaction temperature, and reaction time have also been investigated with the most active silica-supported HSiW catalysts to optimize the PX yield.

Original languageEnglish
Pages (from-to)167-175
Number of pages9
JournalCatalysis Today
StatePublished - 2017


  • 2,5-Dimethylfuran
  • Biomass
  • Diels-Alder
  • Heteropolyacids
  • p-Xylene


Dive into the research topics of 'Heteropolyacid catalysts for Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to renewable p-xylene'. Together they form a unique fingerprint.

Cite this