Catalytic Conversion Furfuryl Alcohol to Tetrahydrofurfuryl Alcohol and 2-Methylfuran at Terrace, Step, and Corner Sites on Ni

Lifang Chen, Jingyun Ye, Yusen Yang, Pan Yin, Haisong Feng, Chunyuan Chen, Xin Zhang, Min Wei, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

Abstract

The surface structures at catalytic sites are critical factors for determining catalytic selectivity. Here, we use periodic density functional theory and microkinetic modeling to systematically investigate the effect of surface structures on the conversion of furfuryl alcohol (FA). We consider nine surface terminations of Ni with various coordination numbers representing terrace, step, and corner sites. We study three reaction paths for FA conversion on various surfaces and find that the surface structure impacts the adsorption configuration and causes significant differences in selectivity. Barrier height analysis shows that terrace sites favor hydrogenation to tetrahydrofurfuryl alcohol (THFA), whereas corner sites favor C-OH bond scission to produce 2-methylfuran (2-MF); step sites show similar barriers for the two reactions. We explain this by identifying three characteristics of the reactant adsorption structures that have a significant effect on selectivity, namely, that a shorter distance between the adsorbed hydrogen atom and the C3 carbon of FA favors hydrogenation to produce THFA, and more negative charge transfer to Oalcohol and a longer C-Oalcohol bond length favor C-Oalcohol bond scission to produce 2-MF. Since the reactions have similar barriers at a step site, microkinetic calculations are employed to calculate the product selectivity on a step site under experimental conditions. At lower temperatures and higher generalized coordination number (CN), THFA is the most favorable product, while the selectivity to 2-MF is higher at lower CN and at higher temperature. This work provides guidance for the rational design catalysts to control the product distribution of FA conversion.

Original languageEnglish (US)
Pages (from-to)7240-7249
Number of pages10
JournalACS Catalysis
Volume10
Issue number13
DOIs
StatePublished - Jul 2 2020

Bibliographical note

Funding Information:
This work was supported by the National Natural Science Foundation of China (NSFC: 91741104, 21871021, and 21521005), the National Key Research and Development Program of China (2017YFA0206804), the buctylkxj01, XK1802-6, and 12060093063 (buctylkxj01, XK1802-6, and 12060093063), the National Science Foundation (CHE–14645360), and the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0012702.

Funding Information:
This work was supported by the National Natural Science Foundation of China (NSFC: 91741104, 21871021, and 21521005) the National Key Research and Development Program of China (2017YFA0206804) the buctylkxj01, XK1802-6, and 12060093063 (buctylkxj01, XK1802-6 and 12060093063), the National Science Foundation (CHE??"14645360) and the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0012702.

Keywords

  • barrier heights
  • biomass
  • catalysis
  • furfural
  • hydrodeoxygenation
  • hydrogenation
  • microkinetic modeling
  • selectivity

Fingerprint Dive into the research topics of 'Catalytic Conversion Furfuryl Alcohol to Tetrahydrofurfuryl Alcohol and 2-Methylfuran at Terrace, Step, and Corner Sites on Ni'. Together they form a unique fingerprint.

Cite this