Experimental and Computational Studies of the Production of 1,3-Butadiene from 2,3-Butanediol Using SiO2-Supported H3PO4 Derivatives

Juan Alegre-Requena, Glenn Hafenstine, Xiangchen Huo, Yanfei Guan, Jim Stunkel, Frederick Baddour, Kinga Unocic, Bruno Klein, Ryan Davis, Robert Paton, Derek Vardon, Seonah Kim

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2 Scopus Citations


Silica-supported phosphoric acid and metal phosphate catalyzed 1,3-butadiene (BDE) production from 2,3-butanediol (2,3-BDO) was studied using experimental and computational techniques. The catalyst was initially tested in a continuous flow reactor using commercially available 2,3-BDO, leading to maximum BDE yields of 63C%. Quantum chemical mechanistic studies revealed 1,2-epoxybutane is a kinetically viable and thermodynamically stable intermediate, supported by experimental demonstration that this epoxide can be converted to BDE under standard reaction conditions. Newly proposed E2 and SN2′ elementary steps were studied to rationalize the formation of BDE and all detected side-products. Additionally, using quantum mechanics/molecular mechanics (QM/MM) calculations, we modeled silica-supported phosphate catalysts to study the effect of the alkali metal center. Natural population analysis showed that phosphate oxygen atoms are more negatively charged in CsH2PO4/SiO2 than in H3PO4/SiO2. In combination with temperature-programmed desorption experiments using CO2, the results of this study suggest that the improved selectivity achieved when adding the metal center is related to an increase in the basicity of the catalyst.

Original languageAmerican English
Article number143346
Number of pages9
JournalChemical Engineering Journal
StatePublished - 2023

Bibliographical note

Publisher Copyright:
© 2023

NREL Publication Number

  • NREL/JA-5100-86476


  • 2,3-butanediol
  • Butadiene
  • Computational chemistry
  • HPO derivatives
  • Heterogeneous catalysis
  • Mechanistic studies
  • QM/MM


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