TY - JOUR
T1 - Experimental and Computational Studies of the Production of 1,3-Butadiene from 2,3-Butanediol Using SiO2-Supported H3PO4 Derivatives
T2 - Article No. 143346
AU - Alegre-Requena, Juan
AU - Hafenstine, Glenn
AU - Huo, Xiangchen
AU - Guan, Yanfei
AU - Stunkel, Jim
AU - Baddour, Frederick
AU - Unocic, Kinga
AU - Klein, Bruno
AU - Davis, Ryan
AU - Paton, Robert
AU - Vardon, Derek
AU - Kim, Seonah
PY - 2023
Y1 - 2023
N2 - 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.
AB - 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.
KW - butadiene
KW - butanediol
KW - computational chemistry
KW - H3PO4 derivatives
KW - heterogeneous catalysis
KW - mechanistic studies
KW - QM/MM
UR - http://www.scopus.com/inward/record.url?scp=85159106985&partnerID=8YFLogxK
U2 - 10.1016/j.cej.2023.143346
DO - 10.1016/j.cej.2023.143346
M3 - Article
SN - 1369-703X
VL - 466
JO - Biochemical Engineering Journal
JF - Biochemical Engineering Journal
ER -