Abstract
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 language | English |
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Article number | 143346 |
Journal | Chemical Engineering Journal |
Volume | 466 |
DOIs | |
State | Published - Jun 15 2023 |
Funding
R.S.P. and J.V.A.-R. acknowledge the RMACC Summit supercomputer, supported by the NSF (ACI-1532235 and ACI1532236), and the Extreme Science and Engineering Discovery Environment (XSEDE) allocations TG-CHE180056 and TG-CHE200033. J.V.A.-R. acknowledges financial support through the Gobierno de Aragón-Fondo Social Europeo (Research Group E07_23R) and a Juan de la Cierva Incorporación contract from the Ministry of Science and Innovation (MCIN) and the State Research Agency (AEI) of Spain, and the European Union (NextGenerationEU/PRTR) under grant reference IJC2020-044217-I. S.K. acknowledges XSEDE allocation TG-CHE210034 and the National Renewable Energy Laboratory Computational Science Center. This work was authored in part by the National Renewable Energy Laboratory, managed and operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding was provided by U.S. Department of Energy Office of Energy Efficiency and Renewable Energy Bioenergy Technologies Office and in collaboration with the Consortium for Computational Physics and Chemistry (CCPC) and the Chemical Catalysis for Bioenergy Consortium (ChemCatBio). G.R.H., X.H., F.G.B, K.A.U., B.C.K., R.E.D., and D.R.V. acknowledge funding from the Chemical Catalysis for Bioenergy consortium by the Bioenergy Technologies Office in the DOE Office of Energy Efficiency and Renewable Energy. Microscopy was performed in collaboration with the Chemical Catalysis for Bioenergy Consortium under contract no. DE-AC05-00OR22725 with Oak Ridge National Laboratory (ORNL) and through a user project supported by ORNL’s Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Part of the microscopy research was also supported by the Office of Nuclear Energy, Fuel Cycle R&D Program and the Nuclear Science User Facilities. Authors thank Shawn K. Reeves for assistance with TEM sample preparation. We would also like to thank Stephen Tifft for his support on spinning band distillation, as well as Rick Elander and Min Zhang for their support and discussions regarding BDO fermentation. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allows others to do so, for U.S. Government purposes. The results and analysis presented in this paper were partially possible thanks to the access granted to computing resources at the Galicia Supercomputing Center, CESGA, including access to the FinisTerrae supercomputer, the Red Española de Supercomputación (grant number QH-2023-1-0003) and the Drago cluster facility of SGAI-CSIC. R.S.P. and J.V.A.-R. acknowledge the RMACC Summit supercomputer, supported by the NSF (ACI-1532235 and ACI1532236), and the Extreme Science and Engineering Discovery Environment (XSEDE) allocations TG-CHE180056 and TG-CHE200033. J.V.A.-R. acknowledges financial support through the Gobierno de Aragón-Fondo Social Europeo (Research Group E07_23R) and a Juan de la Cierva Incorporación contract from the Ministry of Science and Innovation (MCIN) and the State Research Agency (AEI) of Spain, and the European Union (NextGenerationEU/PRTR) under grant reference IJC2020-044217-I. S.K. acknowledges XSEDE allocation TG-CHE210034 and the National Renewable Energy Laboratory Computational Science Center. This work was authored in part by the National Renewable Energy Laboratory, managed and operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding was provided by U.S. Department of Energy Office of Energy Efficiency and Renewable Energy Bioenergy Technologies Office and in collaboration with the Consortium for Computational Physics and Chemistry (CCPC) and the Chemical Catalysis for Bioenergy Consortium (ChemCatBio). G.R.H. X.H. F.G.B, K.A.U. B.C.K. R.E.D. and D.R.V. acknowledge funding from the Chemical Catalysis for Bioenergy consortium by the Bioenergy Technologies Office in the DOE Office of Energy Efficiency and Renewable Energy. Microscopy was performed in collaboration with the Chemical Catalysis for Bioenergy Consortium under contract no. DE-AC05-00OR22725 with Oak Ridge National Laboratory (ORNL) and through a user project supported by ORNL's Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Part of the microscopy research was also supported by the Office of Nuclear Energy, Fuel Cycle R&D Program and the Nuclear Science User Facilities. Authors thank Shawn K. Reeves for assistance with TEM sample preparation. We would also like to thank Stephen Tifft for his support on spinning band distillation, as well as Rick Elander and Min Zhang for their support and discussions regarding BDO fermentation. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allows others to do so, for U.S. Government purposes. The results and analysis presented in this paper were partially possible thanks to the access granted to computing resources at the Galicia Supercomputing Center, CESGA, including access to the FinisTerrae supercomputer, the Red Española de Supercomputación (grant number QH-2023-1-0003) and the Drago cluster facility of SGAI-CSIC.
Keywords
- 2,3-butanediol
- Butadiene
- Computational chemistry
- HPO derivatives
- Heterogeneous catalysis
- Mechanistic studies
- QM/MM