skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

Abstract

The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxyl groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases.more » Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.« less

Authors:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]
  1. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China
  2. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  3. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1417432
Report Number(s):
PNNL-SA-112607
Journal ID: ISSN 2155-5435; 47800; BM0102060
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 8; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Aqueous Phase; Ketonization; Acetic Acid; Zirconia; Density Functional Theory; Environmental Molecular Sciences Laboratory

Citation Formats

Cai, Qiuxia, Lopez-Ruiz, Juan A., Cooper, Alan R., Wang, Jian-guo, Albrecht, Karl O., and Mei, Donghai. Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b03298.
Cai, Qiuxia, Lopez-Ruiz, Juan A., Cooper, Alan R., Wang, Jian-guo, Albrecht, Karl O., & Mei, Donghai. Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia. United States. doi:10.1021/acscatal.7b03298.
Cai, Qiuxia, Lopez-Ruiz, Juan A., Cooper, Alan R., Wang, Jian-guo, Albrecht, Karl O., and Mei, Donghai. Wed . "Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia". United States. doi:10.1021/acscatal.7b03298.
@article{osti_1417432,
title = {Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia},
author = {Cai, Qiuxia and Lopez-Ruiz, Juan A. and Cooper, Alan R. and Wang, Jian-guo and Albrecht, Karl O. and Mei, Donghai},
abstractNote = {The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxyl groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.},
doi = {10.1021/acscatal.7b03298},
journal = {ACS Catalysis},
number = 1,
volume = 8,
place = {United States},
year = {Wed Dec 13 00:00:00 EST 2017},
month = {Wed Dec 13 00:00:00 EST 2017}
}