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Title: Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5

Abstract

Here, to account for thermal and entropic effects caused by the dynamics of the motion of the reaction intermediates, ethanol adsorption on the Brønsted acid site of the H-ZSM-5 catalyst has been studied at different temperatures and ethanol loadings using ab initio molecular dynamics (AIMD) simulations, infrared (IR) spectroscopy and calorimetric measurements. At low temperatures (T ≤ 400 K) and ethanol loading, a single ethanol molecule adsorbed in H-ZSM-5 forms a Zundel-like structure where the proton is equally shared between the oxygen of the zeolite and the oxygen of the alcohol. At higher ethanol loading, a second ethanol molecule helps to stabilize the protonated ethanol at all temperatures by acting as a solvating agent. The vibrational density of states (VDOS), as calculated from the AIMD simulations, are in excellent agreement with measured IR spectra for C2H5OH, C2H5OD and C2D5OH isotopomers and support the existence of both monomers and dimers. A quasi-harmonic approximation (QHA), applied to the VDOS obtained from the AIMD simulations, provides estimates of adsorption free energy within ~10 kJ/mol of the experimentally determined quantities, whereas the traditional approach, employing harmonic frequencies from a single ground state minimum, strongly overestimates the adsorption free energy by at least ~30 kJ/mol.more » This discrepancy is traced back to the inability of the harmonic approximation to represent the contributions to the vibrational motions of the ethanol molecule upon confinement in the zeolite. KA, MFR, GBM were supported by the Long Term Structural Methusalem Funding by the Flemish Government – grant number BOF09/01M00409. MSL, VAG, RR and JAL were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL, the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory and the Stevin Supercomputer Infrastructure at Ghent University.« less

Authors:
 [1];  [2];  [3];  [3];  [3];  [1];  [1];  [2];  [2];  [2]
  1. Ghent Univ., Gent (Belgium)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. TU Munchen, Garching (Germany)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1253826
Report Number(s):
PNNL-SA-116157
Journal ID: ISSN 1932-7447; 48772; KC0302010
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 13; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

Alexopoulos, Konstantinos, Lee, Mal -Soon, Liu, Yue, Zhi, Yuchun, Liu, Yuanshuai, Reyniers, Marie -Francoise, Marin, Guy B., Glezakou, Vassiliki -Alexandra, Rousseau, Roger, and Lercher, Johannes A. Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b00923.
Alexopoulos, Konstantinos, Lee, Mal -Soon, Liu, Yue, Zhi, Yuchun, Liu, Yuanshuai, Reyniers, Marie -Francoise, Marin, Guy B., Glezakou, Vassiliki -Alexandra, Rousseau, Roger, & Lercher, Johannes A. Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5. United States. https://doi.org/10.1021/acs.jpcc.6b00923
Alexopoulos, Konstantinos, Lee, Mal -Soon, Liu, Yue, Zhi, Yuchun, Liu, Yuanshuai, Reyniers, Marie -Francoise, Marin, Guy B., Glezakou, Vassiliki -Alexandra, Rousseau, Roger, and Lercher, Johannes A. Mon . "Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5". United States. https://doi.org/10.1021/acs.jpcc.6b00923. https://www.osti.gov/servlets/purl/1253826.
@article{osti_1253826,
title = {Anharmonicity and confinement in zeolites: Structure, spectroscopy, and adsorption free energy of ethanol in H-ZSM-5},
author = {Alexopoulos, Konstantinos and Lee, Mal -Soon and Liu, Yue and Zhi, Yuchun and Liu, Yuanshuai and Reyniers, Marie -Francoise and Marin, Guy B. and Glezakou, Vassiliki -Alexandra and Rousseau, Roger and Lercher, Johannes A.},
abstractNote = {Here, to account for thermal and entropic effects caused by the dynamics of the motion of the reaction intermediates, ethanol adsorption on the Brønsted acid site of the H-ZSM-5 catalyst has been studied at different temperatures and ethanol loadings using ab initio molecular dynamics (AIMD) simulations, infrared (IR) spectroscopy and calorimetric measurements. At low temperatures (T ≤ 400 K) and ethanol loading, a single ethanol molecule adsorbed in H-ZSM-5 forms a Zundel-like structure where the proton is equally shared between the oxygen of the zeolite and the oxygen of the alcohol. At higher ethanol loading, a second ethanol molecule helps to stabilize the protonated ethanol at all temperatures by acting as a solvating agent. The vibrational density of states (VDOS), as calculated from the AIMD simulations, are in excellent agreement with measured IR spectra for C2H5OH, C2H5OD and C2D5OH isotopomers and support the existence of both monomers and dimers. A quasi-harmonic approximation (QHA), applied to the VDOS obtained from the AIMD simulations, provides estimates of adsorption free energy within ~10 kJ/mol of the experimentally determined quantities, whereas the traditional approach, employing harmonic frequencies from a single ground state minimum, strongly overestimates the adsorption free energy by at least ~30 kJ/mol. This discrepancy is traced back to the inability of the harmonic approximation to represent the contributions to the vibrational motions of the ethanol molecule upon confinement in the zeolite. KA, MFR, GBM were supported by the Long Term Structural Methusalem Funding by the Flemish Government – grant number BOF09/01M00409. MSL, VAG, RR and JAL were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided at W. R. Wiley Environmental Molecular Science Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL, the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory and the Stevin Supercomputer Infrastructure at Ghent University.},
doi = {10.1021/acs.jpcc.6b00923},
journal = {Journal of Physical Chemistry. C},
number = 13,
volume = 120,
place = {United States},
year = {2016},
month = {3}
}

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