DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane

Abstract

Fluids confined in nanopores exhibit significant deviations in their structure and dynamics from the bulk behavior. Although phase, structural and diffusive behaviors of confined fluids have been investigated and reported extensively, confinement effects on the vibrational properties are less understood. Here, we study the vibrational behavior of propane confined in 1.5 nm nanopores of MCM-41-S using inelastic neutron scattering (INS) and molecular dynamics (MD) simulations. Vibrational spectra have been obtained from INS data as functions of temperature and pressure. At ambient pressure, a strong quasielastic signal observed in the INS spectrum at 80 K suggests that confined propane remains liquid below the bulk phase melting point of 85 K. The quasielastic signal is heavily suppressed when either the pressure is increased to 1 kbar, or the temperature is lowered to 30 K, indicating solidification of pore-confined propane. Confinement in MCM-41-S pores results in a glass-like state of propane that exhibits a relatively featureless low-energy vibrational spectrum compared to the bulk crystalline propane. Increasing the pressure to 3 kbar results in hardening of the intermolecular and methyl torsional modes. The INS data are used for estimating the isochoric specific heat of confined propane, which is compared with the specific heat ofmore » bulk propane reported in literature. Data from MD simulations is used to calculate the vibrational power spectra that agree qualitatively with the experimental data. Simulation data also suggests a reduction in the structural ordering (positional, orientational and intramolecular) of propane under confinement.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3];  [4];  [1]
  1. The Ohio State Univ., Columbus, OH (United States). School of Earth Sciences
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Jilin Univ., Changchun (China). State Key Lab. of Inorganic Synthesis and Preparative Chemistry and College of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Contributing Org.:
Science and Technology Facilities Council (STFC), Daresbury (United Kingdom). Daresbury Lab.; Rensselaer Polytechnic Inst., Troy, NY (United States)
OSTI Identifier:
1462830
Grant/Contract Number:  
AC05-00OR22725; SC0006878
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: TBD; Journal Issue: TBD; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gautam, Siddharth, Kolesnikov, Alexander I., Rother, Gernot, Dai, Sheng, Qiao, Zhen-An, and Cole, David R. Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b05028.
Gautam, Siddharth, Kolesnikov, Alexander I., Rother, Gernot, Dai, Sheng, Qiao, Zhen-An, & Cole, David R. Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane. United States. https://doi.org/10.1021/acs.jpca.8b05028
Gautam, Siddharth, Kolesnikov, Alexander I., Rother, Gernot, Dai, Sheng, Qiao, Zhen-An, and Cole, David R. Tue . "Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane". United States. https://doi.org/10.1021/acs.jpca.8b05028. https://www.osti.gov/servlets/purl/1462830.
@article{osti_1462830,
title = {Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane},
author = {Gautam, Siddharth and Kolesnikov, Alexander I. and Rother, Gernot and Dai, Sheng and Qiao, Zhen-An and Cole, David R.},
abstractNote = {Fluids confined in nanopores exhibit significant deviations in their structure and dynamics from the bulk behavior. Although phase, structural and diffusive behaviors of confined fluids have been investigated and reported extensively, confinement effects on the vibrational properties are less understood. Here, we study the vibrational behavior of propane confined in 1.5 nm nanopores of MCM-41-S using inelastic neutron scattering (INS) and molecular dynamics (MD) simulations. Vibrational spectra have been obtained from INS data as functions of temperature and pressure. At ambient pressure, a strong quasielastic signal observed in the INS spectrum at 80 K suggests that confined propane remains liquid below the bulk phase melting point of 85 K. The quasielastic signal is heavily suppressed when either the pressure is increased to 1 kbar, or the temperature is lowered to 30 K, indicating solidification of pore-confined propane. Confinement in MCM-41-S pores results in a glass-like state of propane that exhibits a relatively featureless low-energy vibrational spectrum compared to the bulk crystalline propane. Increasing the pressure to 3 kbar results in hardening of the intermolecular and methyl torsional modes. The INS data are used for estimating the isochoric specific heat of confined propane, which is compared with the specific heat of bulk propane reported in literature. Data from MD simulations is used to calculate the vibrational power spectra that agree qualitatively with the experimental data. Simulation data also suggests a reduction in the structural ordering (positional, orientational and intramolecular) of propane under confinement.},
doi = {10.1021/acs.jpca.8b05028},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = TBD,
volume = TBD,
place = {United States},
year = {Tue Jul 24 00:00:00 EDT 2018},
month = {Tue Jul 24 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Anomalous Behavior of Proton Zero Point Motion in Water Confined in Carbon Nanotubes
journal, December 2006


Quantum Tunneling of Water in Beryl: A New State of the Water Molecule
journal, April 2016


Local structure and density fluctuations in confined fluids
journal, April 2016


Effects of confinement on freezing and melting
journal, January 2006

  • Alba-Simionesco, C.; Coasne, B.; Dosseh, G.
  • Journal of Physics: Condensed Matter, Vol. 18, Issue 6
  • DOI: 10.1088/0953-8984/18/6/R01

Effect of Confinement on Pressure/Volume/Temperature Properties of Hydrocarbons in Shale Reservoirs
journal, April 2016

  • Pitakbunkate, Termpan; Balbuena, Perla B.; Moridis, George J.
  • SPE Journal, Vol. 21, Issue 02
  • DOI: 10.2118/170685-PA

Motions and Relaxations of Confined Liquids
journal, September 1991


High H 2 Sorption Energetics in Zeolitic Imidazolate Frameworks
journal, January 2017

  • Pham, Tony; Forrest, Katherine A.; Furukawa, Hiroyasu
  • The Journal of Physical Chemistry C, Vol. 121, Issue 3
  • DOI: 10.1021/acs.jpcc.6b11466

Diffusive and rotational dynamics of condensed n-H 2 confined in MCM-41
journal, January 2014

  • Prisk, T. R.; Bryan, M. S.; Sokol, P. E.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 33
  • DOI: 10.1039/C4CP02281E

Properties of immobile hydrogen confined in microporous carbon
journal, June 2017


Restricted dynamics of molecular hydrogen confined in activated carbon nanopores
journal, March 2012


Phases of superfluid helium in smooth cylindrical pores
journal, July 2013


Subcontinuum mass transport of condensed hydrocarbons in nanoporous media
journal, April 2015

  • Falk, Kerstin; Coasne, Benoit; Pellenq, Roland
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7949

Shales at all scales: Exploring coupled processes in mudrocks
journal, March 2017


Molecular self-diffusion of methane in zeolite ZSM-5 by quasi-elastic neutron scattering and nuclear magnetic resonance pulsed field gradient technique
journal, January 1989

  • Jobic, Hervé; Bée, Marc; Caro, Jürgen
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 12
  • DOI: 10.1039/f19898504201

Molecular dynamics simulation of propane and methane in silicalite
journal, April 1993

  • Nicholas, John B.; Trouw, Frans R.; Mertz, John E.
  • The Journal of Physical Chemistry, Vol. 97, Issue 16
  • DOI: 10.1021/j100118a035

Unidirectional and Single-File Diffusion of Molecules in One-Dimensional Channel Systems. A Quasi-Elastic Neutron Scattering Study
journal, July 1997

  • Jobic, Hervé; Hahn, Karsten; Kärger, Jörg
  • The Journal of Physical Chemistry B, Vol. 101, Issue 30
  • DOI: 10.1021/jp970773i

Dynamics of methane molecules in porous TiO 2
journal, February 2000


Structural and dynamic properties of confined ethane in AlPO4-5 model microporous aluminophosphate: Does the predicted quasi-(1D) phase transition exist?
journal, May 2011


Role of Confinement on Adsorption and Dynamics of Ethane and an Ethane–CO 2 Mixture in Mesoporous CPG Silica
journal, February 2016

  • Patankar, Sumant; Gautam, Siddharth; Rother, Gernot
  • The Journal of Physical Chemistry C, Vol. 120, Issue 9
  • DOI: 10.1021/acs.jpcc.5b09984

Location dependent orientational structure and dynamics of ethane in ZSM5
journal, March 2016


Dynamics of ethane and propane in zeolite ZSM-5 studied by quasi-elastic neutron scattering
journal, February 1992


Molecular dynamics simulation study of meso-confined propane in TiO2
journal, September 2015


Dynamics of Propane in Nanoporous Silica Aerogel: A Quasielastic Neutron Scattering Study
journal, July 2015

  • Gautam, Siddharth; Liu, Tingting; Rother, Gernot
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b03444

Molecular dynamics simulations of propane in slit shaped silica nano-pores: direct comparison with quasielastic neutron scattering experiments
journal, January 2017

  • Gautam, Siddharth; Le, Thu; Striolo, Alberto
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 48
  • DOI: 10.1039/C7CP05715F

Effect of molecular shape on rotation under severe confinement
journal, April 2018


Propane on Titan
journal, October 2003

  • Roe, H. G.; Greathouse, T. K.; Richter, M. J.
  • The Astrophysical Journal, Vol. 597, Issue 1
  • DOI: 10.1086/379816

Why Propane?
journal, February 2013

  • Podsiadło, Marcin; Olejniczak, Anna; Katrusiak, Andrzej
  • The Journal of Physical Chemistry C, Vol. 117, Issue 9
  • DOI: 10.1021/jp311747m

Thermodynamic Study on Simple Molecular Glasses
journal, January 2012


Glass Transition, Crystallization, Melting, and Decomposition of Nanoconfined Propane Films at Cryogenic Temperatures
journal, July 2016


Methyl Libration in Propane Measured with Neutron Inelastic Scattering
journal, May 1970

  • Grant, David M.; Pugmire, Ronald J.; Livingston, Robert C.
  • The Journal of Chemical Physics, Vol. 52, Issue 9
  • DOI: 10.1063/1.1673668

First high resolution analysis of the ν21 band of propane CH3CH2CH3 at 921.382cm−1: Evidence of large amplitude tunneling effects
journal, September 2015


A Review: Fundamental Aspects of Silicate Mesoporous Materials
journal, December 2012


A comparison of four direct geometry time-of-flight spectrometers at the Spallation Neutron Source
journal, April 2014

  • Stone, M. B.; Niedziela, J. L.; Abernathy, D. L.
  • Review of Scientific Instruments, Vol. 85, Issue 4
  • DOI: 10.1063/1.4870050

SEQUOIA: A Newly Operating Chopper Spectrometer at the SNS
journal, November 2010


Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments
journal, November 2014

  • Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764
  • DOI: 10.1016/j.nima.2014.07.029

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism
journal, January 2006

  • Todorov, Ilian T.; Smith, William; Trachenko, Kostya
  • Journal of Materials Chemistry, Vol. 16, Issue 20, p. 1911-1918
  • DOI: 10.1039/b517931a

Factors affecting molecular dynamics simulated vitreous silica structures
journal, August 1999


Propane simulated in silica pores: Adsorption isotherms, molecular structure, and mobility
journal, January 2015


Propane–Water Mixtures Confined within Cylindrical Silica Nanopores: Structural and Dynamical Properties Probed by Molecular Dynamics
journal, September 2017


The Melting Point Alternation in the Short-Chainn-Alkanes: Single-Crystal X-Ray Analyses of Propane at 30 K and ofn-Butane ton-Nonane at 90 K
journal, April 1999


Thermal Conductivity of MgO Periclase from Equilibrium First Principles Molecular Dynamics
journal, September 2009


Global phase diagrams for freezing in porous media
journal, January 2002

  • Radhakrishnan, Ravi; Gubbins, Keith E.; Sliwinska-Bartkowiak, Malgorzata
  • The Journal of Chemical Physics, Vol. 116, Issue 3
  • DOI: 10.1063/1.1426412

Neutron spectroscopy of magnesium dihydride
journal, September 2011


Specific heats of saturated and compressed liquid propane
journal, September 1978

  • Goodwin, R. D.
  • Journal of Research of the National Bureau of Standards, Vol. 83, Issue 5
  • DOI: 10.6028/jres.083.031

Excess heat capacities due to the low-energy excitations of molecular glasses: An approach using the soft potential model
journal, October 1997

  • Lindqvist, Anna; Yamamuro, Osamu; Tsukushi, Itaru
  • The Journal of Chemical Physics, Vol. 107, Issue 13
  • DOI: 10.1063/1.474873

Inelastic neutron scattering study of low-energy excitations in vapor-deposited glassy propylene
journal, February 1997

  • Yamamuro, Osamu; Tsukushi, Itaru; Matsuo, Takasuke
  • The Journal of Chemical Physics, Vol. 106, Issue 8
  • DOI: 10.1063/1.473045

Works referencing / citing this record:

Effects of water on the stochastic motions of propane confined in MCM-41-S pores
journal, January 2019

  • Gautam, Siddharth; Le, Tran Thi Bao; Rother, Gernot
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 45
  • DOI: 10.1039/c9cp04741g

Adsorption and Diffusion of Hydrogen in Carbon Honeycomb
journal, February 2020