Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Effect of Confinement on the Density and Diffusivity of Organic Molecules in Single-Digit Nanopores Relative to Bulk Fluid Behavior

Abstract

Prediction of fluid properties in microporous and mesoporous confinement is non-trivial due to distinct influences from pore surface functionality and shape and fluid molecular characteristics. The vast majority of literature focuses nearly exclusively on a small number of components that are generally low molecular weight gases and vapors. Missing are studies that utilize a relatively large number of compounds that are liquid at ambient conditions to probe the impact of molecular shape and size on confined fluid properties. Such materials are of great interest in the extraction of oil and gas from shale reservoirs or for the design of selective adsorbents for chemical separation. In this work, we reveal non-intuitive relationships that emerge when comparing bulk fluid properties to those when confined in amorphous silica single-digit nanopores (approx. 5 nm SBA-15), specifically the confined density and self-diffusivity. A counterintuitive result was obtained where larger molecules had relatively faster self-diffusivities; however, this behavior was revealed to be caused by these larger compounds exhibiting a relatively low density when confined. As the prediction of confined fluid properties impacts a diversity of disciplines, the results highlight the need for additional investigations where consistent and large-scale experimental procedures are employed.

Authors:
 [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
OSTI Identifier:
1808587
Grant/Contract Number:  
SC0019285; 1C06RR017539-01A1; 3R01GM063540-17W1; 1S10OD25241-01
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 125; Journal Issue: 20; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Transport properties; Liquids; Diffusion; Fluids; Aromatic compounds

Citation Formats

Agrawal, Siddharth, Elmehlawy, Mahmoud, and Hoepfner, Michael P. Effect of Confinement on the Density and Diffusivity of Organic Molecules in Single-Digit Nanopores Relative to Bulk Fluid Behavior. United States: N. p., 2021. Web. doi:10.1021/acs.jpcc.1c00159.
Copy to clipboard
Agrawal, Siddharth, Elmehlawy, Mahmoud, & Hoepfner, Michael P. Effect of Confinement on the Density and Diffusivity of Organic Molecules in Single-Digit Nanopores Relative to Bulk Fluid Behavior. United States. https://doi.org/10.1021/acs.jpcc.1c00159
Copy to clipboard
Agrawal, Siddharth, Elmehlawy, Mahmoud, and Hoepfner, Michael P. Fri . "Effect of Confinement on the Density and Diffusivity of Organic Molecules in Single-Digit Nanopores Relative to Bulk Fluid Behavior". United States. https://doi.org/10.1021/acs.jpcc.1c00159. https://www.osti.gov/servlets/purl/1808587.
Copy to clipboard
@article{osti_1808587,
title = {Effect of Confinement on the Density and Diffusivity of Organic Molecules in Single-Digit Nanopores Relative to Bulk Fluid Behavior},
author = {Agrawal, Siddharth and Elmehlawy, Mahmoud and Hoepfner, Michael P.},
abstractNote = {Prediction of fluid properties in microporous and mesoporous confinement is non-trivial due to distinct influences from pore surface functionality and shape and fluid molecular characteristics. The vast majority of literature focuses nearly exclusively on a small number of components that are generally low molecular weight gases and vapors. Missing are studies that utilize a relatively large number of compounds that are liquid at ambient conditions to probe the impact of molecular shape and size on confined fluid properties. Such materials are of great interest in the extraction of oil and gas from shale reservoirs or for the design of selective adsorbents for chemical separation. In this work, we reveal non-intuitive relationships that emerge when comparing bulk fluid properties to those when confined in amorphous silica single-digit nanopores (approx. 5 nm SBA-15), specifically the confined density and self-diffusivity. A counterintuitive result was obtained where larger molecules had relatively faster self-diffusivities; however, this behavior was revealed to be caused by these larger compounds exhibiting a relatively low density when confined. As the prediction of confined fluid properties impacts a diversity of disciplines, the results highlight the need for additional investigations where consistent and large-scale experimental procedures are employed.},
doi = {10.1021/acs.jpcc.1c00159},
journal = {Journal of Physical Chemistry. C},
number = 20,
volume = 125,
place = {United States},
year = {Fri May 14 00:00:00 EDT 2021},
month = {Fri May 14 00:00:00 EDT 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.1c00159
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)
journal, October 2015

  • Thommes, Matthias; Kaneko, Katsumi; Neimark, Alexander V.
  • Pure and Applied Chemistry, Vol. 87, Issue 9-10
  • DOI: 10.1515/pac-2014-1117

A review on capillary condensation in nanoporous media: Implications for hydrocarbon recovery from tight reservoirs
journal, November 2016

Nanoconfinement in Slit Pores Enhances Water Self-Dissociation
journal, July 2017

Critical Knowledge Gaps in Mass Transport through Single-Digit Nanopores: A Review and Perspective
journal, May 2019

  • Faucher, Samuel; Aluru, Narayana; Bazant, Martin Z.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 35
  • DOI: 10.1021/acs.jpcc.9b02178

Molecular dynamics simulations of NMR relaxation and diffusion of bulk hydrocarbons and water
journal, April 2017

  • Singer, Philip M.; Asthagiri, Dilip; Chapman, Walter G.
  • Journal of Magnetic Resonance, Vol. 277
  • DOI: 10.1016/j.jmr.2017.02.001

Diffusion of Simple Liquids in Porous Sol-Gel Glass
journal, November 1995

  • Koone, N.; Shao, Y.; Zerda, T. W.
  • The Journal of Physical Chemistry, Vol. 99, Issue 46
  • DOI: 10.1021/j100046a025

NMR study of the geometric confinement effects on the anisotropic rotational diffusion of acetonitrile-d3
journal, August 1993

  • Zhang, Jing; Jonas, Jiri
  • The Journal of Physical Chemistry, Vol. 97, Issue 34
  • DOI: 10.1021/j100136a028

Diffusion of fluids in confined geometry
journal, January 1994

Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons
journal, April 2018

  • Singer, P. M.; Asthagiri, D.; Chen, Z.
  • The Journal of Chemical Physics, Vol. 148, Issue 16
  • DOI: 10.1063/1.5023240

Neutron Scattering and Dielectric Studies on Dynamics of Methanol and Ethanol Confined in MCM-41
journal, July 2008

  • Takahara, Shuichi; Kittaka, Shigeharu; Mori, Toshinori
  • The Journal of Physical Chemistry C, Vol. 112, Issue 37
  • DOI: 10.1021/jp8015062

Flow enhancement of water-based nanoparticle dispersion through microscale sedimentary rocks
journal, March 2015

  • Yu, Haiyang; He, Youwei; Li, Peng
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08702

Measurement of diffusion coefficients in supercritical carbon dioxide and correlation with the equation of Wilke and Chang
journal, April 1987

  • Sassiat, Patrick R.; Mourier, Pierre.; Caude, Marcel H.
  • Analytical Chemistry, Vol. 59, Issue 8
  • DOI: 10.1021/ac00135a020

A GPU-accelerated package for simulation of flow in nanoporous source rocks with many-body dissipative particle dynamics
journal, February 2020

Nano/Micromotors in (Bio)chemical Science Applications
journal, April 2014

  • Guix, Maria; Mayorga-Martinez, Carmen C.; Merkoçi, Arben
  • Chemical Reviews, Vol. 114, Issue 12
  • DOI: 10.1021/cr400273r

Fundamental transport mechanisms, fabrication and potential applications of nanoporous atomically thin membranes
journal, June 2017

  • Wang, Luda; Boutilier, Michael S. H.; Kidambi, Piran R.
  • Nature Nanotechnology, Vol. 12, Issue 6
  • DOI: 10.1038/nnano.2017.72

Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes
journal, November 2016

  • Agrawal, Kumar Varoon; Shimizu, Steven; Drahushuk, Lee W.
  • Nature Nanotechnology, Vol. 12, Issue 3
  • DOI: 10.1038/nnano.2016.254

Diffusion in Confined Geometries
journal, January 2009

  • Burada, P. Sekhar; Hänggi, Peter; Marchesoni, Fabio
  • ChemPhysChem, Vol. 10, Issue 1
  • DOI: 10.1002/cphc.200800526

Adsorption of nitrogen, neopentane, n-hexane, benzene and methanol for the evaluation of pore sizes in silica grades of MCM-41
journal, October 2001

  • Ribeiro Carrott, M. M. L.; Candeias, A. J. E.; Carrott, P. J. M.
  • Microporous and Mesoporous Materials, Vol. 47, Issue 2-3
  • DOI: 10.1016/S1387-1811(01)00394-8

A new family of mesoporous molecular sieves prepared with liquid crystal templates
journal, December 1992

  • Beck, J. S.; Vartuli, J. C.; Roth, W. J.
  • Journal of the American Chemical Society, Vol. 114, Issue 27, p. 10834-10843
  • DOI: 10.1021/ja00053a020

The structures of liquid pyridine and naphthalene: the effects of heteroatoms and core size on aromatic interactions
journal, January 2018

  • Headen, T. F.; Cullen, P. L.; Patel, R.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 4
  • DOI: 10.1039/C7CP06689A

Confinement Effects on the Benzene Orientational Structure
journal, March 2018

  • Falkowska, Marta; Bowron, Daniel T.; Manyar, Haresh
  • Angewandte Chemie International Edition, Vol. 57, Issue 17
  • DOI: 10.1002/anie.201713115

Ion Transport in Nanofluidic Channels
journal, January 2004

  • Daiguji, Hirofumi; Yang, Peidong; Majumdar, Arun
  • Nano Letters, Vol. 4, Issue 1
  • DOI: 10.1021/nl0348185

Trends in the condensation/evaporation and adsorption enthalpies of volatile organic compounds on mesoporous silica materials
journal, March 2012

Existence of Multiple Phases of Water at Nanotube Interfaces
journal, October 2016

  • Barati Farimani, Amir; Aluru, Narayana R.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 41
  • DOI: 10.1021/acs.jpcc.6b06156

Molecular Dynamics Simulation of Diffusion of Shale Oils in Montmorillonite
journal, April 2016

  • Wang, Hui; Wang, Xiaoqi; Jin, Xu
  • The Journal of Physical Chemistry C, Vol. 120, Issue 16
  • DOI: 10.1021/acs.jpcc.6b01660

Equation-of-state modeling of confined-fluid phase equilibria in nanopores
journal, May 2015

Applications of biological pores in nanomedicine, sensing, and nanoelectronics
journal, August 2010

Reminiscent capillarity in subnanopores
journal, October 2019

Low-dimensional effects on frequency dependence of proton NMR relaxation in liquid cyclohexane confined to porous glasses
journal, January 1993

Characterization of Micro- and Mesoporosity in SBA-15 Materials from Adsorption Data by the NLDFT Method
journal, July 2001

  • Ravikovitch, Peter I.; Neimark, Alexander V.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 29
  • DOI: 10.1021/jp010621u

Structure of liquid and glassy methanol confined in cylindrical pores
journal, July 2004

  • Morineau, Denis; Guégan, Régis; Xia, Yongde
  • The Journal of Chemical Physics, Vol. 121, Issue 3
  • DOI: 10.1063/1.1762872

Unexpected Interactions between Sol−Gel Silica Glass and Guest Molecules. Extraction of Aromatic Hydrocarbons into Polar Silica from Hydrophobic Solvents
journal, November 2000

  • Badjić, Jovica D.; Kostić, Nenad M.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 47
  • DOI: 10.1021/jp0021042

Freezing and Melting of Water Confined in Silica Nanopores
journal, November 2008

  • Findenegg, Gerhard H.; Jähnert, Susanne; Akcakayiran, Dilek
  • ChemPhysChem, Vol. 9, Issue 18
  • DOI: 10.1002/cphc.200800616

Multiscale nuclear magnetic relaxation dispersion of complex liquids in bulk and confinement
journal, February 2018

Recommendations for the characterization of porous solids (Technical Report)
journal, January 1994

  • Rouquerol, J.; Avnir, D.; Fairbridge, C. W.
  • Pure and Applied Chemistry, Vol. 66, Issue 8, p. 1739-1758
  • DOI: 10.1351/pac199466081739

Asymmetric Diffusion through Synthetic Nanopores
journal, February 2005

Adsorption Behavior on Defect Structure of Mesoporous Molecular Sieve MCM-41
journal, October 1998

  • Long, Yingcai; Xu, Taiming; Sun, Yaojun
  • Langmuir, Vol. 14, Issue 21
  • DOI: 10.1021/la971127d

Preparation and characterization of mesoporous SBA-15 supported dye-sensitized TiO2 photocatalyst
journal, January 2005

Perspective: Dynamics of confined liquids
journal, November 2018

  • Thompson, Ward H.
  • The Journal of Chemical Physics, Vol. 149, Issue 17
  • DOI: 10.1063/1.5057759

CRC Handbook of Chemistry and Physics
book, June 2014

Surface Dynamics of Liquids in Nanopores
journal, September 1996

Study of Hexane Adsorption in Nanoporous MCM-41 Silica
journal, December 2003

  • Qiao, S. Z.; Bhatia, S. K.; Nicholson, D.
  • Langmuir, Vol. 20, Issue 2
  • DOI: 10.1021/la0353430

Adsorption of Aromatic Hydrocarbons on Highly Siliceous MCM-41
journal, August 2000

  • Choudhary, Vasant R.; Mantri, Kshudiram
  • Langmuir, Vol. 16, Issue 17
  • DOI: 10.1021/la991714u

Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins
journal, August 2017

  • Tunuguntla, Ramya H.; Henley, Robert Y.; Yao, Yun-Chiao
  • Science, Vol. 357, Issue 6353
  • DOI: 10.1126/science.aan2438

The effect of nanopore shape on the structure and isotherms of adsorbed fluids
journal, January 1996

  • Keffer, D.; Davis, H. Ted; McCormick, Alon V.
  • Adsorption, Vol. 2, Issue 1
  • DOI: 10.1007/BF00127094

Study of the Interaction between Hydroxyl Groups of Aerosil Silica and Adsorbed Non-polar Molecules by Infrared Spectrometry 1
journal, February 1957

  • McDonald, R. S.
  • Journal of the American Chemical Society, Vol. 79, Issue 4
  • DOI: 10.1021/ja01561a018

Hydrogen Bonding Interaction between Adsorbate Molecules and Surface Hydroxyl Groups on Silica
journal, October 1961

  • Basila, Michael R.
  • The Journal of Chemical Physics, Vol. 35, Issue 4
  • DOI: 10.1063/1.1732016

Pore structure and surface area of silica SBA-15: influence of washing and scale-up
journal, January 2011

  • Thielemann, Jörg P.; Girgsdies, Frank; Schlögl, Robert
  • Beilstein Journal of Nanotechnology, Vol. 2
  • DOI: 10.3762/bjnano.2.13

Enhanced n-hexane diffusion in partially filled MCM-41 of different surface hydrophobicity probed by NMR
journal, May 2000

13 C NMR Relaxation Studies of Pyridine and Pentafluoropyridine Liquids Confined to Nanopores of Porous Silica Glasses
journal, January 1996

  • Xu, Shu; Jonas, Jiri
  • The Journal of Physical Chemistry, Vol. 100, Issue 40
  • DOI: 10.1021/jp960769r

Quenched molecular reorientation and angular momentum for liquids confined to nanopores of silica glasses
journal, September 1997

  • Korb, J. -P.; Xu, Shu; Cros, F.
  • The Journal of Chemical Physics, Vol. 107, Issue 10
  • DOI: 10.1063/1.474760

Ordered porous materials for emerging applications
journal, June 2002

Structure of π−π Interactions in Aromatic Liquids
journal, January 2010

  • Headen, Thomas F.; Howard, Christopher A.; Skipper, Neal T.
  • Journal of the American Chemical Society, Vol. 132, Issue 16
  • DOI: 10.1021/ja909084e

NMR studies on simple liquids in confinement
journal, October 2010

Adsorption on MCM-41 mesoporous molecular sieves. Part 2.—Cyclopentane isotherms and their temperature dependence
journal, January 1995

  • Rathouský, J.; Zukal, A.; Franke, O.
  • J. Chem. Soc., Faraday Trans., Vol. 91, Issue 5
  • DOI: 10.1039/FT9959100937

NMR studies of the diffusion of cyclohexane in porous silica
journal, December 1992

Nanofiltration membranes review: Recent advances and future prospects
journal, January 2015

Modeling Self-Diffusion of Simple Fluids in Nanopores
journal, October 2011

  • Bhatia, Suresh K.; Nicholson, David
  • The Journal of Physical Chemistry B, Vol. 115, Issue 40
  • DOI: 10.1021/jp206811a

Diffusion processes in confined materials
journal, June 1998

Effects of Heteroatoms on Aromatic π−π Interactions: Benzene−Pyridine and Pyridine Dimer
journal, February 2009

  • Hohenstein, Edward G.; Sherrill, C. David
  • The Journal of Physical Chemistry A, Vol. 113, Issue 5
  • DOI: 10.1021/jp809062x

Adsorption of Benzene and Ethanol on MCM-41 Material
journal, August 1998

  • Nguyen, C.; Sonwane, C. G.; Bhatia, S. K.
  • Langmuir, Vol. 14, Issue 17
  • DOI: 10.1021/la971203c

CHEMISTRY: Learning Nature's Way: Biosensing with Synthetic Nanopores
journal, July 2007

NMR spin-rotation relaxation and diffusion of methane
journal, May 2018

  • Singer, P. M.; Asthagiri, D.; Chapman, W. G.
  • The Journal of Chemical Physics, Vol. 148, Issue 20
  • DOI: 10.1063/1.5027097

Physisorption of alcohols and water vapour by MCM-41, a model mesoporous adsorbent
journal, January 1995

  • Branton, Peter J.; Hall, Peter G.; Sing, Kenneth S. W.
  • Adsorption, Vol. 1, Issue 1
  • DOI: 10.1007/BF00704147

Pulsed field gradient NMR study of the diffusion of n-hexane confined in hydroxylated and dehydroxylated MCM-41 of various pore diameters
journal, April 2000

Diffusion coefficients in supercritical fluids: available data and graphical correlations
journal, November 1998

Accurate correlations for the self-diffusion coefficients of CO2, CH4, C2H4, H2O, and D2O over wide ranges of temperature and pressure
journal, December 1995

Nature of Adsorption and Desorption Branches in Cylindrical Pores
journal, May 2004

  • Morishige, Kunimitsu; Nakamura, Yuka
  • Langmuir, Vol. 20, Issue 11
  • DOI: 10.1021/la030414g

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

Adsorption Interactions of Aromatics and Heteroaromatics with Hydrated and Dehydrated Silica Surfaces by Raman and FTIR Spectroscopies
journal, December 1999

  • Ringwald, Steven C.; Pemberton, Jeanne E.
  • Environmental Science & Technology, Vol. 34, Issue 2
  • DOI: 10.1021/es980970a

Density functional theory methods for characterization of porous materials
journal, November 2013

  • Landers, John; Gor, Gennady Yu.; Neimark, Alexander V.
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 437
  • DOI: 10.1016/j.colsurfa.2013.01.007
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: