Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22

Kummali, Mohammed Musthafa; Cole, David; Gautam, Siddharth

doi:10.3390/membranes11020113

Title: Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22

Abstract

The behavior of fluids under nano-confinement varies from that in bulk due to an interplay of several factors including pore connectivity. In this work, we use molecular dynamics simulations to study the behavior of two fluids—ethane and CO2 confined in ZSM-22, a zeolite with channel-like pores of diameter 0.55 nm isolated from each other. By comparing the behavior of the two fluids in ZSM-22 with that reported earlier in ZSM-5, a zeolite with pores of similar shape and size connected to each other via sinusoidal pores running perpendicular to them, we reveal the important role of pore connectivity. Further, by artificially imposing pore connectivity in ZSM-22 via inserting a 2-dimensional slab-like inter-crystalline space of thickness 0.5 nm, we also studied the effect of the dimensionality and geometry of pore connectivity. While the translational motion of both ethane and CO2 in ZSM-22 is suppressed as a result of connecting the pores by perpendicular quasi-one-dimensional pores of similar dimensions, the effect of connecting the pores by inserting the inter-crystalline space is different on the translational motion of the two fluids. For ethane, pores connected via inter-crystalline space facilitate translational motion but suppress rotational motion, whereas in the case of CO2, both typesmore »« less

Authors:

; Cole, David;

Publication Date:: Fri Feb 05 00:00:00 EST 2021

Sponsoring Org.:: USDOE

OSTI Identifier:: 1765020

Grant/Contract Number:: DESC000687

Resource Type:: Published Article

Journal Name:: Membranes

Additional Journal Information:: Journal Name: Membranes Journal Volume: 11 Journal Issue: 2; Journal ID: ISSN 2077-0375

Publisher:: MDPI AG

Country of Publication:: Switzerland

Language:: English

Citation Formats


                    Kummali, Mohammed Musthafa, Cole, David, and Gautam, Siddharth. Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22.  Switzerland: N. p., 2021. 
Web.  doi:10.3390/membranes11020113.

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                    Kummali, Mohammed Musthafa, Cole, David, & Gautam, Siddharth. Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22.  Switzerland.  https://doi.org/10.3390/membranes11020113

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                    Kummali, Mohammed Musthafa, Cole, David, and Gautam, Siddharth. Fri .  
"Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22".  Switzerland.  https://doi.org/10.3390/membranes11020113.

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@article{osti_1765020,

  title        = {Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22},

  author       = {Kummali, Mohammed Musthafa and Cole, David and Gautam, Siddharth},

  abstractNote = {The behavior of fluids under nano-confinement varies from that in bulk due to an interplay of several factors including pore connectivity. In this work, we use molecular dynamics simulations to study the behavior of two fluids—ethane and CO2 confined in ZSM-22, a zeolite with channel-like pores of diameter 0.55 nm isolated from each other. By comparing the behavior of the two fluids in ZSM-22 with that reported earlier in ZSM-5, a zeolite with pores of similar shape and size connected to each other via sinusoidal pores running perpendicular to them, we reveal the important role of pore connectivity. Further, by artificially imposing pore connectivity in ZSM-22 via inserting a 2-dimensional slab-like inter-crystalline space of thickness 0.5 nm, we also studied the effect of the dimensionality and geometry of pore connectivity. While the translational motion of both ethane and CO2 in ZSM-22 is suppressed as a result of connecting the pores by perpendicular quasi-one-dimensional pores of similar dimensions, the effect of connecting the pores by inserting the inter-crystalline space is different on the translational motion of the two fluids. For ethane, pores connected via inter-crystalline space facilitate translational motion but suppress rotational motion, whereas in the case of CO2, both types of motion are suppressed by pore connection due to the strong interaction of CO2 with the surface of the substrate.},

  doi          = {10.3390/membranes11020113},

  journal      = {Membranes},

  number       = 2,

  volume       = 11,

  place        = {Switzerland},

  year         = {Fri Feb 05 00:00:00 EST 2021},

  month        = {Fri Feb 05 00:00:00 EST 2021}

}

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Works referenced in this record:

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

Gautam, Siddharth; Liu, Tingting; Patankar, Sumant
Chemical Physics Letters, Vol. 648
DOI: 10.1016/j.cplett.2016.02.021

Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field
journal, January 2004

Cygan, Randall T.; Liang, Jian-Jie; Kalinichev, Andrey G.
The Journal of Physical Chemistry B, Vol. 108, Issue 4
DOI: 10.1021/jp0363287

Anomalous Diffusivity in Porous Solids: Levitation Effect
book, July 2020

Nag, Shubhadeep; Subramanian, Yashonath; Margeta, Karmen
Zeolites - New Challenges
DOI: 10.5772/intechopen.92685

The framework topology of ZSM-22: A high silica zeolite
journal, November 1985

Kokotailo, G. T.; Schlenker, J. L.; Dwyer, F. G.
Zeolites, Vol. 5, Issue 6
DOI: 10.1016/0144-2449(85)90122-8

Adsorption Equilibria of C ₁ to C ₄ Alkanes, CO ₂ , and SF ₆ on Silicalite
journal, February 1998

Sun, Matthew S.; Shah, D. B.; Xu, Heather H.
The Journal of Physical Chemistry B, Vol. 102, Issue 8
DOI: 10.1021/jp9730196

Simulations on “Powder” Samples for Better Agreement with Macroscopic Measurements
journal, May 2019

Thomas, Angela Mary; Subramanian, Yashonath
The Journal of Physical Chemistry C, Vol. 123, Issue 26
DOI: 10.1021/acs.jpcc.9b02599

Structure and Dynamics of Confined C-O-H Fluids Relevant to the Subsurface: Application of Magnetic Resonance, Neutron Scattering, and Molecular Dynamics Simulations
journal, June 2017

Gautam, Siddharth S.; Ok, Salim; Cole, David R.
Frontiers in Earth Science, Vol. 5
DOI: 10.3389/feart.2017.00043

Effects of inter-crystalline space on the adsorption of ethane and CO ₂ in silicalite: implications for enhanced adsorption
journal, January 2020

Gautam, Siddharth; Cole, David R.
Physical Chemistry Chemical Physics, Vol. 22, Issue 25
DOI: 10.1039/D0CP01206H

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

Influence of molecular shape on self-diffusion under severe confinement: A molecular dynamics study
journal, January 2019

Dhiman, I.; Shrestha, U. R.; Bhowmik, D.
Chemical Physics, Vol. 516
DOI: 10.1016/j.chemphys.2018.08.033

Preferential Adsorption in Ethane/Carbon Dioxide Fluid Mixtures Confined within Silica Nanopores
journal, November 2019

Elola, M. Dolores; Rodriguez, Javier
The Journal of Physical Chemistry C, Vol. 123, Issue 51
DOI: 10.1021/acs.jpcc.9b07969

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

Dhiman, I.; Bhowmik, D.; Shrestha, Utsab R.
Chemical Engineering Science, Vol. 180
DOI: 10.1016/j.ces.2018.01.027

Automated analysis and benchmarking of GCMC simulation programs in application to gas adsorption
journal, September 2017

Gowers, Richard J.; Farmahini, Amir H.; Friedrich, Daniel
Molecular Simulation, Vol. 44, Issue 4
DOI: 10.1080/08927022.2017.1375492

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Momma, Koichi; Izumi, Fujio
Journal of Applied Crystallography, Vol. 44, Issue 6
DOI: 10.1107/S0021889811038970

Diffusion processes in a poly-crystalline zeolitic material: A molecular dynamics study
journal, August 2018

Thomas, Angela Mary; Subramanian, Yashonath
The Journal of Chemical Physics, Vol. 149, Issue 6
DOI: 10.1063/1.5037146

Molecular dynamics simulations on single-file diffusions: Effects of channel potential periods and particle-particle interactions
journal, October 2009

Yang, Xiaofeng; Wu, Mingzhong; Qin, Zhangfeng
Journal of Applied Physics, Vol. 106, Issue 8
DOI: 10.1063/1.3247576

On the location and disorder of the tetrapropylammonium (TPA) ion in zeolite ZSM-5 with improved framework accuracy
journal, April 1987

van Koningsveld, H.; van Bekkum, H.; Jansen, J. C.
Acta Crystallographica Section B Structural Science, Vol. 43, Issue 2
DOI: 10.1107/S0108768187098173

CO2 Adsorption in Metal-Organic Framework Mg-MOF-74: Effects of Inter-Crystalline Space
journal, November 2020

Gautam, Siddharth; Cole, David
Nanomaterials, Vol. 10, Issue 11
DOI: 10.3390/nano10112274

Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes
March 1998

Martin, Marcus G.; Siepmann, J. Ilja
DOI: 10.1021/jp972543+

High CO ₂ /CH ₄ and C2 Hydrocarbons/CH ₄ Selectivity in a Chemically Robust Porous Coordination Polymer
journal, February 2013

Duan, Jingui; Higuchi, Masakazu; Horike, Satoshi
Advanced Functional Materials, Vol. 23, Issue 28
DOI: 10.1002/adfm.201203288

Structure and dynamics of ethane confined in silica nanopores in the presence of CO ₂
journal, February 2020

Liu, Tingting; Gautam, Siddharth; Cole, David R.
The Journal of Chemical Physics, Vol. 152, Issue 8
DOI: 10.1063/1.5134451

Sorption, Structure and Dynamics of CO2 and Ethane in Silicalite at High Pressure: A Combined Monte Carlo and Molecular Dynamics Simulation Study
journal, December 2018

Gautam, Siddharth; Liu, Tingting; Cole, David
Molecules, Vol. 24, Issue 1
DOI: 10.3390/molecules24010099

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

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

Highly Selective Separation of CO 2 , CH 4 , and C 2 –C 4 Hydrocarbons in Ultramicroporous Semicycloaliphatic Polyimides
journal, July 2018

Yan, Jun; Zhang, Biao; Wang, Zhonggang
ACS Applied Materials & Interfaces, Vol. 10, Issue 31
DOI: 10.1021/acsami.8b07294

A novel approach to identify accessible and inaccessible pores in gas shales using combined low-pressure sorption and SAXS/SANS analysis
journal, August 2020

Chandra, Debanjan; Vishal, Vikram; Bahadur, Jitendra
International Journal of Coal Geology, Vol. 228
DOI: 10.1016/j.coal.2020.103556

CO ₂ –C ₄ H ₁₀ Mixtures Simulated in Silica Slit Pores: Relation between Structure and Dynamics
journal, June 2015

Le, Thu; Striolo, Alberto; Cole, David R.
The Journal of Physical Chemistry C, Vol. 119, Issue 27
DOI: 10.1021/acs.jpcc.5b03160

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Title: Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22

Abstract

Citation Formats

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

Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field journal, January 2004

Anomalous Diffusivity in Porous Solids: Levitation Effect book, July 2020

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

Influence of molecular shape on self-diffusion under severe confinement: A molecular dynamics study journal, January 2019

Preferential Adsorption in Ethane/Carbon Dioxide Fluid Mixtures Confined within Silica Nanopores journal, November 2019

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

Automated analysis and benchmarking of GCMC simulation programs in application to gas adsorption journal, September 2017

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Diffusion processes in a poly-crystalline zeolitic material: A molecular dynamics study journal, August 2018

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Sorption, Structure and Dynamics of CO2 and Ethane in Silicalite at High Pressure: A Combined Monte Carlo and Molecular Dynamics Simulation Study journal, December 2018

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

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CO 2 –C 4 H 10 Mixtures Simulated in Silica Slit Pores: Relation between Structure and Dynamics journal, June 2015

Location dependent orientational structure and dynamics of ethane in ZSM5
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Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field
journal, January 2004

Anomalous Diffusivity in Porous Solids: Levitation Effect
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The framework topology of ZSM-22: A high silica zeolite
journal, November 1985

Adsorption Equilibria of C ₁ to C ₄ Alkanes, CO ₂ , and SF ₆ on Silicalite
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Simulations on “Powder” Samples for Better Agreement with Macroscopic Measurements
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Structure and Dynamics of Confined C-O-H Fluids Relevant to the Subsurface: Application of Magnetic Resonance, Neutron Scattering, and Molecular Dynamics Simulations
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Effects of inter-crystalline space on the adsorption of ethane and CO ₂ in silicalite: implications for enhanced adsorption
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Influence of molecular shape on self-diffusion under severe confinement: A molecular dynamics study
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Preferential Adsorption in Ethane/Carbon Dioxide Fluid Mixtures Confined within Silica Nanopores
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Effect of molecular shape on rotation under severe confinement
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Diffusion processes in a poly-crystalline zeolitic material: A molecular dynamics study
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Molecular dynamics simulations on single-file diffusions: Effects of channel potential periods and particle-particle interactions
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