Effects of pore connectivity and tortuosity on the dynamics of fluids confined in sub-nanometer pores

Gautam, Siddharth; Cole, David R.

doi:10.1039/d1cp04955k

Effects of pore connectivity and tortuosity on the dynamics of fluids confined in sub-nanometer pores

Journal Article · Wed Apr 27 00:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp04955k· OSTI ID:1978764

^[1]; Cole, David R. ^[2]

The Ohio State University, Columbus, OH (United States); OSTI
The Ohio State University, Columbus, OH (United States)

Dynamical behavior of fluids under nano-pore confinement is studied extensively as it has important implications for several industrial as well as geological processes. Pore network in many porous materials exhibits a varied degree of inter connections. The extent of this pore connectivity may affect the structural and dynamical behavior of the confined fluid. However, studies of fluid confinement addressing these effects systematically are lacking. In this paper we report molecular dynamics simulation studies addressing the effects of pore connectivity on the dynamics of two representative fluids – CO₂ and ethane in silicalite by systematically varying the degree of pore connectivity through selectively blocking some pore space with immobile methane molecules. By selectively turning off the pore spaces in the shape of straight, or tortuous zigzag channels, we also probe the effects of pore tortuosity. In general, pore connectivity is found to facilitate both the translational as well as rotational dynamics of both fluids, while the intermolecular modes of vibration in both fluids remain largely unaffected. The effects of providing connections between a set of straight or zigzag channel-like pores are however more nuanced. Pore tortuosity facilitates the rotational motion, but suppresses the translational motion of CO₂, while its effects on the rotational and translational motion of ethane are less pronounced. The intermolecular vibrational modes of both fluids shift to higher energies with an increase in the number of tortuous pores. The results reported here provide a detailed molecular level understanding of the effects of pore connectivity on the dynamics of fluids and thus have implications for applications like fluid separation.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State University, Columbus, OH (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0006878

OSTI ID:: 1978764

Alternate ID(s):: OSTI ID: 1866655

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 19 Vol. 24; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

Vapor–liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen Potoff, Jeffrey J.; Siepmann, J. Ilja AIChE Journal, Vol. 47, Issue 7, p. 1676-1682 https://doi.org/10.1002/aic.690470719	journal	July 2001
Effect of pore structure, randomness and size on effective mass diffusivity Mezedur, Minas M.; Kaviany, Massoud; Moore, Wayne AIChE Journal, Vol. 48, Issue 1, p. 15-24 https://doi.org/10.1002/aic.690480104	journal	January 2002
On tortuosity and the tortuosity factor in flow and diffusion through porous media Epstein, Norman Chemical Engineering Science, Vol. 44, Issue 3 https://doi.org/10.1016/0009-2509(89)85053-5	journal	January 1989
The framework topology of ZSM-22: A high silica zeolite Kokotailo, G. T.; Schlenker, J. L.; Dwyer, F. G. Zeolites, Vol. 5, Issue 6 https://doi.org/10.1016/0144-2449(85)90122-8	journal	November 1985
MCM-41, MCM-48 and related mesoporous adsorbents: their synthesis and characterisation Kumar, D.; Schumacher, K.; du Fresne von Hohenesche, C. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 187-188 https://doi.org/10.1016/S0927-7757(01)00638-0	journal	August 2001
Molecular dynamics as a tool to study heterogeneity in zeolites – Effect of Na+ cations on diffusion of CO2 and N2 in Na-ZSM-5 Newsome, David; Coppens, Marc-Olivier Chemical Engineering Science, Vol. 121 https://doi.org/10.1016/j.ces.2014.09.024	journal	January 2015
Influence of molecular shape on self-diffusion under severe confinement: A molecular dynamics study Dhiman, I.; Shrestha, U. R.; Bhowmik, D. Chemical Physics, Vol. 516 https://doi.org/10.1016/j.chemphys.2018.08.033	journal	January 2019
A novel approach to identify accessible and inaccessible pores in gas shales using combined low-pressure sorption and SAXS/SANS analysis Chandra, Debanjan; Vishal, Vikram; Bahadur, Jitendra International Journal of Coal Geology, Vol. 228 https://doi.org/10.1016/j.coal.2020.103556	journal	August 2020
Location dependent orientational structure and dynamics of ethane in ZSM5 Gautam, Siddharth; Liu, Tingting; Patankar, Sumant Chemical Physics Letters, Vol. 648 https://doi.org/10.1016/j.cplett.2016.02.021	journal	March 2016
Quasi-elastic neutron scattering and molecular dynamics simulation as complementary techniques for studying diffusion in zeolites Jobic, Hervé; Theodorou, Doros N. Microporous and Mesoporous Materials, Vol. 102, Issue 1-3 https://doi.org/10.1016/j.micromeso.2006.12.034	journal	May 2007
Effects of Confinement and Pressure on the Vibrational Behavior of Nano-Confined Propane Gautam, Siddharth; Kolesnikov, Alexander I.; Rother, Gernot The Journal of Physical Chemistry A, Vol. 122, Issue 33 https://doi.org/10.1021/acs.jpca.8b05028	journal	July 2018
Propane–Water Mixtures Confined within Cylindrical Silica Nanopores: Structural and Dynamical Properties Probed by Molecular Dynamics Le, Tran Thi Bao; Striolo, Alberto; Gautam, Siddharth S. Langmuir, Vol. 33, Issue 42 https://doi.org/10.1021/acs.langmuir.7b03093	journal	September 2017
Mechanism of the Accelerated Water Formation Reaction under Interfacial Confinement Wang, Mengen; Zhou, Chen; Akter, Nusnin ACS Catalysis, Vol. 10, Issue 11 https://doi.org/10.1021/acscatal.9b05289	journal	April 2020
Membrane Gas Separation: A Review/State of the Art Bernardo, P.; Drioli, E.; Golemme, G. Industrial & Engineering Chemistry Research, Vol. 48, Issue 10 https://doi.org/10.1021/ie8019032	journal	May 2009
Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field Cygan, Randall T.; Liang, Jian-Jie; Kalinichev, Andrey G. The Journal of Physical Chemistry B, Vol. 108, Issue 4 https://doi.org/10.1021/jp0363287	journal	January 2004
Diffusion in Pore Networks: Effective Self-Diffusivity and the Concept of Tortuosity Rincon Bonilla, Mauricio; Bhatia, Suresh K. The Journal of Physical Chemistry C, Vol. 117, Issue 7 https://doi.org/10.1021/jp3070954	journal	February 2013
Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes Martin, Marcus G.; Siepmann, J. Ilja https://doi.org/10.1021/jp972543+		March 1998
Effects of water on the stochastic motions of propane confined in MCM-41-S pores Gautam, Siddharth; Le, Tran Thi Bao; Rother, Gernot Physical Chemistry Chemical Physics, Vol. 21, Issue 45 https://doi.org/10.1039/C9CP04741G	journal	January 2019
Effects of inter-crystalline space on the adsorption of ethane and CO ₂ in silicalite: implications for enhanced adsorption Gautam, Siddharth; Cole, David R. Physical Chemistry Chemical Physics, Vol. 22, Issue 25 https://doi.org/10.1039/D0CP01206H	journal	January 2020
DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism Todorov, Ilian T.; Smith, William; Trachenko, Kostya Journal of Materials Chemistry, Vol. 16, Issue 20, p. 1911-1918 https://doi.org/10.1039/b517931a	journal	January 2006
DL_MONTE: a general purpose program for parallel Monte Carlo simulation Purton, J. A.; Crabtree, J. C.; Parker, S. C. Molecular Simulation, Vol. 39, Issue 14-15 https://doi.org/10.1080/08927022.2013.839871	journal	December 2013
Diffusion of confined fluids in microporous zeolites and clay materials Mitra, S.; Sharma, V. K.; Mukhopadhyay, R. Reports on Progress in Physics, Vol. 84, Issue 6 https://doi.org/10.1088/1361-6633/abf085	journal	May 2021
Understanding nano effects in catalysis Yang, Fan; Deng, Dehui; Pan, Xiulian National Science Review, Vol. 2, Issue 2 https://doi.org/10.1093/nsr/nwv024	journal	May 2015
Computer Simulation of Liquids Allen, Michael P.; Tildesley, Dominic J. https://doi.org/10.1093/oso/9780198803195.001.0001	book	June 2017
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
On the location and disorder of the tetrapropylammonium (TPA) ion in zeolite ZSM-5 with improved framework accuracy van Koningsveld, H.; van Bekkum, H.; Jansen, J. C. Acta Crystallographica Section B Structural Science, Vol. 43, Issue 2 https://doi.org/10.1107/S0108768187098173	journal	April 1987
Revealing pore connectivity across scales and resolutions with X‐ray CT Lucas, Maik; Vetterlein, Doris; Vogel, Hans‐Jörg European Journal of Soil Science, Vol. 72, Issue 2 https://doi.org/10.1111/ejss.12961	journal	April 2020
Characterization and Analysis of Porosity and Pore Structures Anovitz, Lawrence M.; Cole, David R. Reviews in Mineralogy and Geochemistry, Vol. 80, Issue 1 https://doi.org/10.2138/rmg.2015.80.04	journal	January 2015
Structure and Dynamics of Confined C-O-H Fluids Relevant to the Subsurface: Application of Magnetic Resonance, Neutron Scattering, and Molecular Dynamics Simulations Gautam, Siddharth S.; Ok, Salim; Cole, David R. Frontiers in Earth Science, Vol. 5 https://doi.org/10.3389/feart.2017.00043	journal	June 2017
Effects of Pore Connectivity on the Sorption of Fluids in Nanoporous Material: Ethane and CO2 Sorption in Silicalite Gautam, Siddharth; Cole, David R. ChemEngineering, Vol. 5, Issue 3 https://doi.org/10.3390/chemengineering5030055	journal	August 2021
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 Membranes, Vol. 11, Issue 2 https://doi.org/10.3390/membranes11020113	journal	February 2021
Contribution of Pore-Connectivity to Permeation Performance of Silicalite-1 Membrane; Part I, Pore Volume and Effective Pore Size Sakai, Motomu; Sasaki, Yukichi; Kaneko, Takuya Membranes, Vol. 11, Issue 6 https://doi.org/10.3390/membranes11060382	journal	May 2021
Contribution of Pore-Connectivity to Permeation Performance of Silicalite-1 Membrane; Part II, Diffusivity of C6 Hydrocarbon in Micropore Sakai, Motomu; Sasaki, Yukichi; Kaneko, Takuya Membranes, Vol. 11, Issue 6 https://doi.org/10.3390/membranes11060399	journal	May 2021
Sorption, Structure and Dynamics of CO2 and Ethane in Silicalite at High Pressure: A Combined Monte Carlo and Molecular Dynamics Simulation Study Gautam, Siddharth; Liu, Tingting; Cole, David Molecules, Vol. 24, Issue 1 https://doi.org/10.3390/molecules24010099	journal	December 2018

Similar Records

Ethane-CO2 Mixture Adsorption in Silicalite: Influence of Tortuosity and Connectivity of Pores on Selectivity

Journal Article · Sun Dec 03 19:00:00 EST 2023 · C · OSTI ID:2228360

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

Journal Article · Thu Feb 04 19:00:00 EST 2021 · Membranes · OSTI ID:1765020

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS

Effects of pore connectivity and tortuosity on the dynamics of fluids confined in sub-nanometer pores

Citation Formats

References (34)

Similar Records

Related Subjects