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Title: Water Dynamics in Nanoporous Silica: Ultrafast Vibrational Spectroscopy and Molecular Dynamics Simulations

Abstract

Nanoporous silica materials are important in catalysis, energy, and materials applications in which water is an essential component. System performance is intimately connected to the water dynamics occurring in the confined environment. However, the dynamics and associated structures of water in mesoporous silica are challenging to measure or predict. Here, water dynamics subject to nanoscale confinement are examined via the ultrafast infrared spectroscopy of selenocyanate (SeCN-) dissolved in the hydrated ~2.4 nm silica nanopores of MCM41. Polarization selective pump-probe and two-dimensional infrared measurements on the CN stretching mode of SeCN- are used to probe the effect of confinement on orientational relaxation and spectral diffusion dynamics. The dynamics of SeCN- provide information on water hydrogen bond dynamics. The long CN stretch lifetime (~36 ps), relative to the water hydroxyl stretch (< 2 ps), significantly extends the timescales that can be accessed. Complete orientational relaxation (C2(t), orientational correlation function) and spectral diffusion (Cω(t), frequency-frequency correlation function) dynamics are presented and compared to the simulated time correlation functions in a model silica pore of the same size. A slow decay component not present in the bulk liquid is observed in both experiments, indicating that the hydrogen bond dynamics are significantly altered by confinement.more » The simulations reveal a qualitative difference in the functional dependence of C2(t;d) and Cω(t;d) on d, the distance from the interface. The former becomes exponentially faster with distance while the latter makes an abrupt transition from slower to faster dynamics midway between the surface and pore center, d≅ 6 Å.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Stanford Univ., CA (United States)
  2. Univ. of Kansas, Lawrence, KS (United States)
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR)
OSTI Identifier:
1783279
Alternate Identifier(s):
OSTI ID: 1804116
Grant/Contract Number:  
FG02-84ER13251; CHE-1339661; FA9550-16-1-0104
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 9; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 14 SOLAR ENERGY; Liquids; Diffusion; Silica; Infrared light; Probes

Citation Formats

Yamada, Steven A., Shin, Jae Yoon, Thompson, Ward H., and Fayer, Michael D. Water Dynamics in Nanoporous Silica: Ultrafast Vibrational Spectroscopy and Molecular Dynamics Simulations. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.9b00593.
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Yamada, Steven A., Shin, Jae Yoon, Thompson, Ward H., & Fayer, Michael D. Water Dynamics in Nanoporous Silica: Ultrafast Vibrational Spectroscopy and Molecular Dynamics Simulations. United States. https://doi.org/10.1021/acs.jpcc.9b00593
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Yamada, Steven A., Shin, Jae Yoon, Thompson, Ward H., and Fayer, Michael D. Wed . "Water Dynamics in Nanoporous Silica: Ultrafast Vibrational Spectroscopy and Molecular Dynamics Simulations". United States. https://doi.org/10.1021/acs.jpcc.9b00593. https://www.osti.gov/servlets/purl/1783279.
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@article{osti_1783279,
title = {Water Dynamics in Nanoporous Silica: Ultrafast Vibrational Spectroscopy and Molecular Dynamics Simulations},
author = {Yamada, Steven A. and Shin, Jae Yoon and Thompson, Ward H. and Fayer, Michael D.},
abstractNote = {Nanoporous silica materials are important in catalysis, energy, and materials applications in which water is an essential component. System performance is intimately connected to the water dynamics occurring in the confined environment. However, the dynamics and associated structures of water in mesoporous silica are challenging to measure or predict. Here, water dynamics subject to nanoscale confinement are examined via the ultrafast infrared spectroscopy of selenocyanate (SeCN-) dissolved in the hydrated ~2.4 nm silica nanopores of MCM41. Polarization selective pump-probe and two-dimensional infrared measurements on the CN stretching mode of SeCN- are used to probe the effect of confinement on orientational relaxation and spectral diffusion dynamics. The dynamics of SeCN- provide information on water hydrogen bond dynamics. The long CN stretch lifetime (~36 ps), relative to the water hydroxyl stretch (< 2 ps), significantly extends the timescales that can be accessed. Complete orientational relaxation (C2(t), orientational correlation function) and spectral diffusion (Cω(t), frequency-frequency correlation function) dynamics are presented and compared to the simulated time correlation functions in a model silica pore of the same size. A slow decay component not present in the bulk liquid is observed in both experiments, indicating that the hydrogen bond dynamics are significantly altered by confinement. The simulations reveal a qualitative difference in the functional dependence of C2(t;d) and Cω(t;d) on d, the distance from the interface. The former becomes exponentially faster with distance while the latter makes an abrupt transition from slower to faster dynamics midway between the surface and pore center, d≅ 6 Å.},
doi = {10.1021/acs.jpcc.9b00593},
journal = {Journal of Physical Chemistry. C},
number = 9,
volume = 123,
place = {United States},
year = {Wed Jan 30 00:00:00 EST 2019},
month = {Wed Jan 30 00:00:00 EST 2019}
}
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https://doi.org/10.1021/acs.jpcc.9b00593
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Works referenced in this record:

Comparison of the Orientational Dynamics of Water Confined in Hydrophobic and Hydrophilic Nanopores
journal, October 2002

  • Scodinu, Alessandra; Fourkas, John T.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 40
  • DOI: 10.1021/jp026349l

Translational and rotational dynamics of water in mesoporous silica materials: MCM-41-S and MCM-48-S
journal, August 2003

  • Faraone, Antonio; Liu, Li; Mou, Chung-Yuan
  • The Journal of Chemical Physics, Vol. 119, Issue 7
  • DOI: 10.1063/1.1584653

Fragile-to-strong liquid transition in deeply supercooled confined water
journal, January 2004

  • Faraone, A.; Liu, L.; Mou, C. -Y.
  • The Journal of Chemical Physics, Vol. 121, Issue 22
  • DOI: 10.1063/1.1832595

Neutron Scattering Study on Dynamics of Water Molecules in MCM-41. 2. Determination of Translational Diffusion Coefficient
journal, June 2005

  • Takahara, Shuichi; Sumiyama, Naoya; Kittaka, Shigeharu
  • The Journal of Physical Chemistry B, Vol. 109, Issue 22
  • DOI: 10.1021/jp046036l

Finite Size Effects on Hydrogen Bonds in Confined Water
journal, October 2008

  • Musat, Raluca; Renault, Jean Philippe; Candelaresi, Marco
  • Angewandte Chemie International Edition, Vol. 47, Issue 42
  • DOI: 10.1002/anie.200802630

Structure and dynamics of water confined in silica nanopores
journal, November 2011

  • Milischuk, Anatoli A.; Ladanyi, Branka M.
  • The Journal of Chemical Physics, Vol. 135, Issue 17
  • DOI: 10.1063/1.3657408

Reorientation dynamics of nanoconfined water: Power-law decay, hydrogen-bond jumps, and test of a two-state model
journal, January 2012

  • Laage, Damien; Thompson, Ward H.
  • The Journal of Chemical Physics, Vol. 136, Issue 4
  • DOI: 10.1063/1.3679404

Polarizability anisotropy relaxation in nanoconfinement: Molecular simulation study of water in cylindrical silica pores
journal, November 2014

  • Milischuk, Anatoli A.; Ladanyi, Branka M.
  • The Journal of Chemical Physics, Vol. 141, Issue 18
  • DOI: 10.1063/1.4896218

Origins of the non-exponential reorientation dynamics of nanoconfined water
journal, November 2014

  • Fogarty, Aoife C.; Duboué-Dijon, Elise; Laage, Damien
  • The Journal of Chemical Physics, Vol. 141, Issue 18
  • DOI: 10.1063/1.4896983

Simulations of the infrared, Raman, and 2D-IR photon echo spectra of water in nanoscale silica pores
journal, May 2016

  • Burris, Paul C.; Laage, Damien; Thompson, Ward H.
  • The Journal of Chemical Physics, Vol. 144, Issue 19
  • DOI: 10.1063/1.4949766

Photochemistry and Photophysics in Silica-Based Materials: Ultrafast and Single Molecule Spectroscopy Observation
journal, October 2017

Organic Reactions on Silica in Water
journal, February 2009

  • Minakata, Satoshi; Komatsu, Mitsuo
  • Chemical Reviews, Vol. 109, Issue 2
  • DOI: 10.1021/cr8003955

Dynamic Crossover in Supercooled Confined Water: Understanding Bulk Properties through Confinement
journal, January 2010

  • Gallo, P.; Rovere, M.; Chen, S. -H.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 4
  • DOI: 10.1021/jz9003125

Hydrophilic and hydrophobic sites on dehydrated crystalline and amorphous silicas
journal, January 1991

  • Bolis, Vera; Fubini, Bice; Marchese, Leonardo
  • Journal of the Chemical Society, Faraday Transactions, Vol. 87, Issue 3
  • DOI: 10.1039/ft9918700497

Distinguishing the Silanol Groups in the Mesoporous Molecular Sieve MCM-41
journal, January 1996

  • Chen, Jiesheng; Li, Qinghua; Xu, Ruren
  • Angewandte Chemie International Edition in English, Vol. 34, Issue 2324
  • DOI: 10.1002/anie.199526941

Hydrogen Bonding of Water Confined in Mesoporous Silica MCM-41 and SBA-15 Studied by 1 H Solid-State NMR
journal, October 2004

  • Grünberg, Bob; Emmler, Thomas; Gedat, Egbert
  • Chemistry - A European Journal, Vol. 10, Issue 22
  • DOI: 10.1002/chem.200400351

Characterizing Solvent Dynamics in Nanoscopic Silica Sol–Gel Glass Pores by 2D-IR Spectroscopy of an Intrinsic Vibrational Probe
journal, October 2014

  • Huber, Christopher J.; Massari, Aaron M.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 44
  • DOI: 10.1021/jp508389u

2D-IR Spectroscopy of Porous Silica Nanoparticles: Measuring the Distance Sensitivity of Spectral Diffusion
journal, September 2015

  • Huber, Christopher J.; Egger, Samuel M.; Spector, Ivan C.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 45
  • DOI: 10.1021/acs.jpcc.5b05637

Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water
journal, September 2003

Hydrogen bond dynamics in aqueous NaBr solutions
journal, October 2007

  • Park, S.; Fayer, M. D.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 43
  • DOI: 10.1073/pnas.0707824104

Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations
journal, June 2017

  • Yamada, Steven A.; Thompson, Ward H.; Fayer, Michael D.
  • The Journal of Chemical Physics, Vol. 146, Issue 23
  • DOI: 10.1063/1.4984766

On the orientational relaxation of HDO in liquid water
journal, September 2005

  • Rezus, Y. L. A.; Bakker, H. J.
  • The Journal of Chemical Physics, Vol. 123, Issue 11
  • DOI: 10.1063/1.2009729

Simple fully reflective method of scatter reduction in 2D-IR spectroscopy
journal, January 2015

  • Spector, Ivan C.; Olson, Courtney M.; Huber, Christopher J.
  • Optics Letters, Vol. 40, Issue 8
  • DOI: 10.1364/OL.40.001850

Structural dynamics inside a functionalized metal–organic framework probed by ultrafast 2D IR spectroscopy
journal, December 2014

  • Nishida, Jun; Tamimi, Amr; Fei, Honghan
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 52
  • DOI: 10.1073/pnas.1422194112

How to turn your pump–probe instrument into a multidimensional spectrometer: 2D IR and Vis spectroscopiesvia pulse shaping
journal, January 2009

  • Shim, Sang-Hee; Zanni, Martin T.
  • Phys. Chem. Chem. Phys., Vol. 11, Issue 5
  • DOI: 10.1039/B813817F

Comparisons of 2D IR measured spectral diffusion in rotating frames using pulse shaping and in the stationary frame using the standard method
journal, November 2012

  • Karthick Kumar, S. K.; Tamimi, A.; Fayer, M. D.
  • The Journal of Chemical Physics, Vol. 137, Issue 18
  • DOI: 10.1063/1.4764470

Adsorption of Gases in Multimolecular Layers
journal, February 1938

  • Brunauer, Stephen; Emmett, P. H.; Teller, Edward
  • Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
  • DOI: 10.1021/ja01269a023

The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms
journal, January 1951

  • Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P.
  • Journal of the American Chemical Society, Vol. 73, Issue 1
  • DOI: 10.1021/ja01145a126

Adsorption Study of Surface and Structural Properties of MCM-41 Materials of Different Pore Sizes
journal, January 1997

  • Kruk, M.; Jaroniec, M.; Sayari, A.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 4
  • DOI: 10.1021/jp962000k

Determination of Pore Size and Pore Wall Structure of MCM-41 by Using Nitrogen Adsorption, Transmission Electron Microscopy, and X-ray Diffraction
journal, January 2000

  • Kruk, Michal; Jaroniec, Mietek; Sakamoto, Yasuhiro
  • The Journal of Physical Chemistry B, Vol. 104, Issue 2
  • DOI: 10.1021/jp992718a

Enthalpy and interfacial free energy changes of water capillary condensed in mesoporous silica, MCM-41 and SBA-15
journal, January 2006

  • Kittaka, Shigeharu; Ishimaru, Shinji; Kuranishi, Miki
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 27
  • DOI: 10.1039/b518365k

Hydration of MCM-41 Studied by Sorption Calorimetry
journal, September 2007

  • Kocherbitov, Vitaly; Alfredsson, Viveka
  • The Journal of Physical Chemistry C, Vol. 111, Issue 35
  • DOI: 10.1021/jp072474r

Concepts and Methods of 2D Infrared Spectroscopy
book, January 2011

Frequency-frequency correlation functions and apodization in two-dimensional infrared vibrational echo spectroscopy: A new approach
journal, September 2007

  • Kwak, Kyungwon; Park, Sungnam; Finkelstein, Ilya J.
  • The Journal of Chemical Physics, Vol. 127, Issue 12
  • DOI: 10.1063/1.2772269

Taking apart the two-dimensional infrared vibrational echo spectra: More information and elimination of distortions
journal, May 2008

  • Kwak, Kyungwon; Rosenfeld, Daniel E.; Fayer, M. D.
  • The Journal of Chemical Physics, Vol. 128, Issue 20
  • DOI: 10.1063/1.2927906

The missing term in effective pair potentials
journal, November 1987

  • Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a038

Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes
journal, March 1977

  • Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C.
  • Journal of Computational Physics, Vol. 23, Issue 3
  • DOI: 10.1016/0021-9991(77)90098-5

Testing a Two-State Model of Nanoconfined Liquids:  Conformational Equilibrium of Ethylene Glycol in Amorphous Silica Pores
journal, December 2006

  • Gulmen, Tolga S.; Thompson, Ward H.
  • Langmuir, Vol. 22, Issue 26
  • DOI: 10.1021/la062285k

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

On the Diffusion of Acetonitrile in Nanoscale Amorphous Silica Pores. Understanding Anisotropy and the Effects of Hydrogen Bonding
journal, September 2013

  • Norton, Cassandra D.; Thompson, Ward H.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 37
  • DOI: 10.1021/jp407830f

Reorientation Dynamics of Nanoconfined Acetonitrile: A Critical Examination of Two-State Models
journal, April 2014

  • Norton, Cassandra D.; Thompson, Ward H.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 28
  • DOI: 10.1021/jp501363q

Simulations of Infrared Spectra of Nanoconfined Liquids: Acetonitrile Confined in Nanoscale, Hydrophilic Silica Pores †
journal, March 2009

  • Morales, Christine M.; Thompson, Ward H.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 10
  • DOI: 10.1021/jp8072969

Is the Ewald summation still necessary? Pairwise alternatives to the accepted standard for long-range electrostatics
journal, June 2006

  • Fennell, Christopher J.; Gezelter, J. Daniel
  • The Journal of Chemical Physics, Vol. 124, Issue 23
  • DOI: 10.1063/1.2206581

Ligand Exchange Dynamics in Aqueous Solution Studied with 2DIR Spectroscopy
journal, May 2010

  • Park, Sungnam; Ji, Minbiao; Gaffney, Kelly J.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 19
  • DOI: 10.1021/jp100833t

Contact Ion Pair Formation between Hard Acids and Soft Bases in Aqueous Solutions Observed with 2DIR Spectroscopy
journal, August 2013

  • Sun, Zheng; Zhang, Wenkai; Ji, Minbiao
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp4033854

A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

The Solvation of Acetonitrile
journal, April 1999

  • Reimers, Jeffrey R.; Hall, Lachlan E.
  • Journal of the American Chemical Society, Vol. 121, Issue 15
  • DOI: 10.1021/ja983878n

Theory of third-order spectroscopic methods to extract detailed molecular orientational dynamics for planar surfaces and other uniaxial systems
journal, April 2014

  • Nishida, Jun; Fayer, Michael D.
  • The Journal of Chemical Physics, Vol. 140, Issue 14
  • DOI: 10.1063/1.4870436

A NMR technique for the analysis of pore structure: Application to materials with well-defined pore structure
journal, September 1987

  • Gallegos, David P.; Munn, Kevin; Smith, Douglas M.
  • Journal of Colloid and Interface Science, Vol. 119, Issue 1
  • DOI: 10.1016/0021-9797(87)90251-7

Relative role of surface interactions and topological effects in nuclear magnetic resonance of confined liquids
journal, October 1994

  • Korb, J. ‐P.; Delville, A.; Xu, Shu
  • The Journal of Chemical Physics, Vol. 101, Issue 8
  • DOI: 10.1063/1.468333

Testing the Core/Shell Model of Nanoconfined Water in Reverse Micelles Using Linear and Nonlinear IR Spectroscopy
journal, April 2006

  • Piletic, Ivan R.; Moilanen, David E.; Spry, D. B.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 15
  • DOI: 10.1021/jp061065c

Water dynamics in large and small reverse micelles: From two ensembles to collective behavior
journal, July 2009

  • Moilanen, David E.; Fenn, Emily E.; Wong, Daryl
  • The Journal of Chemical Physics, Vol. 131, Issue 1
  • DOI: 10.1063/1.3159779

Dynamics in a Water Interfacial Boundary Layer Investigated with IR Polarization-Selective Pump–Probe Experiments
journal, April 2017

  • Yuan, Rongfeng; Yan, Chang; Nishida, Jun
  • The Journal of Physical Chemistry B, Vol. 121, Issue 17
  • DOI: 10.1021/acs.jpcb.7b01028

Vibrational Spectroscopy and Dynamics of Water Confined inside Reverse Micelles
journal, November 2009

  • Pieniazek, Piotr A.; Lin, Yu-Shan; Chowdhary, Janamejaya
  • The Journal of Physical Chemistry B, Vol. 113, Issue 45
  • DOI: 10.1021/jp906784t

Water Dynamics:  Vibrational Echo Correlation Spectroscopy and Comparison to Molecular Dynamics Simulations
journal, February 2004

  • Asbury, John B.; Steinel, Tobias; Stromberg, C.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 7
  • DOI: 10.1021/jp036266k

Dynamics of water probed with vibrational echo correlation spectroscopy
journal, January 2004

  • Asbury, John B.; Steinel, Tobias; Kwak, Kyungwon
  • The Journal of Chemical Physics, Vol. 121, Issue 24
  • DOI: 10.1063/1.1818107

Combined electronic structure/molecular dynamics approach for ultrafast infrared spectroscopy of dilute HOD in liquid H2O and D2O
journal, May 2004

  • Corcelli, S. A.; Lawrence, C. P.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 120, Issue 17
  • DOI: 10.1063/1.1683072

Separation of experimental 2D IR frequency-frequency correlation functions into structural and reorientation-induced contributions
journal, September 2015

  • Kramer, Patrick L.; Nishida, Jun; Fayer, Michael D.
  • The Journal of Chemical Physics, Vol. 143, Issue 12
  • DOI: 10.1063/1.4931402

Observation and theory of reorientation-induced spectral diffusion in polarization-selective 2D IR spectroscopy
journal, May 2015

  • Kramer, Patrick L.; Nishida, Jun; Giammanco, Chiara H.
  • The Journal of Chemical Physics, Vol. 142, Issue 18
  • DOI: 10.1063/1.4920949

On the Molecular Mechanism of Water Reorientation
journal, November 2008

  • Laage, Damien; Hynes, James T.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 45
  • DOI: 10.1021/jp805217u

Raman scattering study of liquid ethylene glycol confined to nanoporous silica glasses
journal, January 2001

  • Luo, Ren-Sheng; Jonas, Jiri
  • Journal of Raman Spectroscopy, Vol. 32, Issue 11
  • DOI: 10.1002/jrs.786

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

Picosecond orientational dynamics of water in living cells
journal, October 2017

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