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2H NMR Studies on Water Dynamics in Functionalized Mesoporous Silica

  • Max Weigler , Martin Brodrecht , Hergen Breitzke , Felix Dietrich , Matthias Sattig , Gerd Buntkowsky EMAIL logo and Michael Vogel EMAIL logo
Published/Copyright: January 5, 2018
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 232 Issue 7-8

Abstract

Mesoporous silica MCM-41 is prepared, for which the inner surfaces are modified by 3-(aminopropyl)triethoxysilane (APTES) in a controlled manner. Nitrogen gas adsorpition yields a pore diameter of 2.2 nm for the APTES functionalized MCM-41. 2H nuclear magnetic resonance (NMR) and broadband dielectric spectroscopy (BDS) provide detailed and consistent insights into the temperature-dependent reorientation dynamics of water in this confinement. We find that a liquid water species becomes accompanied by a solid water species when cooling through ~210 K, as indicated by an onset of bimodal 2H spin-lattice relaxation. The reorientation of the liquid water species is governed by pronounced dynamical heterogeneity in the whole temperature range. Its temperature dependence shows a mild dynamic crossover when the solid water species emerges and, hence, the volume accessible to the liquid water species further shrinks. Therefore, we attribute this variation in the temperature dependence to a change from bulk-like behavior towards interface-dominated dynamics. Below this dynamic crossover, 2H line-shape and stimulted-echo studies show that water reorientation becomes anisotropic upon cooling, suggesting that these NMR approaches, but also BDS measurements do no longer probe the structural (α) relaxation, but rather a secondary (β) relaxation of water at sufficiently low temperatures. Then, another dynamic crossover at ~180 K can be rationalized in terms of a change of the temperature dependence of the β relaxation in response to a glassy freezing of the α relaxation of confined water. Comparing these results for APTES modied MCM-41 with previous findings for mesoporous silica with various pore diameters, we obtain valuable information about the dependence of water dynamics in restricted geometries on the size of the nanoscopic confinements and the properties of the inner surfaces.

Keywords: confined water; 2H NMR; mesoporous silica

Acknowledgement

Financial support of the Deutsche Forschungsgemeinschaft (DFG) in the framework of Forschergruppe FOR 1583 through grants Bu-911/18-1/2 and Vo-905/8-1/2 is gratefully acknowledged.

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Received: 2017-09-14
Accepted: 2017-11-09
Published Online: 2018-01-05
Published in Print: 2018-07-26

©2018 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Editorial: Molecules in Prison
  4. Properties of Hydrogen-Bonded Liquids at Interfaces
  5. Ab-Initio Molecular Dynamics Simulations and Calculations of Spectroscopic Parameters in Hydrogen-Bonding Liquids in Confinement (Project 8)
  6. Liquid Water Confined in Cellulose with Variable Interfacial Hydrophilicity
  7. A Combined Solid-State NMR, Dielectric Spectroscopy and Calorimetric Study of Water in Lowly Hydrated MCM-41 Samples
  8. Triplet Solvation Dynamics of Hydrogen Bonding Liquids in Confinement
  9. 2H NMR Studies on Water Dynamics in Functionalized Mesoporous Silica
  10. 2H NMR Studies on the Dynamics of Pure and Mixed Hydrogen-Bonded Liquids in Confinement
  11. Water/PEG Mixtures: Phase Behavior, Dynamics and Soft Confinement
  12. Effects of Cosolvents and Macromolecular Crowding on the Phase Transitions and Temperature-Pressure Stability of Chiral and Racemic Poly-Lysine
  13. Chemically Modified Silica Materials as Model Systems for the Characterization of Water-Surface Interactions
  14. Nanoscale Structuring in Confined Geometries using Atomic Layer Deposition: Conformal Coating and Nanocavity Formation
  15. Surface Enhanced DNP Assisted Solid-State NMR of Functionalized SiO2 Coated Polycarbonate Membranes
  16. Molecular Dynamics Simulations of Water, Silica, and Aqueous Mixtures in Bulk and Confinement
  17. Monitoring the Process of Nanocavity Formation on a Monomolecular Level
  18. Elastin-like Peptide in Confinement: FT-IR and NMR T1 Relaxation Data
https://doi.org/10.1515/zpch-2017-1034
Keywords for this article
confined water; 2H NMR; mesoporous silica

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Editorial: Molecules in Prison
  4. Properties of Hydrogen-Bonded Liquids at Interfaces
  5. Ab-Initio Molecular Dynamics Simulations and Calculations of Spectroscopic Parameters in Hydrogen-Bonding Liquids in Confinement (Project 8)
  6. Liquid Water Confined in Cellulose with Variable Interfacial Hydrophilicity
  7. A Combined Solid-State NMR, Dielectric Spectroscopy and Calorimetric Study of Water in Lowly Hydrated MCM-41 Samples
  8. Triplet Solvation Dynamics of Hydrogen Bonding Liquids in Confinement
  9. 2H NMR Studies on Water Dynamics in Functionalized Mesoporous Silica
  10. 2H NMR Studies on the Dynamics of Pure and Mixed Hydrogen-Bonded Liquids in Confinement
  11. Water/PEG Mixtures: Phase Behavior, Dynamics and Soft Confinement
  12. Effects of Cosolvents and Macromolecular Crowding on the Phase Transitions and Temperature-Pressure Stability of Chiral and Racemic Poly-Lysine
  13. Chemically Modified Silica Materials as Model Systems for the Characterization of Water-Surface Interactions
  14. Nanoscale Structuring in Confined Geometries using Atomic Layer Deposition: Conformal Coating and Nanocavity Formation
  15. Surface Enhanced DNP Assisted Solid-State NMR of Functionalized SiO2 Coated Polycarbonate Membranes
  16. Molecular Dynamics Simulations of Water, Silica, and Aqueous Mixtures in Bulk and Confinement
  17. Monitoring the Process of Nanocavity Formation on a Monomolecular Level
  18. Elastin-like Peptide in Confinement: FT-IR and NMR T1 Relaxation Data
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