Skip to main content
SpringerLink
Log in

Molecular Structure and Dynamics of Nano-Confined Water: Computer Simulations of Aqueous Species in Clay, Cement, and Polymer Membranes

  • Conference paper
  • First Online:
Book cover Transport and Reactivity of Solutions in Confined Hydrosystems

Abstract

Molecular-level knowledge of the thermodynamic, structural, and transport properties of water confined by interfaces and nanopores of various materials is crucial for quantitative understanding and prediction of many natural and technological processes, including carbon sequestration, water desalination, nuclear waste storage, cement chemistry, fuel cell technology, etc. Computational molecular modeling is capable to significantly complement the experimental investigations of such systems by providing invaluable atomic-scale information leading to improved understanding of the specific effects of the substrate structure and composition on the structure, dynamics and reactivity of interfacial and nano-confined aqueous solutions. This paper offers a brief overview of recent efforts to quantify some of these effects for individual H2O molecules and hydrated ions confined at the interfaces and in nanopores of several typical hydrophilic and hydrophobic materials. The first molecular layer of aqueous solution at all substrates is often highly ordered, indicating reduced translational and orientational mobility of the H2O molecules. This ordering cannot be simply described as “ice-like”, but rather resembles the behavior of supercooled water or amorphous ice, although with very significant substrate-specific variations.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Brown GE (2001) Surface science – How minerals react with water. Science 294:67–69

    Article  CAS  Google Scholar 

  2. Sverjensky DA (2006) Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions. Geochim Cosmochim Acta 70:2427–2453

    Article  CAS  Google Scholar 

  3. Brown GE, Calas G (2012) Mineral-aqueous solution interfaces and their impact on the environment. Geochem Perspect 1(4–5):483–742

    Article  Google Scholar 

  4. Fenter P, Sturchio NC (2004) Mineral-water interfacial structures revealed by synchrotron X-ray scattering. Prog Surf Sci 77:171–258

    Article  CAS  Google Scholar 

  5. Wenk H-R (ed) (2006) Neutron scattering in earth sciences. Rev Miner Geochem 63:1–471

    Google Scholar 

  6. Shen YR, Ostroverkhov V (2006) Sum-frequency vibrational spectroscopy on water interfaces: polar orientation of water molecules at interfaces. Chem Rev 106:1140–1154

    Article  CAS  Google Scholar 

  7. Cole DR, Mamontov E, Rother G (2009) Structure and dynamics of fluids in microporous and mesoporous earth and engineered materials. In: Liang L, Rinaldi R, Schober H (eds) Neutron applications in earth, energy and environmental sciences. Springer, New York

    Google Scholar 

  8. Arbogast T (ed) (2007) Computational needs for the subsurface sciences. Workshop report. U.S. DOE Office of Science, Washington D.C., April 2007, 291pp

    Google Scholar 

  9. Frenkel D, Smit B (2002) Understanding molecular simulation: from algorithms to applications, 2nd edn. Academic, San Diego

    Google Scholar 

  10. Cygan RT, Kubicki JD (eds) (2001) Molecular modeling theory and applications in the geosciences. Rev Miner Geochem 42:1–531

    Google Scholar 

  11. Kalinichev AG, Kirkpatrick RJ (2002) Molecular dynamics modeling of chloride binding to the surfaces of Ca hydroxide, hydrated Ca-aluminate and Ca-silicate phases. Chem Mater 14:3539–3549

    Article  CAS  Google Scholar 

  12. Cygan RT, Liang J-J, Kalinichev AG (2004) Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field. J Phys Chem B 108:1255–1266

    Article  CAS  Google Scholar 

  13. Rustad JR, Felmy AR (2005) The influence of edge sites on the development of surface charge on goethite nanoparticles: a molecular dynamics study. Geochim Cosmochim Acta 69:1405–1411

    Article  CAS  Google Scholar 

  14. Tossell JA (2005) Theoretical study on the dimerization of Si(OH)4 in aqueous solution and its dependence on temperature and dielectric constant. Geochim Cosmochim Acta 69:283–291

    Article  CAS  Google Scholar 

  15. Criscenti LJ, Kubicki JD, Brantley SL (2006) Silicate glass and mineral dissolution: calculated reaction paths and activation energies for hydrolysis of a Q3 Si by H3O+ using ab initio methods. J Phys Chem A 110:198–206

    Article  CAS  Google Scholar 

  16. Kerisit S, Rosso KM (2006) Computer simulation of electron transfer at hematite surfaces. Geochim Cosmochim Acta 70:1888–1903

    Article  CAS  Google Scholar 

  17. Spagnoli D, Cooke DJ, Kerisit S, Parker SC (2006) Molecular dynamics simulations of the interaction between the surfaces of polar solids and aqueous solutions. J Mater Chem 16:1997–2006

    Article  CAS  Google Scholar 

  18. Wang J, Kalinichev AG, Kirkpatrick RJ (2006) Effects of substrate structure and composition on the structure, dynamics and energetics of water on mineral surfaces: MD modeling study. Geochim Cosmochim Acta 70:562–582

    Article  CAS  Google Scholar 

  19. Churakov SV (2007) Structure and dynamics of the water films confined between edges of pyrophyllite: a first principle study. Geochim Cosmochim Acta 71:1130–1144

    Article  CAS  Google Scholar 

  20. Kalinichev AG, Wang J, Kirkpatrick RJ (2007) Molecular dynamics modeling of the structure, dynamics and energetics of mineral-water interfaces: application to cement materials. Cem Concr Res 37:337–347

    Article  CAS  Google Scholar 

  21. Larentzos JP, Greathouse JA, Cygan RT (2007) An ab initio and classical molecular dynamics investigation of the structural and vibrational properties of talc and pyrophyllite. J Phys Chem C 111:12752–12759

    Article  CAS  Google Scholar 

  22. de Leeuw NH, Cooper TG (2007) Surface simulation studies of the hydration of white rust Fe(OH)2, goethite α-FeO(OH) and hematite α-Fe2O3. Geochim Cosmochim Acta 71:1655–1673

    Article  Google Scholar 

  23. Predota M, Cummings PT, Wesolowski DJ (2007) Electric double layer at the rutile (110) surface. 3. Inhomogeneous viscosity and diffusivity measurement by computer simulations. J Phys Chem C 111:3071–3079

    Article  CAS  Google Scholar 

  24. Allen JP, Gren W, Molinari M, Arrouvel C, Maglia F, Parker SC (2009) Atomistic modelling of adsorption and segregation at inorganic solid interfaces. Mol Simul 35:584–608

    Article  CAS  Google Scholar 

  25. Cygan RT, Greathouse JA, Heinz H, Kalinichev AG (2009) Molecular models and simulations of layered materials. J Mater Chem 19:2470–2481

    Article  CAS  Google Scholar 

  26. Suter JL, Anderson RL, Greenwell HC, Coveney PV (2009) Recent advances in large-scale atomistic and coarse-grained molecular dynamics simulation of clay minerals. J Mater Chem 19:2482–2493

    Article  CAS  Google Scholar 

  27. Wang J, Kalinichev AG, Kirkpatrick RJ (2009) Asymmetric hydrogen bonding and orientational ordering of water at hydrophobic and hydrophilic surfaces: a comparison of water/vapor, water/talc, and water/mica interfaces. J Phys Chem C 113:11077–11085

    Article  CAS  Google Scholar 

  28. Argyris D, Cole DR, Striolo A (2010) Ion-specific effects under confinement: the role of interfacial water. ACS Nano 4:2035–2042

    Article  CAS  Google Scholar 

  29. Bourg IC, Sposito G (2010) Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media. Environ Sci Technol 44:2085–2091

    Article  CAS  Google Scholar 

  30. Malikova N, Dubois E, Marry V, Rotenberg B, Turq P (2010) Dynamics in clays – combining neutron scattering and microscopic simulation. Zeitschrift Phys Chem 224:153–181

    Article  CAS  Google Scholar 

  31. Fenter P, Lee SS, Skelton AA, Cummings PT (2011) Direct and quantitative comparison of pixelated density profiles with high-resolution X-ray reflectivity data. J Synchrotron Radiat 18:257–265

    Article  CAS  Google Scholar 

  32. Ferrage E, Sakharov BA, Michot LJ, Delville A, Bauer A, Lanson B, Grangeon S, Frapper G, Jimenez-Ruiz M, Cuello GJ (2011) Hydration properties and interlayer organization of water and ions in synthetic Na-smectite with tetrahedral layer charge. 2. Toward a precise coupling between molecular simulations and diffraction data. J Phys Chem C 115:1867–1881

    Article  CAS  Google Scholar 

  33. Rotenberg B, Patel AJ, Chandler D (2011) Molecular explanation for why talc surfaces can be both hydrophilic and hydrophobic. J Am Chem Soc 133:20521–20527

    Article  CAS  Google Scholar 

  34. Liu X, Lu X, Meijer EJ, Wang R, Zhou H (2012) Atomic-scale structures of interfaces between phyllosilicate edges and water. Geochim Cosmochim Acta 81:56–68

    Article  CAS  Google Scholar 

  35. Tazi S, Rotenberg B, Salanne M, Sprik M, Sulpizi M (2012) Absolute acidity of clay edge sites from ab-initio simulations. Geochim Cosmochim Acta 94:1–11

    Article  CAS  Google Scholar 

  36. Sahai N (2002) Is silica really an anomalous oxide? Surface acidity and aqueous hydrolysis revisited. Environ Sci Technol 36:445–452

    Article  CAS  Google Scholar 

  37. Morrow CP, Yazaydin AO, Krishnan M, Bowers GM, Kalinichev AG, Kirkpatrick RJ (2013) Structure, energetics, and dynamics of smectite clay interlayer hydration: molecular dynamics and metadynamics investigation of Na-hectorite. J Phys Chem C 117:5172–5187

    Article  CAS  Google Scholar 

  38. Duval Y, Mielczarski JA, Pokrovsky OS, Mielczarski E, Ehrhardt JJ (2002) Evidence of the existence of three types of species at the quartz-aqueous solution interface at pH 0-10: XPS surface group quantification and surface complexation modeling. J Phys Chem B 106:2937–2945

    Article  CAS  Google Scholar 

  39. Ahn WY, Kalinichev AG, Clark MM (2008) Effects of background cations on the fouling of polyethersulfone membranes by natural organic matter: experimental and molecular modeling study. J Membr Sci 309:128–140

    Article  CAS  Google Scholar 

  40. Wang JW, Kalinichev AG, Kirkpatrick RJ (2005) Structure and decompression melting of a novel, high-pressure nanoconfined 2-D ice. J Phys Chem B 109:14308–14313

    Article  CAS  Google Scholar 

  41. Wang JW, Kalinichev AG, Kirkpatrick RJ (2004) Molecular modeling of the 10Å phase at subduction zone conditions. Earth Planet Sci Lett 222:517–527

    Article  CAS  Google Scholar 

  42. Kalinichev AG (2001) Molecular simulations of liquid and supercritical water: thermodynamics, structure, and hydrogen bonding. Rev Mineral Geochem 42:83–129

    Article  CAS  Google Scholar 

  43. Korb JP (2010) Multi-scales nuclear spin relaxation of liquids in porous media. Compt Rend Phys 11:192–203

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences (grant number DE-FG02-08ER-15929) and by the industrial chair “Storage and Management of Nuclear Waste” at the Ecole des Mines de Nantes, funded by ANDRA, Areva, and EDF. The supercomputing resources of the NSF TeraGrid (grant number TG-EAR000002) and of the US DOE National Energy Research Scientific Computing Center (NERSC) were used for the simulations.

Author information

Authors and Affiliations

  1. Laboratoire Subatech, UMR 6457, Ecole des Mines de Nantes, 44307, Nantes, France

    Andrey G. Kalinichev

  2. Department of Chemistry, Michigan State University, East Lansing, MI, 48824, USA

    Andrey G. Kalinichev

Authors
  1. Andrey G. Kalinichev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Andrey G. Kalinichev .

Editor information

Editors and Affiliations

  1. Institute of Earth Sciences, University of Orléans, Orléans, France

    Lionel Mercury

  2. Department of Transducers Science and Technology, MESA+ Institute for Nanotechnology, University of Twente, Enschede, The Netherlands

    Niels Tas

  3. The Hydrological Service; Research Division, Israeli Water Authority, Jerusalem, Israel

    Michael Zilberbrand

Rights and permissions

Reprints and permissions

Copyright information

© 2014 Springer Science+Business Media Dordrecht

About this paper

Cite this paper

Kalinichev, A.G. (2014). Molecular Structure and Dynamics of Nano-Confined Water: Computer Simulations of Aqueous Species in Clay, Cement, and Polymer Membranes. In: Mercury, L., Tas, N., Zilberbrand, M. (eds) Transport and Reactivity of Solutions in Confined Hydrosystems. NATO Science for Peace and Security Series C: Environmental Security. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-7534-3_9

Download citation

Publish with us

Policies and ethics

Search

Navigation