Dynamics in Geometrical Confinement pp 127-149

Part of the Advances in Dielectrics book series (ADVDIELECT) | Cite as

Rotational Diffusion of Guest Molecules Confined in Uni-directional Nanopores

  • Wycliffe K. Kipnusu
  • Ciprian Iacob
  • Malgorzata Jasiurkowska-Delaporte
  • Wilhelm Kossack
  • Joshua R. Sangoro
  • Friedrich Kremer
Chapter

Abstract

Broadband dielectric spectroscopy (BDS) is employed to study the rotational diffusion of Tris(2-ethylhexyl)phosphate (TEHP), a glass-former, and 4-heptyl-4\(^\prime \)-isothiocyanatobiphenyl (7BT), a liquid crystal, both confined in nanoporous silica membranes having uni-directional pores with diameters in the range 4–10.4 nm. It is observed that upon cooling, the glassy dynamics (\(\alpha \)-process) of TEHP is enhanced near the calorimetric glass transition. This confinement effect is attributed to a slight reduction in density of the liquid in the nanopores. The secondary \(\beta \)-relaxation in TEHP is however unaffected by the geometrical confinement. Silanization of the inner pore surfaces has no measurable effect on the mobility of the guest molecules. For the case of liquid crystal 7BT, two relaxation processes originating from librations about the molecule’s short (\(\delta \)-process) and long axes (\(\beta _{\text {LC}}\)-process) are observed. The former becomes suppressed with decreasing pore diameter, while the latter is nearly unaffected with a tendency to become faster with decreasing pore diameter, an effect caused by orientational ordering due to geometrical constraints.

Keywords

Uni-directional nanopores Rotational diffusion Electrochemical etching 4-heptyl-4\(^\prime \)-isothiocyanatobiphenyl 

Abbreviations

BDS

Broadband dielectric spectroscopy

TEHP

Tris(2-ethylhexyl)phosphate

7BT

4-heptyl-4\(^\prime \)-isothiocyanatobiphenyl

NMR

Nuclear magnetic resonance

DSC

Differential scanning calorimetry

MWS

Maxwell–Wagner–Sillars

LCs

Liquid crystals

SmE

Smectic E

HF

Hydrofluoric acid

Si

Silicon

pSi

Porous silicon

pSiO\(_{2 }\)

Porous silica

SEM

Scanning electron micrograph

h

Hour(s)

s

Second(s)

HMDS

Hexamethyldisilazane

FTIR

Fourier transform infrared

HP

Hewlett Packard

HN

Havriliak–Negami

\(I\)

Isotropic

N

Nematic

S

Smetic

RTD

Relaxation time distribution

VFT

Vogel–Fulcher–Tammann

T

Temperature

\(T_{\text {g}}\)

Glass transition temperature

DFT

Density functional theory

NCS

Isothiocyanate

Hz

Hertz

References

  1. 1.
    Crupi V, Magazù S, Majolino D, Maisano G, Migliardo P (1999) Dynamical response and H-bond effects in confined liquid water. J Mol Liq 80(2–3):133–147CrossRefGoogle Scholar
  2. 2.
    Patkowski A, Ruths T, Fischer EW (2003) Dynamics of supercooled liquids confined to the pores of sol–gel glass: a dynamic light scattering study. Phys Rev E 67(2):021501CrossRefGoogle Scholar
  3. 3.
    Morishige K, Nobuoka K (1997) X-ray diffraction studies of freezing and melting of water confined in a mesoporous adsorbent (MCM-41). J Chem Phys 107(17):6965–6969CrossRefGoogle Scholar
  4. 4.
    Crupi V, Majolino D, Migliardo P, Venuti V (2002) Neutron scattering study and dynamic properties of hydrogen-bonded liquids in mesoscopic confinement. 1. The water case. J Phys Chem B 106(42):10884–10894. doi:10.1021/jp020503m CrossRefGoogle Scholar
  5. 5.
    Luo R-S, Jonas J (2001) Raman scattering study of liquid ethylene glycol confined to nanoporous silica glasses. J Raman Spectrosc 32(11):975–978. doi:10.1002/jrs.786 CrossRefGoogle Scholar
  6. 6.
    Stapf S, Kimmich R, Seitter RO (1995) Proton and deuteron field-cycling NMR relaxometry of liquids in porous glasses: evidence for Lévy–Walk statistics. Phys Rev Lett 75(15):2855–2858CrossRefGoogle Scholar
  7. 7.
    Brandani S, Ruthven DM, Kärger J (1995) Concentration dependence of self-diffusivity of methanol in NaX zeolite crystals. Zeolites 15(6):494–495CrossRefGoogle Scholar
  8. 8.
    Buntkowsky G, Breitzke H, Adamczyk A, Roelofs F, Emmler T, Gedat E, Grunberg B, Xu Y, Limbach H-H, Shenderovich I, Vyalikh A, Findenegg G (2007) Structural and dynamical properties of guest molecules confined in mesoporous silica materials revealed by NMR. Phys Chem Chem Phys 9(35):4843–4853. doi:10.1039/b707322d CrossRefGoogle Scholar
  9. 9.
    Li Y, Ishida H (2002) A differential scanning calorimetry study of the assembly of hexadecylamine molecules in the nanoscale confined space of silicate galleries. Chem Mater 14(3):1398–1404. doi:10.1021/cm0103747 CrossRefGoogle Scholar
  10. 10.
    Elamin K, Jansson H, Kittaka S, Swenson J (2013) Different behavior of water in confined solutions of high and low solute concentrations. Phys Chem Chem Phys 15(42):18437–18444. doi:10.1039/c3cp51786a CrossRefGoogle Scholar
  11. 11.
    Farrer RA, Fourkas JT (2003) Orientational dynamics of liquids confined in nanoporous Sol-gel glasses studied by optical kerr effect spectroscopy. Acc Chem Res 36(8):605–612. doi:10.1021/ar0200302 CrossRefGoogle Scholar
  12. 12.
    Loughnane BJ, Scodinu A, Fourkas JT (1999) Extremely slow dynamics of a weakly wetting liquid at a solid/liquid interface: CS2 confined in nanoporous glasses. J Phys Chem B 103(29):6061–6068. doi:10.1021/jp991176u CrossRefGoogle Scholar
  13. 13.
    Arndt M, Stannarius R, Gorbatschow W, Kremer F (1996) Dielectric investigations of the dynamic glass transition in nanopores. Phys Rev E: Stat Phys Plasmas Fluids Relat Interdisc Top 54(5):5377–5390CrossRefGoogle Scholar
  14. 14.
    Arndt M, Stannarius R, Groothues H, Hempel E, Kremer F (1997) Length scale of cooperativity in the dynamic glass transition. Phys Rev Lett 79(11):2077–2080CrossRefGoogle Scholar
  15. 15.
    Brás AR, Dionísio M, Schönhals, A (2008) Confinement and surface effects on the molecular dynamics of a nematic mixture investigated by dielectric relaxation spectroscopy. J Phys Chem B 112(28):8227–8235. doi:10.1021/jp802133e
  16. 16.
    Brás AR, Frunza S, Guerreiro L, Fonseca IM, Corma A, Frunza L, Dionísio M, Schönhals A (2010) Molecular mobility of nematic E7 confined to molecular sieves with a low filling degree. J Chem Phys 132(22):224508Google Scholar
  17. 17.
    Schönhals A, Goering H, Schick C, Frick B, Zorn R (2003) Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments. Eur Phys J E 12(1):173–178. doi:10.1140/epje/i2003-10036-4 CrossRefGoogle Scholar
  18. 18.
    Schönhals A, Goering H, Schick C, Frick B, Zorn R (2004) Glass transition of polymers confined to nanoporous glasses. Colloid Polym Sci 282(8):882–891. doi:10.1007/s00396-004-1106-3 CrossRefGoogle Scholar
  19. 19.
    Schönhals A, Goering H, Schick C, Frick B, Zorn R (2005) Polymers in nanoconfinement: What can be learned from relaxation and scattering experiments? J Non-Cryst Solids 351(33,36):2668–2677Google Scholar
  20. 20.
    Kremer F (2002) Dielectric spectroscopy, yesterday, today and tomorrow. J Non-Cryst Solids 305(1,3):1–9Google Scholar
  21. 21.
    Frunza L, Kosslick H, Pitsch I, Frunza S, Schönhals A (2005) Rotational fluctuations of water inside the nanopores of SBA-type molecular sieves. J Phys Chem B 109(18):9154–9159. doi:10.1021/jp044503t CrossRefGoogle Scholar
  22. 22.
    Sinha GP, Aliev FM (1998) Dielectric spectroscopy of liquid crystals in smectic, nematic, and isotropic phases confined in random porous media. Phys Rev E 58(2):2001–2010CrossRefGoogle Scholar
  23. 23.
    Streck C, Mel’nichenko YB, Richert R (1996) Dynamics of solvation in supercooled liquids confined to the pores of sol–gel glasses. Phys Rev B 53(9):5341CrossRefGoogle Scholar
  24. 24.
    Ryabov Ya, Gutina A, Arkhipov V, Feldman Y (2001) Dielectric relaxation of water absorbed in porous glass. J Phys Chem B 105(9):1845–1850Google Scholar
  25. 25.
    Prisk TR, Tyagi M, Sokol PE (2011) Dynamics of small-molecule glass formers confined in nanopores. J Chem Phys 134:114506(114501–114509)Google Scholar
  26. 26.
    Cerveny S, Mattsson J, Swenson J, Bergman R (2004) Relaxations of hydrogen-bonded liquids confined in two-dimensional vermiculite clay. J Phys Chem B 108(31):11596–11603. doi:10.1021/jp037346r
  27. 27.
    Aliev FM, Nazario Z, Sinha GP (2002) Broadband dielectric spectroscopy of confined liquid crystals. J Non-Cryst Solids 305(1,3):218–225Google Scholar
  28. 28.
    Schönhals A, Frunza S, Frunza L, Unruh T, Frick B, Zorn R (2010) Vibrational and molecular dynamics of a nanoconfined liquid crystal. Eur Phys J Spec Top 189(1):251–255. doi:10.1140/epjst/e2010-01329-5 CrossRefGoogle Scholar
  29. 29.
    Frunza L, Frunza S, Kosslick H, Schönhals A (2008) Phase behavior and molecular mobility of n-octylcyanobiphenyl confined to molecular sieves: dependence on the pore size. Phys Rev E 78(5):051701CrossRefGoogle Scholar
  30. 30.
    Cramer C, Cramer T, Arndt M, Kremer F, Naji L, Stannarius R (1997) NMR and dielectric studies of nano-confined nematic liquid crystals. Molecular crystals and liquid crystals science and technology. Mol Cryst Liq Cryst Sect A 303(1):209–217. doi:10.1080/10587259708039426 CrossRefGoogle Scholar
  31. 31.
    Massalska-Arodz M, Gorbachev VY, Krawczyk J, Hartmann L, Kremer F (2002) Molecular dynamics of the liquid crystal 6O2OCB in nanopores. J Phys: Condens Matter 14(36):8435Google Scholar
  32. 32.
    Crawford GP, Ondris-Crawford R, Žumer S, Doane JW (1993) Anchoring and orientational wetting transitions of confined liquid crystals. Phys Rev Lett 70(12):1838–1841CrossRefGoogle Scholar
  33. 33.
    Kipnusu WK, Kossack W, Iacob C, Jasiurkowska M, Sangoro JR, Kremer F (2012) Molecular order and dynamics of tris(2-ethylhexyl)phosphate confined in uni-directional nanopores. In: Zeitschrift für Physikalische Chemie international journal of research in physical chemistry and chemical physics, vol 226(7–8), p 797Google Scholar
  34. 34.
    Iacob C, Sangoro JR, Kipnusu WK, Valiullin R, Karger J, Kremer F (2012) Enhanced charge transport in nano-confined ionic liquids. Soft Matter 8(2):289–293. doi:10.1039/c1sm06581e CrossRefGoogle Scholar
  35. 35.
    Jasiurkowska M, Kossack W, Ene R, Iacob C, Kipnusu WK, Papadopoulos P, Sangoro JR, Massalska-Arodz M, Kremer F (2012) Molecular dynamics and morphology of confined 4-heptyl-4\(^\prime \)-isothiocyanatobiphenyl liquid crystals. Soft Matter 8(19):5194–5200. doi:10.1039/c2sm07258k
  36. 36.
    Richert R (2010) Dielectric spectroscopy and dynamics in confinement. Eur Phys J Spec Top 189(1):37–46. doi:10.1140/epjst/e2010-01308-x CrossRefGoogle Scholar
  37. 37.
    Kremer F, Schönhals A (2003) Broadband dielectric spectroscopy. Springer, BerlinCrossRefGoogle Scholar
  38. 38.
    Richert R (2011) Dynamics of nanoconfined supercooled liquids. Ann Rev Phys Chem 62:65–84CrossRefGoogle Scholar
  39. 39.
    Cordoyiannis G, Zidanšek A, Lahajnar G, Kutnjak Z, Amenitsch H, Nounesis G, Kralj S (2009) Influence of confinement in controlled-pore glass on the layer spacing of smectic-A liquid crystals. Phys Rev E 79(5):051703CrossRefGoogle Scholar
  40. 40.
    Kutnjak Z, Kralj S, Lahajnar G, Žumer S (2004) Influence of finite size and wetting on nematic and smectic phase behavior of liquid crystal confined to controlled-pore matrices. Phys Rev E 70(5):051703CrossRefGoogle Scholar
  41. 41.
    Bellini T, Radzihovsky L, Toner J, Clark NA (2001) Universality and scaling in the disordering of a smectic liquid crystal. Science 294(5544):1074–1079. doi:10.1126/science.1057480 CrossRefGoogle Scholar
  42. 42.
    Guégan R, Morineau D, Loverdo C, Béziel W, Guendouz M (2006) Evidence of anisotropic quenched disorder effects on a smectic liquid crystal confined in porous silicon. Phys Rev E 73(1):011707CrossRefGoogle Scholar
  43. 43.
    Kityk AV, Wolff M, Knorr K, Morineau D, Lefort R, Huber P (2008) Continuous paranematic-to-nematic ordering transitions of liquid crystals in tubular silica nanochannels. Phys Rev Lett 101(18):187801CrossRefGoogle Scholar
  44. 44.
    Chahine G, Kityk AV, Knorr K, Lefort R, Guendouz M, Morineau D, Huber P (2010) Criticality of an isotropic-to-smectic transition induced by anisotropic quenched disorder. Phys Rev E 81(3):031703CrossRefGoogle Scholar
  45. 45.
    Clark NA, Bellini T, Malzbender RM, Thomas BN, Rappaport AG, Muzny CD, Schaefer DW, Hrubesh L (1993) X-ray scattering study of smectic ordering in a silica aerogel. Phys Rev Lett 71(21):3505–3508CrossRefGoogle Scholar
  46. 46.
    Nambiar DC, Gaudh JS, Shinde VM (1994) Tris(2-ethylhexyl)phosphate as an extractant for trivalent gallium, indium and thallium. Talanta 41(11):1951–1955Google Scholar
  47. 47.
    Rizos AK, Petihakis L, Ngai KL, Wu J, Yee AF (1999) A dielectric relaxation study of the \(\gamma \)-relaxation in tetramethylbisphenol A polycarbonate plasticized by tris(2-ethylhexyl) phosphate. Macromolecules 32(23):7921–7924. doi:10.1021/ma980204o CrossRefGoogle Scholar
  48. 48.
    Katsu T, Ido K, Kataoka K (2002) Poly(vinyl chloride) membrane electrode for a stimulant, phentermine, using tris(2-ethylhexyl) phosphate as a solvent mediator. Sens Actuators B: Chem 81(2–3):267–272CrossRefGoogle Scholar
  49. 49.
    Ueda K, Rei Y, Komagoe K, Masuda K, Hanioka N, Narimatsu S, Katsu T (2006) Tris(2-ethylhexyl)phosphine oxide as an effective solvent mediator for constructing a serotonin-selective membrane electrode. Anal Chim Acta 565(1):36–41Google Scholar
  50. 50.
    Feng JK, Sun XJ, Ai XP, Cao YL, Yang HX (2008) Dimethyl methyl phosphate: a new nonflammable electrolyte solvent for lithium-ion batteries. J Power Sources 184(2):570–573Google Scholar
  51. 51.
    Lalia BS, Fujita T, Yoshimoto N, Egashira M, Morita M (2009) Electrochemical performance of nonflammable polymeric gel electrolyte containing triethylphosphate. J Power Sources 186(1):211–215Google Scholar
  52. 52.
    Czupryński K, Januszko A (1992) Preparation of nematic mixtures from smectic compounds. Molecular crystals and liquid crystals science and technology. Mol Cryst Liq Cryst Sect A 215(1):199–204. doi:10.1080/10587259208038525 CrossRefGoogle Scholar
  53. 53.
    Czupryński K (1990) Phase diagrams of mixtures consisting of polar compounds SE and SA d. Mol Cryst Liq Cryst Incorporating Nonlinear Opt 192(1):47–52. doi:10.1080/00268949008035604 CrossRefGoogle Scholar
  54. 54.
    Jasiurkowska M, Ściesiński J, Czub J, Massalska-Arodź M, Pełka R, Juszyńska E, Yamamura Y, Saito K (2009) Infrared spectroscopic and X-ray studies of the 4-Propyl-4-n-alkyl-4\(^\prime \) isothiocyanatobiphenyl (nTCB). J Phys Chem B 113(21):7435–7442. doi:10.1021/jp901339c CrossRefGoogle Scholar
  55. 55.
    Jasiurkowska M, Budziak A, Czub J, Massalska-Arodź M, Urban S (2008) X-ray studies on the crystalline E phase of the 4-n-alkyl-4\(^\prime \)-isothiocyanatobiphenyl homologous series (nBT, n = 2–10). Liq Cryst 35(4):513–518. doi:10.1080/02678290801989975 CrossRefGoogle Scholar
  56. 56.
    Jasiurkowska M, Zieliński PM, Massalska-Arodź M, Yamamura Y, Saito K (2011) Study of polymorphism of 4-Hexyl-4\(^\prime \)-isothiocyanatobiphenyl by complementary methods. J Phys Chem B 115(43):12327–12335. doi:10.1021/jp201936x CrossRefGoogle Scholar
  57. 57.
    Beale MIJ, Benjamin JD, Uren MJ, Chew NG, Cullis AG (1985) An experimental and theoretical study of the formation and microstructure of porous silicon. J Cryst Growth 73(3):622–636CrossRefGoogle Scholar
  58. 58.
    Smith RL, Collins SD (1992) Porous silicon formation mechanisms. J Appl Phys 71(8):R1–R22. doi:10.1063/1.350839 CrossRefGoogle Scholar
  59. 59.
    Lehmann V, Gösele U (1991) Porous silicon formation: a quantum wire effect. Appl Phys Lett 58(8):856–858CrossRefGoogle Scholar
  60. 60.
    Zhang G (2006) Porous silicon: morphology and formation mechanisms. In: Vayenas CG, White R, Gamboa-Adelco M (eds) Modern aspects of electrochemistry, vol 39. Springer, US, pp 65–133Google Scholar
  61. 61.
    Zhang XG, Collins SD, Smith RL (1989) Porous silicon formation and electropolishing of silicon by anodic polarization in HF solution. J Electrochem Soc 136(5):1561–1565. doi:10.1149/1.2096961 CrossRefGoogle Scholar
  62. 62.
    Valiullin R, Khokhlov A (2006) Orientational ordering of linear n -alkanes in silicon nanotubes. Phys Rev E 73(5):051605CrossRefGoogle Scholar
  63. 63.
    Johari GP, Andersson O (2006) On the nonlinear variation of dc conductivity with dielectric relaxation time. J Chem Phys 125(12):124501Google Scholar
  64. 64.
    Demus D, Goodby J, Gray GW, Spiess HW (1998) Handbook of liquid crystals: fundamentals, vol 1. Wiley-VCH, New YorkCrossRefGoogle Scholar
  65. 65.
    Donth E-J (2001) The glass transition: relaxation dynamics in liquids and disordered materials. In: Hull R, Jagadish C, Osgood RM, Parisi J, Wang ZM, Uchida S-I (eds), vol 48. Springer series in materials science. Springer, HeidelbergGoogle Scholar
  66. 66.
    Floudas G, Mpoukouvalas K, Papadopoulos P (2006) The role of temperature and density on the glass-transition dynamics of glass formers. J Chem Phys 124(7):74905Google Scholar
  67. 67.
    Thomas JA, McGaughey AJH (2008) Density, distribution, and orientation of water molecules inside and outside carbon nanotubes. J Chem Phys 128(8):084715Google Scholar
  68. 68.
    Shi W, Sorescu DC (2010) Molecular simulations of CO2 and H2 sorption into ionic liquid 1-n-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)amide (hmim[Tf2N]) confined in carbon nanotubes. J Phys Chem B 114(46):15029–15041. doi:10.1021/jp106500p CrossRefGoogle Scholar
  69. 69.
    Kawasaki T, Takeaki A, Tanaka H (2007) Correlation between dynamic heterogeneity and medium-range order in two-dimensional glass-forming liquids. Phys Rev Lett 99(21):215701Google Scholar
  70. 70.
    Spiess HW (2010) Interplay of structure and dynamics in macromolecular and supramolecular systems. Macromolecules 43(13):5479–5491. doi:10.1021/ma1005952 CrossRefGoogle Scholar
  71. 71.
    Stenzel O (2005) The physics of thin film optical spectra. Springer, BerlinGoogle Scholar
  72. 72.
    Urban S, Czuprynski K, Da̧browski R, Gestblom B, Janik J, Kresse H, Schmalfuss H (2001) Dielectric studies of the 4-n-alkyl-4\(^\prime \)-thiocyanatobiphenyl (nBT) homologous series (n=2-10) in the isotropic and E phases. Liq Cryst 28(5):691–696. doi:10.1080/02678290010023343
  73. 73.
    Różańskia SA, Kremer F, Groothues H, Stannarius R (1997) The dielectric properties of nematic liquid crystal, 5CB confined to treated and untreated anopore membranes. Molecular crystals and liquid crystals science and technology. Mol Cryst Liq Cryst Sect A 303(1):319–324. doi:10.1080/10587259708039441 CrossRefGoogle Scholar
  74. 74.
    Iannacchione GS, Crawford GP, Qian S, Doane JW, Finotello D, Zumer S (1996) Nematic ordering in highly restrictive Vycor glass. Phys Rev E 53(3):2402–2411CrossRefGoogle Scholar
  75. 75.
    Ziherl P, Vilfan M, Vrbancic-Kopac N, Žumer S, Ondris-Crawford RJ, Crawford GP (2000) Substrate-induced order in the isotropic phase of a smectogenic liquid crystal: a deuteron NMR study. Phys Rev E 61(3):2792–2798Google Scholar
  76. 76.
    Lefort R, Morineau D, Guégan R, Guendouz M, Zanotti J-M, Frick B (2008) Relation between static short-range order and dynamic heterogeneities in a nanoconfined liquid crystal. Phys Rev E 78(4):040701CrossRefGoogle Scholar
  77. 77.
    Sinha G, Leys J, Glorieux C, Thoen J (2005) Dielectric spectroscopy of aerosil-dispersed liquid crystal embedded in Anopore membranes. Phys Rev E 72(5):051710CrossRefGoogle Scholar
  78. 78.
    Rozanski SA, Stannarius R, Groothues H, Kremer F (1996) Dielectric properties of the nematic liquid crystal 4-n-pentyl-4\(^\prime \)-cyanobiphenyl in porous membranes. Liq Cryst 20(1):59–66. doi:10.1080/02678299608032027

Copyright information

© Springer International Publishing Switzerland 2014

Authors and Affiliations

  • Wycliffe K. Kipnusu
    • 1
  • Ciprian Iacob
    • 2
  • Malgorzata Jasiurkowska-Delaporte
    • 3
  • Wilhelm Kossack
    • 1
  • Joshua R. Sangoro
    • 4
  • Friedrich Kremer
    • 1
  1. 1.Institute of Experimental Physics IUniversity of LeipzigLeipzigGermany
  2. 2.Department of Materials Science and EngineeringPenn State UniversityUniversity ParkUSA
  3. 3.NanoBioMedical CentreAdam Mickiewicz UniversityPoznanPoland
  4. 4.Department of Chemical and Biomolecular EngineeringUniversity of TennesseeKnoxvilleUSA

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