Comptes Rendus
no. 1
Les systèmes hétérogènes « eau–zéolithe hydrophobe »: de nouveaux ressorts moléculaires
Valentin Eroshenko1 ; Robert-Charles Regis2  ; Michel Soulard3 ; Joël Patarin3
1 Laboratoire énergétique thermomoléculaire, X-technologies, École polytechnique, 91128 Palaiseau cedex, France
2 Société méditerranéenne des zéolithes, 7, rue Auguste-Comte, 34000 Montpellier, France
3 Laboratoire de matériaux minéraux, UMR-7016, ENSCMu, UHA, 3, rue Alfred-Werner, 68093 Mulhouse cedex, France
Comptes Rendus. Physique, Volume 3 (2002) no. 1, pp. 111-119.

Des isothermes pression–volume ont été déterminées sur trois systèmes hétérogènes « eau–zéolithe ». Les deux premiers concernent des zéolithes très hydrophobes, purement siliciques, la silicalite-1 (F−) et la zéolithe β (F−) ; le troisième est constitué par une zéolithe commerciale, plus hydrophile de type ZSM-5. Le diagramme P–V pour le système eau–silicalite-1 (F−), est caractérisé par un palier attribué à l'intrusion de l'eau dans les pores du matériau. A la détente, le phénomène est réversible. Ce système, capable d'accumuler et de restituer de l'énergie superficielle, constitue un ressort moléculaire. La courbe P–V pour la zéolithe β, présente un palier à la compression mais à la détente, le phénomène n'est pas réversible. Dans ce cas, le système capable d'absorber de l'énergie mécanique se comporte comme un pare-chocs. Le troisième système, basé sur la ZSM-5, plus hydrophile, présente une isotherme linéaire, sans palier. Ces résultats ouvrent des perspectives d'applications dans le domaine de l'énergétique pour des zéolithes très hydrophobes en contact avec l'eau.

Pressure–volume isotherms have been determined for three heterogeneous ‘water–zeolite’ systems. The first two concern hydrophobic purely siliceous zeolites: silicalite-1 (F−) and zeolite β (F−); the third comprises a more hydrophilic commercial zeolite of the type ZSM-5. The P–V diagram for the water–silicalite-1 (F−) system is characterized by a plateau corresponding to the intrusion of water inside the pores of the solid. During the release the phenomenon is reversible. This system, which is able to accumulate and restore superficial energy, constitutes a molecular spring. For zeolite β, the P–V curve displays a plateau during the compression, but during the release, the phenomenon is not reversible. In that case, the system absorbs mechanical energy and acts as a bumper. The third system, based on the more hydrophilic ZSM-5 zeolite shows a linear isotherm without any plateau. These results open new applications perspectives in the field of the energetics for hydrophobic zeolites in contact with water.

Reçu le :
Révisé le :
Publié le :
DOI : 10.1016/S1631-0705(02)01285-9
Mots-clés : ressorts moléculaires, zéolithes hydrophobes, isotherme pression–volume, intrusion–extrusion d'eau, énergétique
Keywords: molecular springs, hydrophobic zeolites, pressure–volume isotherm, water intrusion–extrusion, energetics

Valentin Eroshenko 1 ; Robert-Charles Regis 2 ; Michel Soulard 3 ; Joël Patarin 3

1 Laboratoire énergétique thermomoléculaire, X-technologies, École polytechnique, 91128 Palaiseau cedex, France
2 Société méditerranéenne des zéolithes, 7, rue Auguste-Comte, 34000 Montpellier, France
3 Laboratoire de matériaux minéraux, UMR-7016, ENSCMu, UHA, 3, rue Alfred-Werner, 68093 Mulhouse cedex, France 
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Valentin Eroshenko; Robert-Charles Regis; Michel Soulard; Joël Patarin. Les systèmes hétérogènes « eau–zéolithe hydrophobe »: de nouveaux ressorts moléculaires. Comptes Rendus. Physique, Volume 3 (2002) no. 1, pp. 111-119. doi : 10.1016/S1631-0705(02)01285-9. https://comptes-rendus.academie-sciences.fr/physique/articles/10.1016/S1631-0705(02)01285-9/

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  • Lydie Tzanis; Mickaël Trzpit; Michel Soulard; Joël Patarin Energetic Performances of STT-Type Zeosil: Influence of the Nature of the Mineralizing Agent Used for the Synthesis, The Journal of Physical Chemistry C, Volume 116 (2012) no. 7, p. 4802 | DOI:10.1021/jp211819p
  • A. Laouir; D. Tondeur Thermodynamic analysis of capillary flows in the presence of hydrodynamic slip, AIChE Journal, Volume 57 (2011) no. 8, p. 2251 | DOI:10.1002/aic.12431
  • Joël Patarin Nanoporous Solids: Materials for a Sustainable Development, Advanced Materials Research, Volume 324 (2011), p. 26 | DOI:10.4028/www.scientific.net/amr.324.26
  • V. D. Borman; A. A. Belogorlov; V. A. Byrkin; G. V. Lisichkin; V. N. Tronin; V. I. Troyan Correlation effects during liquid infiltration into hydrophobic nanoporous media, Journal of Experimental and Theoretical Physics, Volume 112 (2011) no. 3, p. 385 | DOI:10.1134/s1063776111010055
  • V D Borman; A A Belogorlov; V A Byrkin; G V Lisichkin; V N Tronin; V I Troyan The infiltration of nonwetting liquid into nanoporous media and the thermal effect, Journal of Physics: Conference Series, Volume 291 (2011), p. 012044 | DOI:10.1088/1742-6596/291/1/012044
  • M. Göktuğ Ahunbay Monte Carlo Simulation of Water Adsorption in Hydrophobic MFI Zeolites with Hydrophilic Sites, Langmuir, Volume 27 (2011) no. 8, p. 4986 | DOI:10.1021/la200685c
  • Lydie Tzanis; Mickaël Trzpit; Michel Soulard; Joël Patarin High pressure water intrusion investigation of pure silica 1D channel AFI, MTW and TON-type zeolites, Microporous and Mesoporous Materials, Volume 146 (2011) no. 1-3, p. 119 | DOI:10.1016/j.micromeso.2011.03.043
  • Mohamed Ali Saada; Michel Soulard; Bernd Marler; Hermann Gies; Joël Patarin High-Pressure Water Intrusion Investigation of Pure Silica RUB-41 and S-SOD Zeolite Materials, The Journal of Physical Chemistry C, Volume 115 (2011) no. 2, p. 425 | DOI:10.1021/jp109064e
  • Yuriy G. Bushuev; German Sastre Atomistic Simulation of Water Intrusion–Extrusion in ITQ-4 (IFR) and ZSM-22 (TON): The Role of Silanol Defects, The Journal of Physical Chemistry C, Volume 115 (2011) no. 44, p. 21942 | DOI:10.1021/jp207020w
  • Jean‐Louis Paillaud; Philippe Caullet; Jocelyne Brendlé; Angélique Simon‐Masseron; Joël Patarin The Fluoride Route: A Good Opportunity for the Preparation of 2D and 3D Inorganic Microporous Frameworks, Functionalized Inorganic Fluorides (2010), p. 489 | DOI:10.1002/9780470660768.ch16
  • Konstantin S Smirnov; Daniel Bougeard Water behaviour in nanoporous aluminosilicates, Journal of Physics: Condensed Matter, Volume 22 (2010) no. 28, p. 284115 | DOI:10.1088/0953-8984/22/28/284115
  • Thomas Karbowiak; Christian Paulin; Jean-Pierre Bellat Determination of water intrusion heat in hydrophobic microporous materials by high pressure calorimetry, Microporous and Mesoporous Materials, Volume 134 (2010) no. 1-3, p. 8 | DOI:10.1016/j.micromeso.2010.05.001
  • Thomas Karbowiak; Mohamed-Ali Saada; Séverinne Rigolet; Anthony Ballandras; Guy Weber; Igor Bezverkhyy; Michel Soulard; Joël Patarin; Jean-Pierre Bellat New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure, Physical Chemistry Chemical Physics, Volume 12 (2010) no. 37, p. 11454 | DOI:10.1039/c000931h
  • Mohamed Ali Saada; Séverinne Rigolet; Jean-Louis Paillaud; Nicolas Bats; Michel Soulard; Joël Patarin Investigation of the Energetic Performance of Pure Silica ITQ-4 (IFR) Zeolite under High Pressure Water Intrusion, The Journal of Physical Chemistry C, Volume 114 (2010) no. 26, p. 11650 | DOI:10.1021/jp102663f
  • Mickaël Trzpit; Michel Soulard; Joël Patarin Water intrusion in mesoporous silicalite-1: An increase of the stored energy, Microporous and Mesoporous Materials, Volume 117 (2009) no. 3, p. 627 | DOI:10.1016/j.micromeso.2008.08.005
  • Fabien Cailliez; Anne Boutin; Isabelle Demachy; Alain H. Fuchs Thermodynamic study of water confinement in hydrophobic zeolites by Monte Carlo simulations, Molecular Simulation, Volume 35 (2009) no. 1-2, p. 24 | DOI:10.1080/08927020802398900
  • Roland J.-M. Pellenq; Thomas Roussel; Joël Puibasset Molecular simulations of water in hydrophobic microporous solids, Adsorption, Volume 14 (2008) no. 4-5, p. 733 | DOI:10.1007/s10450-008-9135-8
  • Fabien Cailliez; Mickael Trzpit; Michel Soulard; Isabelle Demachy; Anne Boutin; Joël Patarin; Alain H. Fuchs Thermodynamics of water intrusion in nanoporous hydrophobic solids, Physical Chemistry Chemical Physics, Volume 10 (2008) no. 32, p. 4817 | DOI:10.1039/b807471b
  • Joël Puibasset; Roland J.-M. Pellenq Grand Canonical Monte Carlo Simulation Study of Water Adsorption in Silicalite at 300 K, The Journal of Physical Chemistry B, Volume 112 (2008) no. 20, p. 6390 | DOI:10.1021/jp7097153
  • Mickaël Trzpit; Séverinne Rigolet; Jean-Louis Paillaud; Claire Marichal; Michel Soulard; Joël Patarin Pure Silica Chabazite Molecular Spring: A Structural Study on Water Intrusion−Extrusion Processes, The Journal of Physical Chemistry B, Volume 112 (2008) no. 24, p. 7257 | DOI:10.1021/jp711889k
  • Fabien Cailliez; Guillaume Stirnemann; Anne Boutin; Isabelle Demachy; Alain H. Fuchs Does Water Condense in Hydrophobic Cavities? A Molecular Simulation Study of Hydration in Heterogeneous Nanopores, The Journal of Physical Chemistry C, Volume 112 (2008) no. 28, p. 10435 | DOI:10.1021/jp710746b
  • M. Trzpit; M. Soulard; J. Patarin; N. Desbiens; F. Cailliez; A. Boutin; I. Demachy; A. H. Fuchs The Effect of Local Defects on Water Adsorption in Silicalite-1 Zeolite:  A Joint Experimental and Molecular Simulation Study, Langmuir, Volume 23 (2007) no. 20, p. 10131 | DOI:10.1021/la7011205
  • Daniel Bougeard; Konstantin S. Smirnov Modelling studies of water in crystalline nanoporous aluminosilicates, Phys. Chem. Chem. Phys., Volume 9 (2007) no. 2, p. 226 | DOI:10.1039/b614463m
  • V A Eroshenko A new paradigm of mechanical energy dissipation. Part 1: Theoretical aspects and practical solutions, Proceedings of the Institution of Mechanical Engineers, Part D: Journal of Automobile Engineering, Volume 221 (2007) no. 3, p. 285 | DOI:10.1243/09544070d01505
  • Yu Qiao; Venkata K. Punyamurtula; Aijie Han; Xinguo Kong; Falgun B. Surani Temperature dependence of working pressure of a nanoporous liquid spring, Applied Physics Letters, Volume 89 (2006) no. 25 | DOI:10.1063/1.2408664
  • Loïc Coiffard; Valentin A. Eroshenko; Jean‐Pierre E. Grolier Thermomechanics of the variation of interfaces in heterogeneous lyophobic systems, AIChE Journal, Volume 51 (2005) no. 4, p. 1246 | DOI:10.1002/aic.10371
  • Nicolas Desbiens; Isabelle Demachy; Alain H. Fuchs; Helène Kirsch‐Rodeschini; Michel Soulard; Joël Patarin Water Condensation in Hydrophobic Nanopores, Angewandte Chemie, Volume 117 (2005) no. 33, p. 5444 | DOI:10.1002/ange.200501250
  • Nicolas Desbiens; Isabelle Demachy; Alain H. Fuchs; Helène Kirsch‐Rodeschini; Michel Soulard; Joël Patarin Water Condensation in Hydrophobic Nanopores, Angewandte Chemie International Edition, Volume 44 (2005) no. 33, p. 5310 | DOI:10.1002/anie.200501250
  • Sébastien Baliteau; Ricardo Navarette; Philip Llewellyn Anomalous adsorption behavior observed during the characterization of a polystyrene film prepared on a mesoporous material, Journal of Colloid and Interface Science, Volume 275 (2004) no. 1, p. 48 | DOI:10.1016/j.jcis.2004.01.011
  • M. Soulard; J. Patarin; V. Eroshenko; R. Regis Molecular spring or bumper: A new application for hydrophobic zeolitic materials, Recent Advances in the Science and Technology of Zeolites and Related Materials Part B, Proceedings of the 14th International Zeolite Conference, Volume 154 (2004), p. 1830 | DOI:10.1016/s0167-2991(04)80716-x
  • Philip L. Llewellyn Applications of Thermal Analysis and Calorimetry in Adsorption and Surface Chemistry, Applications to Inorganic and Miscellaneous Materials - Handbook of Thermal Analysis and Calorimetry, Volume 2 (2003), p. 1 | DOI:10.1016/s1573-4374(03)80005-5
  • Pierfranco Demontis; Giovanna Stara; Giuseppe B. Suffritti Behavior of Water in the Hydrophobic Zeolite Silicalite at Different Temperatures. A Molecular Dynamics Study, The Journal of Physical Chemistry B, Volume 107 (2003) no. 18, p. 4426 | DOI:10.1021/jp0300849

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