Influence of Strong Confinement on the Structure and Dynamics of Liquids: a Study of the Clay/Water Interface Exploiting 2 H NMR Spectroscopy and Spin-Locking Relaxometry

Patrice Porion (1) , Anne-Marie Faugère (1) , Anne-Laure Rollet (2) , Emmanuelle Dubois (3) , Virginie Marry (4) , Laurent Michot (2) , Alfred Delville (1)

1 ICMN - Interfaces, Confinement, Matériaux et Nanostructures
2 PHENIX - PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX
3 LI2C - Liquides Ioniques et Interfaces Chargées
4 PHENIX - PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX

2H NMR spectroscopy, multiquanta relaxation, and spin-locking relaxometry are used to investigate the structural and dynamical properties of water molecules confined within dense sediments of synthetic fluorohectorite. As shown by the large residual splitting of the 2H NMR resonance line, water molecules confined in the interlamellar space of the clay are strongly oriented to contact with the fluorinated basal surface of the clay. Multiquanta relaxation measurements are used to identify and quantify the contributions of the quadrupolar and heteronuclear dipolar couplings by monitoring the NMR relaxation of the confined water molecules. Finally, the average residence time of the water molecules confined within the interlamellar space of the clay platelets is quantified by detailed analysis of 2H spin-locking relaxometry measurements. Thanks to the significant contributions of both quadripolar and heteronuclear dipolar relaxation mechanisms, 2H spin-locking relaxation measurements probe a broad dynamical range, by sampling angular velocities ranging between 102 and 3 × 105 rad/s.

Domaines: Chimie théorique et/ou physique

Patrice Porion, Anne-Marie Faugère, Anne-Laure Rollet, Emmanuelle Dubois, Virginie Marry, et al.. Influence of Strong Confinement on the Structure and Dynamics of Liquids: a Study of the Clay/Water Interface Exploiting 2 H NMR Spectroscopy and Spin-Locking Relaxometry. Journal of Physical Chemistry C, 2018, 122 (29), pp.16830-16841. ⟨10.1021/acs.jpcc.8b05089⟩. ⟨hal-02383136⟩