Ref HAL: hal-01927357_v1
DOI: 10.1016/j.chemphys.2017.11.012
WoS: WOS:000426452900004
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3 Citations
Résumé:

The aim of the present work is to study by means of thermodynamic measurements, i.e. isotherms of adsorption and desorption of water and Infrared (IR) spectroscopy, the effect of the interlayer cations on the mechanism of adsorption-desorption of water in the case of a montmorillonite exchanged with alkaline-earth metals. For the first time, the net isosteric heat of water adsorption and desorption is determined from isotherms recorded at three temperatures. The net isosteric heat is a very useful parameter for getting more insights into the sorption mechanism since it provides information about the sorption energy evolution which can be complementary to that obtained from structural or gravimetric measurements. The homoionic montmorillonite samples are prepared from purification and cationic exchanged in aqueous solution of the raw material, i.e the reference SWy-2 Wyoming material. XRD at the dry state and elemental chemical analysis confirm that the treatment does not deteriorate the clay structure and yield the expected homoionic composition. The adsorption and desorption isotherms measured at various temperatures show that the nature of the interlayer, i.e. exchangeable, cation changes the adsorbed/desorbed amount of water molecules for a given water relative pressure. The total amount of water adsorbed at = 0.5 follows the cation sequence Ca>Mg>Ba. Although the adsorption isosteric heat also follows the cation sequence Ca>Mg>Ba, that of desorption obeys a slightly different sequence Ca~Mg>Ba. This discrepancy between the adsorption and desorption heat is due to the higher irreversibility of water sorption process in the Ca exchanged montmorillonite. Finally, analysis of the IR spectra recorded at room temperature and under a primary vacuum reveals that the amount of adsorbed water follows the same sequence as that of the isosteric heat of adsorption and shows the coexistence of liquid-like and solid-like water confined in the interlayer space.

Ref HAL: hal-01910272_v1
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Ref HAL: hal-01844602_v1
Ref Arxiv: 1712.01055
DOI: 10.1103/PhysRevE.98.012605
WoS: 000439065200005
Ref. & Cit.: NASA ADS
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6 Citations
Résumé:

The number of precise conductance measurements in nanopores is quickly growing. To clarify the dominant mechanisms at play and facilitate the characterization of such systems for which there is still no clear consensus, we propose an analytical approach to the ionic conductance in nanopores that takes into account (i) electro-osmotic effects, (ii) flow slip at the pore surface for hydrophobic nanopores, (iii) a component of the surface charge density that is modulated by the reservoir pH and salt concentration cs using a simple charge regulation model, and (iv) a fixed surface charge density that is unaffected by pH and cs . Limiting cases are explored for various ranges of salt concentration and our formula is used to fit conductance experiments found in the literature for carbon nanotubes. This approach permits us to catalog the different possible transport regimes and propose an explanation for the wide variety of currently known experimental behavior for the conductance versus cs .

Ref HAL: hal-01930745_v1
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The use of electrochemical template synthesis for the formation of electrochromic composite nickel hydroxide/PVA films with poor inside stress, effective adhesion to substrate and high optical and electrochemical properties is proposed.Influence of the deposition current density and of the amount of PVA on the structure, surface morphology and transparency of the electrodeposit films is investigated. It is thus concluded that the optimal current density is 0.625 mA/cm2 for the pure Ni(OH)2 film whereas the optimal concentration of PVA is 5% weight is. Overall, the electroplated Ni(OH)2/PVA films exhibit an X-ray amorphous structure, due to the Ni(OH)2 particle growth in the nano-size cells of the 3D network of the PVA template. Surface morphology of films, deposited with the template synthesis, is investigated by SEM. The film electrodepositing rate by template synthesis was estimated around the 3.87 μm/h at the current density of the 0.625 mA/cm2. Template incorporating into the nickel hydroxide film has been proved by EDX analysis. Electrochemical and electrochromic properties of films, deposited by electrochemical template synthesis and dried at 20 °C and 90 °C, have been investigated. It was shown that both types of films have high properties (charge/discharge and colorization-bleaching processes). But films, dried at 20 °C, has the best electrochemical properties and larger colorization depth, however the colorization/bleaching process has larger reversibility for the sample dried at 90 °C

Ref HAL: hal-01910269_v1
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Ref HAL: hal-01586169_v1
DOI: 10.1039/c7nr02976d
WoS: WOS:000408435400019
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13 Citations
Résumé:

Ionic transport through single-walled carbon nanotubes (SWCNTs) is promising for many applications but remains both experimentally challenging and highly debated. Here we report ionic current measurements through microfluidic devices containing one or several SWCNTs of diameter of 1.2 to 2 nm unexpectedly showing a linear or a voltage-activated I-V dependence. Transition from an activated to a linear behavior, and stochastic fluctuations between different current levels were notably observed. For linear devices, the high conductance confirmed with different chloride salts indicates that the nanotube/water interface exhibits both a high surface charge density and flow slippage, in agreement with previous reports. In addition, the sublinear dependence of the conductance on the salt concentration points toward a charge-regulation mechanism. Theoretical modelling and computer simulations show that the voltage-activated behavior can be accounted for by the presence of local energy barriers along or at the ends of the nanotube. Raman spectroscopy reveals strain fluctuations along the tubes induced by the polymer matrix but displays insufficient doping or variations of doping to account for the apparent surface charge density and energy barriers revealed by ion transport measurements. Finally, experimental evidence points toward environment-sensitive chemical moieties at the nanotube mouths as being responsible for the energy barriers causing the activated transport of ions through SWCNTs within this diameter range.

Ref HAL: hal-01950212_v1
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We present experimental and theoretical results for the transport of ions and molecules inside carbon nanotubes.