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Fabrizia Foglia, Quentin Berrod, Adam J. Clancy, Keenan Smith, Gérard Gebel, Victoria García Sakai, Markus Appel, Jean-Marc Zanotti, Madhusudan Tyagi, Najet Mahmoudi, Thomas S. Miller, John R. Varcoe, Arun Prakash Periasamy, Daniel J. L. Brett, Paul R. Shearing, Sandrine Lyonnard and Paul F. McMillan

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH− ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100–103 ps) to disentangle the water, polymer relaxation and OH− diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.


J. Wolanin, L. Michel, D. Tabacchioni, J. M. Zanotti, J. Peters, I. Imaz, B. Coasne, M. Plazanet, and C. Picard

With their strong confining porosity and versatile surface chemistry, zeolitic imidazolate frameworks—including the prototypical ZIF-8—display exceptional properties for various applications. In particular, the forced intrusion of water at high pressure (∼25 MPa) into ZIF-8 nanopores is of interest for energy storage. Such a system reveals also ideal to study experimentally water dynamics and thermodynamics in an ultrahydrophobic confinement. Here, we report on neutron scattering experiments to probe the molecular dynamics of water within ZIF-8 nanopores under high pressure up to 38 MPa. In addition to an overall confinement-induced slowing down, we provide evidence for strong dynamical heterogeneities with different underlying molecular dynamics. Using complementary molecular simulations, these heterogeneities are found to correspond to different microscopic mechanisms inherent to vicinal molecules located in strongly adsorbing sites (ligands) and other molecules nanoconfined in the cavity center. These findings unveil a complex microscopic dynamics, which results from the combination of surface residence times and exchanges between the cavity surface and center.



B. Annighöfer , A. Hélary, A. Brulet, A. Colas de la Noue, C. Loupiac and S. Combet
Review of Scientific Instruments 90 (2019) 025106

Abstract :

We report on a high pressure (HP) cell designed for the determination of the structure of molecular solutions by small-angle neutron scattering (SANS). The HP cell is fitted up with two thick metallic windows that make the device very resistant under hydrostatic pressures up to 600 MPa (or 6 kbar). The metallic windows are removable, offering the possibility to adapt the HP cell to a given study with the pressure desired on an appropriate spatial range to study the structure of various molecular solutions by SANS. In this context, we report the absorption, transmission, and scattering properties of different metallic windows. Finally, we describe, as a proof of principle, the solution structure changes of myoglobin, a small globular protein.


Cationic thermoresponsive poly(n-vinylcaprolactam) microgels synthesized by emulsion polymerization using a reactive cationic macro-raft agent
L. Etchenausia, E. Deniau, A. Brûlet, J. Forcada and M. Save,  Macromolecules  (2018) sous presse

Abstract :

A series of reactive poly([2-(acryloyloxy)ethyl]trimethylammonium chloride) (P(AETAC)) cationic polymers with varying degrees of polymerization were synthesized by RAFT/MADIX polymerization and investigated as stabilizers for the emulsion polymerization of N-vinylcaprolactam (PVCL) in the presence of a cross-linker. It was demonstrated that the xanthate chain end of the cationic P(AETAC-X) polymers played a crucial role to produce stable cationic PVCL-based microgels at higher initial solids content (5–10 wt %) than usually reported for the synthesis of PVCL microgels. The thermoresponsive PVCL microgels with cationic shell undergo a reversible volume shrinkage upon heating in the absence of any hysteresis in accordance with the narrow particle size distribution.

The values of the volume phase transition temperature ranged between 28 and 30 °C for the microgels synthesized using 4 and 8 wt % of P(AETAC-X) based on VCL. The presence of a cationic outer shell onto the microgels was evidenced by the positive values of the electrophoretic mobility. The swelling behavior of the thermoresponsive microgel particles can be tuned by playing on two synthesis variables which are the initial solids content and the content of P(AETAC-X) macro-RAFT stabilizer. Furthermore, the inner structure of the synthesized microgels was probed by transverse relaxation nuclear magnetic resonance (T2 NMR) and small-angle neutron scattering (SANS) measurements. The fit of T2 NMR data confirmed a core–shell morphology with different cross-linking density in PVCL microgels. Through the determination of the network mesh size, SANS was suitable to explain the increase of the values of the PVCL microgel swelling ratios by increasing the initial solids content of their synthesis.

Three-legged 2,2′-bipyridine monomer at the air/water interface: monolayer structure and reactions with Ni(II) ions from the subphase,
Wenyang Dai, Lay-Theng Lee, Andri Schütz, Benjamin Zelenay, Zhikun Zheng, Andreas Borgschulte, Max Döbeli, Wasim Abuillan, Oleg V. Konovalov, Motomu Tanaka and A. Dieter Schlüter, Langmuir, 2017, 33 (7),  1646

The behavior of compound 2 [1,3,5-tri(2,2′-bipyridin-5-yl)benzene] with three bipyridine units arranged in a star geometry is investigated in the presence and absence of Ni(ClO4)2. Its properties at the air–water interface as well as after transfer onto a solid substrate are studied by several techniques including Brewster angle microscopy, X-ray reflectivity, neutron reflectivity, X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and atomic force microscopy combined with optical microscopy. It is found that compound 2 within the monolayers formed stays almost vertical at the interface and that at high Ni2+/2 (Ni2+/2 = 4000, 20′000) ratios two of the three bipyridine units of 2 are complexed, resulting in supramolecular sheets that are likely composed of arrays of linear metal–organic complexation polymers.


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