No Arabic abstract
Water management is a key factor that limits PEFCs performance. We show how insights into this problem can be gained from pore-scale simulations of water invasion in a model fibrous medium. We explore the influence of contact angle on the water invasion pattern and water saturation at breakthrough and show that a dramatic change in the invasion pattern, from fractal to compact, occurs as the system changes from hydrophobic to hydrophilic. Then, we explore the case of a system of mixed wettability, i.e. containing both hydrophilic and hydrophobic pores. The saturation at breakthrough is studied as a function of the fraction of hydrophilic pores. The results are discussed in relation with the water management problem, the optimal design of a GDL and the fuel cell performance degradation mechanisms. We outline how the study could be extended to 3D systems, notably from binarised images of GDLs obtained by X ray microtomography.
We investigate the dynamics of water confined in soft ionic nano-assemblies, an issue critical for a general understanding of the multi-scale structure-function interplay in advanced materials. We focus in particular on hydrated perfluoro-sulfonic acid compounds employed as electrolytes in fuel cells. These materials form phase-separated morphologies that show outstanding proton-conducting properties, directly related to the state and dynamics of the absorbed water. We have quantified water motion and ion transport by combining Quasi Elastic Neutron Scattering, Pulsed Field Gradient Nuclear Magnetic Resonance, and Molecular Dynamics computer simulation. Effective water and ion diffusion coefficients have been determined together with their variation upon hydration at the relevant atomic, nanoscopic and macroscopic scales, providing a complete picture of transport. We demonstrate that confinement at the nanoscale and direct interaction with the charged interfaces produce anomalous sub-diffusion, due to a heterogeneous space-dependent dynamics within the ionic nanochannels. This is irrespective of the details of the chemistry of the hydrophobic confining matrix, confirming the statistical significance of our conclusions. Our findings turn out to indicate interesting connections and possibilities of cross-fertilization with other domains, including biophysics. They also establish fruitful correspondences with advanced topics in statistical mechanics, resulting in new possibilities for the analysis of Neutron scattering data.
When analyzing the broadband absorption spectrum of liquid water (10^10 - 10^13 Hz), we find its relaxation-resonance features to be an indication of Frenkels translation-oscillation motion of particles, which is fundamentally inherent to liquids. We have developed a model of water structure, of which the dynamics is due to diffusion of particles, neutral H2O molecules and H3O+ and OH- ions - with their periodic localizations and mutual transformations. This model establishes for the first time a link between the dc conductivity, the Debye and the high frequency sub-Debye relaxations and the infrared absorption peak at 180 cm-1. The model reveals the characteristic times of the relaxations, 50 ps and 3 ps, as the lifetimes of water molecules and water ions, respectively. The model sheds light on the anomalous mobility of a proton and casts doubt on the long lifetime of a water molecule, 10 hours, commonly associated with autoionization.
Formation, evolution, and vanishing of bubbles are common phenomena in our nature, which can be easily observed in boiling or falling waters, carbonated drinks, gas-forming electrochemical reactions, etc. However, the morphology and the growth dynamics of the bubbles at nanoscale have not been fully investigated owing to the lack of proper imaging tools that can visualize nanoscale objects in liquid phase. Here we demonstrate, for the first time, that the nanobubbles in water encapsulated by graphene membrane can be visualized by in situ ultrahigh vacuum transmission electron microscopy (UHV-TEM), showing the critical radius of nanobubbles determining its unusual long-term stability as well as two distinct growth mechanisms of merging nanobubbles (Ostwald ripening and coalescing) depending on their relative sizes. Interestingly, the gas transport through ultrathin water membranes at nanobubble interface is free from dissolution, which is clearly different from conventional gas transport that includes condensation, transmission and evaporation. Our finding is expected to provide a deeper insight to understand unusual chemical, biological and environmental phenomena where nanoscale gas-state is involved.
The phase behavior of membrane proteins stems from a complex synergy with the amphiphilic molecules required for their solubilization. We show that ionization of a pH-sensitive surfactant, LDAO, bound to a bacterial photosynthetic protein, the Reaction Center (RC), leads in a narrow pH range to protein liquid-liquid phase separation in surprisingly stable `droplets, forerunning reversible aggregation at lower pH. Phase segregation is promoted by increasing temperature and hindered by adding salt. RC light-absorption and photoinduced electron cycle are moreover strongly affected by phase segregation.
The dielectric spectrum of liquid water, $10^{4} - 10^{11}$ Hz, is interpreted in terms of diffusion of charges, formed as a result of self-ionization of H$_{2}$O molecules. This approach explains the Debye relaxation and the dc conductivity as two manifestations of this diffusion. The Debye relaxation is due to the charge diffusion with a fast recombination rate, $1/tau_{2}$, while the dc conductivity is a manifestation of the diffusion with a much slower recombination rate, $1/tau_{1}$. Applying a simple model based on Brownian-like diffusion, we find $tau_{2} simeq 10^{-11}$ s and $tau_{1} simeq 10^{-6}$ s, and the concentrations of the charge carriers, involved in each of the two processes, $N_{2} simeq 5 times 10^{26}$ m$^{-3}$ and $N_{1} simeq 10^{14}$ m$^{-3}$. Further, we relate $N_{2}$ and $N_{1}$ to the total concentration of H$_{3}$O$^{+}$--OH$^{-}$ pairs and to the pH index, respectively, and find the lifetime of a single water molecule, $tau_{0} simeq 10^{-9}$ s. Finally, we show that the high permittivity of water results mostly from flickering of separated charges, rather than from reorientations of intact molecular dipoles.