Quaternized Graphene for High-Performance Moisture Swing Direct Air Capture of CO2.

Nowadays, moisture-swing adsorption technology still relies on quaternary ammonium resins with limited CO2 capacity under ambient air conditions. In this work, a groundbreaking moisture-driven sorbent is developed starting from commercial graphene flakes and using glycidyltrimethylammonium chloride for incorporation of CO2-sensitive quaternary ammonium functional groups. Boasting an outstanding CO2 capture performance under ultra-diluted conditions (namely, 3.24 mmol g-1 at CO2 400 ppm and 20% RH), the functionalized sorbent (fGO) features clear competitive advantages over current technologies for direct air capture. Notably, fGO demonstrated unprecedented moisture-swing capacity, ease of regenerability, versatility, selectivity, and longevity. These distinctive features position the fGO as an advanced and promising solution, showcasing its potential to outperform existing methods for moisture-swing direct air capture of CO2.

MWCNTs Decorated with TiO2 as Highly Performing Filler in the Preparation of Nanocomposite Membranes for Scalable Photocatalytic Degradation of Bisphenol A in Water.

Bisphenol A (BPA), an endocrine-disrupting compound with estrogenic behavior, is of great concern within the scientific community due to its high production levels and increasing concentration in various surface aquifers. While several materials exhibit excellent capacity for the photocatalytic degradation of BPA, their powdered nature and poor chemical stability render them unsuitable for practical application in large-scale water decontamination. In this study, a new class of nanocomposite membranes based on sulfonated polyethersulfone (sPES) and multiwalled carbon nanotubes decorated with TiO2 nanoparticles (MWCNTs-TiO2) were investigated as efficient and scalable photocatalysts for the photodegradation of BPA in aqueous solutions. The MWCNTs-TiO2 hybrid material was prepared through a facile and inexpensive hydrothermal method and extensively characterized by XRD, Raman, FTIR, BET, and TGA. Meanwhile, nanocomposite membranes at different filler loadings were prepared by a simple casting procedure. Swelling tests and PFG NMR analyses provided insights into the impact of filler introduction on membrane hydrophilicity and water molecular dynamics, whereas the effectiveness of the various photocatalysts in BPA removal was monitored using HPLC. Among the different MWCNTs-TiO2 content nanocomposites, the one at 10 wt% loading (sP-MT10) showed the best photoactivity. Under UV irradiation at 254 nm and 365 nm for 240 min, photocatalytic oxidation of 5 mg/L bisphenol A by sP-MT10 resulted in 91% and 82% degradation, respectively. Both the effect of BPA concentration and the membrane regenerability were evaluated, revealing that the sP-MT10 maintained its maximum BPA removal capability over more than 10 cycles. Our findings indicate that sP-MT nanocomposite membranes are versatile, scalable, efficient, and highly reusable photocatalysts for the degradation of BPA, as well as potentially for other endocrine disruptors.

Elucidating the Water and Methanol Dynamics in Sulfonated Polyether Ether Ketone Nanocomposite Membranes Bearing Layered Double Hydroxides.

Conventional Nafion membranes demonstrate a strong affinity for methanol, resulting in a high fuel crossover, poor mechanical stability, and thus poor performance in direct methanol fuel cells (DMFCs). This study involves the synthesis and physiochemical characterization of an alternative polymer electrolyte membrane for DMFCs based on sulfonated poly(ether ether ketone) and a layered double hydroxide (LDH) material. Nanocomposite membranes (sPL), with filler loading ranging between 1 wt% and 5 wt%, were prepared by simple solution intercalation and characterized by XRD, DMA, swelling tests, and EIS. For the first time, water and methanol mobility inside the hydrophilic channels of sPEEK-LDH membranes were characterized by NMR techniques. The introduction of LDH nanoplatelets improved the dimensional stability while having a detrimental effect on methanol mobility, with its self-diffusion coefficient almost two orders of magnitude lower than that of water. It is worth noting that anionic lamellae are directly involved in the proton transport mechanism, thus enabling the formation of highly interconnected paths for proton conduction. In this regard, sPL3 yielded a proton conductivity of 110 mS cm-1 at 120 °C and 90% RH, almost attaining the performance of the Nafion benchmark. The nanocomposite membrane also showed an excellent oxidative stability (over more than 24 h) during Fenton's test at 80 °C. These preliminary results demonstrate that an sPL3 nanocomposite can be potentially and successfully applied in DMFCs.

Exploring the Structure-Performance Relationship of Sulfonated Polysulfone Proton Exchange Membrane by a Combined Computational and Experimental Approach.

Sulfonated Polysulfone (sPSU) is emerging as a concrete alternative to Nafion ionomer for the development of proton exchange electrolytic membranes for low cost, environmentally friendly and high-performance PEM fuel cells. This ionomer has recently gained great consideration since it can effectively combine large availability on the market, excellent film-forming ability and remarkable thermo-mechanical resistance with interesting proton conductive properties. Despite the great potential, however, the morphological architecture of hydrated sPSU is still unknown. In this study, computational and experimental advanced tools are combined to preliminary describe the relationship between the microstructure of highly sulfonated sPSU (DS = 80%) and its physico-chemical, mechanical and electrochemical features. Computer simulations allowed for describing the architecture and to estimate the structural parameters of the sPSU membrane. Molecular dynamics revealed an interconnected lamellar-like structure for hydrated sPSU, with ionic clusters of about 14-18 Å in diameter corresponding to the hydrophilic sulfonic-acid-containing phase. Water dynamics were investigated by 1H Pulsed Field Gradient (PFG) NMR spectroscopy in a wide temperature range (20-120 °C) and the self-diffusion coefficients data were analyzed by a "two-sites" model. It allows to estimate the hydration number in excellent agreement with the theoretical simulation (e.g., about 8 mol H2O/mol SO3- @ 80 °C). The PEM performance was assessed in terms of dimensional, thermo-mechanical and electrochemical properties by swelling tests, DMA and EIS, respectively. The peculiar microstructure of sPSU provides a wider thermo-mechanical stability in comparison to Nafion, but lower dimensional and conductive features. Nonetheless, the single H2/O2 fuel cell assembled with sPSU exhibited better features than any earlier published hydrocarbon ionomers, thus opening interesting perspectives toward the design and preparation of high-performing sPSU-based PEMs.

New Insights into Properties of Methanol Transport in Sulfonated Polysulfone Composite Membranes for Direct Methanol Fuel Cells.

Methanol crossover through a polymer electrolyte membrane has numerous negative effects on direct methanol fuel cells (DMFCs) because it decreases the cell voltage due to a mixed potential (occurrence of both oxygen reduction and methanol oxidation reactions) at the cathode, lowers the overall fuel utilization and contributes to long-term membrane degradation. In this work, an investigation of methanol transport properties of composite membranes based on sulfonated polysulfone (sPSf) and modified silica filler is carried out using the PFG-NMR technique, mainly focusing on high methanol concentration (i.e., 5 M). The influence of methanol crossover on the performance of DMFCs equipped with low-cost sPSf-based membranes operating with 5 M methanol solution at the anode is studied, with particular emphasis on the composite membrane approach. Using a surface-modified-silica filler into composite membranes based on sPSf allows reducing methanol cross-over of 50% compared with the pristine membrane, making it a good candidate to be used as polymer electrolyte for high energy DMFCs.

How the Morphology of Nafion-Based Membranes Affects Proton Transport.

This work represents a systematic and in-depth study of how Nafion 1100 membrane preparation procedures affect both the morphology of the polymeric film and the proton transport properties of the electrolyte. The membrane preparation procedure has non-negligible consequences on the performance of the proton-exchange membrane fuel cells (PEMFC) that operate within a wide temperature range (up to 120 °C). A comparison between commercial membranes (Nafion 117 and Nafion 212) and Nafion membranes prepared by three different procedures, namely (a) Nafion-recast, (b) Nafion uncrystallized, and (c) Nafion 117-oriented, was conducted. Electrochemical Impedance Spectroscopy (EIS) and Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) investigations indicated that an anisotropic morphology could be achieved when a Nafion 117 membrane was forced to expand between two fixed and nondeformable surfaces. This anisotropy increased from ~20% in the commercial membrane up to 106% in the pressed membrane, where the ionic clusters were averagely oriented (Nafion 117-oriented) parallel to the surface, leading to a strong directionality in proton transport. Among the membranes obtained by solution-cast, which generally exhibited isotropic proton transport behavior, the Nafion uncrystallized membrane showed the lowest water diffusion coefficients and conductivities, highlighting the correlation between low crystallinity and a more branched and tortuous structure of hydrophilic channels. Finally, the dynamic mechanical analysis (DMA) tests demonstrated the poor elastic modulus for both uncrystallized and oriented membranes, which should be avoided in high-temperature fuel cells.

Titanium Dioxide Grafted on Graphene Oxide: Hybrid Nanofiller for Effective and Low-Cost Proton Exchange Membranes.

A nanostructured hybrid material consisting of TiO2 nanoparticles grown and stabilized on graphene oxide (GO) platelets, was synthesized and tested as nanofiller in a polymeric matrix of sulfonated polysulfone (sPSU) for the preparation of new and low-cost nanocomposite electrolytes for proton exchange membrane fuel cell (PEMFC) applications. GO-TiO2 hybrid material combines the nanoscale structure, large interfacial area, and mechanical features of a 2D, layered material, and the hygroscopicity properties of ceramic oxides, able to maintain a suitable hydration of the membrane under harsh fuel cell operative conditions. GO-TiO2 was synthetized through a new, simple, one-pot hydrothermal procedure, while nanocomposite membranes were prepared by casting using different filler loadings. Both material and membranes were investigated by a combination of XRD, Raman, FTIR, thermo-mechanical analysis (TGA and Dynamic Mechanical Analysis) and SEM microscopy, while extensive studies on the proton transport properties were carried out by Electrochemical Impedance Spectroscopy (EIS) measurements and pulse field gradient (PFG) NMR spectroscopy. The addition of GO-TiO2 to the sPSU produced a highly stable network, with an increasing of the storage modulus three-fold higher than the filler-free sPSU membrane. Moreover, the composite membrane with 3 wt.% of filler content demonstrated very high water-retention capacity at high temperatures as well as a remarkable proton mobility, especially in very low relative humidity conditions, marking a step ahead of the state of the art in PEMs. This suggests that an architecture between polymer and filler was created with interconnected routes for an efficient proton transport.

Transport Properties and Mechanical Features of Sulfonated Polyether Ether Ketone/Organosilica Layered Materials Nanocomposite Membranes for Fuel Cell Applications.

In this work, we study the preparation of new sulfonated polyether ether ketone (sPEEK) nanocomposite membranes, containing highly ionic silica layered nanoadditives, as a low cost and efficient proton exchange membranes for fuel cell applications. To achieve the best compromise among mechanical strength, dimensional stability and proton conductivity, sPEEK polymers with different sulfonation degree (DS) were examined. Silica nanoplatelets, decorated with a plethora of sulfonic acid groups, were synthesized through the one-step process, and composite membranes at 1, 3 and 5 wt% of filler loadings were prepared by a simple casting procedure. The presence of ionic layered additives improves the mechanical strength, the water retention capacity and the transport properties remarkably. The nanocomposite membrane with 5% wt of nanoadditive exhibited an improvement of tensile strength almost 160% (68.32 MPa,) with respect to pristine sPEEK and a ten-times higher rate of proton conductivity (12.8 mS cm-1) under very harsh operative conditions (i.e., 90 °C and 30% RH), compared to a filler-free membrane. These findings represent a significant advance as a polymer electrolyte or a fuel cell application.

Understanding the Effect of UV-Induced Cross-Linking on the Physicochemical Properties of Highly Performing PEO/LiTFSI-Based Polymer Electrolytes.

We report a thorough, multitechnique investigation of the structure and transport properties of a UV-cross-linked polymer electrolyte based on poly(ethylene oxide), tetra(ethylene glycol)dimethyl ether (G4), and lithium bis(trifluoromethane)sulfonimide. The properties of the cross-linked polymer electrolyte are compared to those of a non-cross-linked sample of same composition. The effect of UV-induced cross-linking on the physico/chemical characteristics is evaluated by X-ray diffraction, differential scanning calorimetry, shear rheology, 1H and 7Li magic angle spinning nuclear magnetic resonance (NMR) spectroscopy, 19F and 7Li pulsed field gradient stimulated echo NMR analyses, electrochemical impedance spectroscopy, and Fourier transform Raman spectroscopy. Comprehensive analysis confirms that UV-induced cross-linking is an effective technique to suppress the crystallinity of the polymer matrix and reduce ion aggregation, yielding improved Li+ transport number (>0.5) and ionic conductivity (>0.1 mS cm?1) at ambient temperature, by tailoring the structural/morphological characteristics of the polymer matrix. Finally, the polymer electrolyte allows reversible operation with stable profile for hundreds of cycles upon galvanostatic test at ambient temperature of LiFePO4-based lithium-metal cells, which deliver full capacity at 0.05 or 0.1C current rate and keep high rate capabilities up to 1C. This enforces the role of UV-induced cross-linking in achieving excellent electrochemical characteristics, exploiting a practical, easy up-scalable process.

Gi Protein Modulation of the Potassium Channel TASK-2 Mediates Vesicle Osmotic Swelling to Facilitate the Fusion of Aquaporin-2 Water Channel Containing Vesicles.

Vesicle fusion is a fundamental cell biological process similar from yeasts to humans. For secretory vesicles, swelling is considered a step required for the expulsion of intravesicular content. Here this concept is revisited providing evidence that it may instead represent a general mechanism. We report the first example that non-secretory vesicles, committed to insert the Aquaporin-2 water channel into the plasma membrane, swell and this phenomenon is required for fusion to plasma membrane. Through an interdisciplinary approach, using atomic force microscope (AFM), a fluorescence-based assay of vesicle volume changes and NMR spectroscopy to measure water self-diffusion coefficient, we provide evidence that Gi protein modulation of potassium channel TASK-2 localized in AQP2 vesicles, is required for vesicle swelling. Estimated intravesicular K⁺ concentration in AQP2 vesicles, as measured by inductively coupled plasma mass spectrometry, was 5.3 mM, demonstrating the existence of an inwardly K⁺ chemical gradient likely generating an osmotic gradient causing vesicle swelling upon TASK-2 gating. Of note, abrogation of K⁺ gradient significantly impaired fusion between vesicles and plasma membrane. We conclude that vesicle swelling is a potentially important prerequisite for vesicle fusion to the plasma membrane and may be required also for other non-secretory vesicles, depicting a general mechanism for vesicle fusion.

Composite Gel Polymer Electrolytes Based on Organo-Modified Nanoclays: Investigation on Lithium-Ion Transport and Mechanical Properties.

Composite gel polymer electrolytes (GPEs) based on organo-modified montmorillonite clays have been prepared and investigated. The organo-clay was prepared by intercalation of CTAB molecules in the interlamellar space of sodium smectite clay (SWy) through a cation-exchange reaction. This was used as nanoadditive in polyacrylonitrile/polyethylene-oxide blend polymer, lithium trifluoromethanesulphonate (LiTr) as salt and a mixture of ethylene carbonate/propylene carbonate as plasticizer. GPEs were widely characterized by DSC, SEM, and DMA, while the ion transport properties were investigated by AC impedance spectroscopy and multinuclear NMR spectroscopy. In particular, 7Li and 19F self-diffusion coefficients were measured by the pulse field gradient (PFG) method, and the spin-lattice relaxation times (T1) by the inversion recovery sequence. A complete description of the ions dynamics in so complex systems was achieved, as well as the ion transport number and ionicity index were estimated, proving that the smectite clay surfaces are able to "solvatate" both lithium and triflate ions and to create a preferential pathway for ion conduction.

Toxicity Evaluation of Graphene Oxide and Titania Loaded Nafion Membranes in Zebrafish.

The use of nanomaterials in several application fields has received in the last decades a great attention due to their peculiar properties, but also raised many doubts about possible toxicity when these materials are used for some specific applications, such as water purification. Indeed a careful investigation is needed in order to exclude possible harmful side effects related to the use of nanotechnology. Nanoparticles effects on the marine organisms may depend on their chemical composition, size, surface structure, solubility, shape and how the individual nanoparticles aggregate together. In order to make the most of their potential, without polluting the environment, many researchers are trying to trap them into some kind of matrix that keeps them active but avoids their dispersion in the environment. In this study we have tested nanocomposite membranes prepared using Nafion polymer combined with various fillers, such as anatase-type TiO2 nanoparticles and graphene oxide. The non-toxicity of these nanocomposites, already shown to be effective for water purification applications in our previous studies, was recognized by testing the effect of the different materials on zebrafish embryos. Zebrafish was considered an excellent model for ecotoxicological studies and for this motivation zebrafish embryos were exposed to different concentrations of free nanoparticles and to the nanocomposite membranes. As biomarkers of exposure, we evaluated the expression of heme-oxygenase 1 and inducible Nitric Oxide Synthases by immunohistochemistry and gene expression. Embryo toxicity test showed that nor sublethal effects neither mortality were caused by the different nanoparticles and nano-systems tested. Only zebrafish larvae exposed to free nanoparticles have shown a different response to antibodies anti-heme-oxygenase 1 and anti- inducible Nitric Oxide Synthases. The immunolocalization analysis in fact has highlighted an increase in the synthesis of these biomarkers.

Decoupling of dynamic processes in surfactant-based liquid mixtures: the case of lithium-containing bis(2-ethylhexyl)phosphoric acid/bis(2-ethylhexyl)amine systems.

Pure surfactant liquids and their binary mixtures, because of the amphiphilic nature of the molecules involved, can exhibit nanosegregation and peculiar transport properties. The idea that inspired this work is that the possibility of including in such media salts currently used for technological applications should lead to a synergy between the properties of the salt and those of the medium. Therefore, the dynamic features of bis(2-ethylhexyl)amine (BEEA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) liquid mixtures were investigated as a function of composition and temperature by (1)H nuclear magnetic resonance (NMR) spectroscopy and rheometry. Inclusion of litium trifluoromethanesulfonate (LiT) has been investigated by infrared spectroscopy, pulsed field gradient NMR, and conductimetry methods to highlight the solubilizing and confining properties of these mixtures as well as the lithium conductivity. It was found that BEEA/HDEHP binary liquid mixtures show zero-threshold percolating self-assembly with a maximum in viscosity and a minimum in molecular diffusion at a 1:1 composition. Dissolution of LiT in such system can occur via confinement in the locally self-assembled polar domains. Despite this confinement, Li(+) conduction is scarcely dependent on the medium composition because of the possibility of a field-induced hopping decoupled by the structural and dynamical features of the medium.

Dynamical properties of self-assembled surfactant-based mixtures: triggering of one-dimensional anomalous diffusion in bis(2-ethylhexyl)phosphoric acid/n-octylamine systems.

The dynamic features of bis(2-ethylhexyl)phosphoric acid (HDEHP)/n-octylamine (NOA) mixtures have been investigated as a function of the NOA mole fraction and temperature by (1)H NMR spectroscopy and rheometry. All data consistently suggest a composition-induced glass-forming behavior. The microscopic factors responsible for this behavior have been highlighted and have been explained in terms of driving forces given by HDEHP-to-NOA proton transfer, the tendency of the resulting species to establish H bonds and to spatially segregate the alkyl chains. The study sheds light on the molecular mechanism responsible for the peculiar behavior of transport properties in such systems and furnishes basic knowledge to be used to design novel materials with planned physicochemical properties.

Graphene-based nafion nanocomposite membranes: enhanced proton transport and water retention by novel organo-functionalized graphene oxide nanosheets.

Novel nanostructured organo-modified layered materials based on graphene oxide carrying various hydrophilic functional groups (-NH(2), -OH, -SO(3)H) are prepared and tested as nanofillers for the creation of innovative graphene-based Nafion nanocomposites. The hybrid membranes are characterized by a combination of analytical techniques, which show that highly homogeneous exfoliated nanocomposites are created. The pulsed field gradient NMR technique is used to measure the water self-diffusion coefficients. Remarkable behavior at temperatures up to 140 °C is observed for some composite membranes, thereby verifying the exceptional water retention property of these materials. Dynamic mechanical analysis shows that hybrid membranes are much stiffer and can withstand higher temperatures than pure Nafion.

NMR and Electrochemical Investigation of the Transport Properties of Methanol and Water in Nafion and Clay-Nanocomposites Membranes for DMFCs.

Water and methanol transport behavior, solvents adsorption and electrochemical properties of filler-free Nafion and nanocomposites based on two smectite clays, were investigated using impedance spectroscopy, DMFC tests and NMR methods, including spin-lattice relaxation and pulsed-gradient spin-echo (PGSE) diffusion under variable temperature conditions. Synthetic (Laponite) and natural (Swy-2) smectite clays, with different structural and physical parameters, were incorporated into the Nafion for the creation of exfoliated nanocomposites. Transport mechanism of water and methanol appears to be influenced from the dimensions of the dispersed platelike silicate layers as well as from their cation exchange capacity (CEC). The details of the NMR results and the effect of the methanol solution concentration are discussed. Clays particles, and in particular Swy-2, demonstrate to be a potential physical barrier for methanol cross-over, reducing the methanol diffusion with an evident blocking effect yet nevertheless ensuring a high water mobility up to 130 °C and for several hours, proving the exceptional water retention property of these materials and their possible use in the DMFCs applications. Electrochemical behavior is investigated by cell resistance and polarization measurements. From these analyses it is derived that the addition of clay materials to recast Nafion decreases the ohmic losses at high temperatures extending in this way the operating range of a direct methanol fuel cell.

Effective improvement of water-retention in nanocomposite membranes using novel organo-modified clays as fillers for high temperature PEMFCs.

Toward an enhanced water-retention of polymer electrolyte membranes at high temperatures, novel organo-modified clays were prepared and tested as fillers for the creation of hybrid Nafion nanocomposites. Two smectite clays (Laponite and montmorillonite), with different structural and physical parameters, were loaded with various cationic organic molecules bearing several hydrophilic functional groups (-NH(2), -OH, -SO(3)H) and incorporated in Nafion by solution intercalation. The resulted hybrid membranes were characterized by a combination of powder X-ray diffraction, FTIR spectroscopy, and thermal analysis (DTA/TGA) showing that highly homogeneous exfoliated nanocomposites were created where the individual organoclay layers are uniformly dispersed in the continuous polymeric matrix. In this paper, water-transport properties were investigated by NMR spectroscopy, including pulsed-field-gradient spin-echo diffusion and spectral measurements conducted under variable temperature. Organo-montmorillonite nanofillers demonstrate a considerable effect on the Nafion polymer in terms both of water absorption/retention and water mobility with a remarkable behavior in the region of high temperatures (100-130 °C), denoting that the surface modifications of this clay with acid organic molecules significantly improve the performance of the final composite membrane. (1)H NMR spectral analysis allowed a general description of the water distribution in the system and an estimation of the number of water molecules involved in the hydration shell of the sulfonic groups as well as that absorbed on the organoclay particles.

Effect of shear on vesicle and lamellar phases of DDAB/lecithin ternary systems.

The influence of shear flow on bilayer structures (vesicle and planar lamellar phases, L(α)), formed in DDAB/lecithin ternary systems, is studied by means of conventional rheology, Rheo NMR, and optical microscopy. The vesicles in the diluted (Lam(1)) phase are polydisperse multilamellae which turn into smaller monodisperse vesicles under shear. The concentrated (Lam(2)) phase is formed by non-oriented lamellae that do not surprisingly exhibit any pronounced shear-induced alignment prior to the transition into giant multilamellar vesicles. The biphasic region (Lam(1)+Lam(2)) shows a mosaic texture with a powder pattern indicating the prevalence of lamellae that transform into onions under shear.

Evidence of formation of ammonium perfluorononanoate/2H2O multilamellar vesicles: morphological analysis by rheology and rheo-2H NMR experiments.

Rheology and rheo-(2)H NMR measurements are presented for 30 wt % ammonium perfluorononanoate (APFN)/(2)H(2)O mixture in the temperature range 20-70 °C. A first-order lamellar-to-nematic transition occurs at 42 °C, and a first-order nematic-to-isotropic transition occurs at 49 °C. Different rheological behaviors of the lamellar phase were observed with increasing the temperature. The lamellar structure at low temperature (Lα(-)) has a clear gel-like viscoelasticity, while at high temperature the lamellar structure (Lα(+)) has a liquid-like response. In this study we have observed for the first time, along with the lamellar phase of a surfactant containing fluorinated fatty acid, the formation of multilamellar vesicles (MLVs) ("onions") induced by shear. With the aid of nonlinear rheology and rheo-NMR techniques, onion formation was found to occur in both temperature regimes of the lamellar phase, but at different strain units. It is suggested that the lamellar phase consists of smectic structures in both Lα(-) and Lα(+), but with different percentages of defect density.

NMR investigation of the dynamics of confined water in nafion-based electrolyte membranes at subfreezing temperatures.

The dynamical characteristics and the thermal analysis of water absorbed in filler-free Nafion and in silica or zirconia phosphate Nafion composites, between 20 and -50 degrees C, were investigated by NMR and DSC techniques. Self-diffusion coefficients and longitudinal NMR relaxation times (T(1)) put in evidence a fraction of water freezing at subzero temperatures. The complementary water fraction remains in the liquid state at least down to -50 degrees C. The freezing point (T(f)) depends on the initial water uptake of the electrolyte membrane and, for similar uptake values, water mobility is favorite in composites systems respect to the filler-free Nafion. By DSC thermograms the hydration water molecules number per sulfonic group in the filler-free Nafion was estimated, obtaining 8 molecules/SO(3)(-) group. In the Nafion/Zr(HPO(4))(2) composite, instead, the number of hydration water is about 20 molecules/ionic group, because of the acid nature of the zirconia particles. Below T(f), the presence of this nonfreezable water fraction allows proton transport, and therefore ensures ionic conductivity also at subzero temperatures.