Effect of ion-exchange nanofiber fabrics on water splitting in bipolar membrane

In the present study, the effect of ion-exchange fiber fabric made by electrospray deposition (ESD) on water splitting in a composite bipolar membrane (CBM) was investigated. Cation- and anion-exchange fiber (CEF and AEF) fabrics, which were composed of very thin fibers, were prepared by ESD and postdeposition chemical modification and then used as the intermediate layer of a CBM. The current-voltage characteristics under reverse bias conditions showed that the AEF fabrics enhanced water splitting. The water dissociation is accelerated by the AEF fabric, which contains both tertiary pyridyl groups and quaternary pyridinium groups and has a high specific surface area. On the other hand, the CEF fabric, which contains sulfonic acid groups and has an insufficient specific surface area, reduced water splitting. These results indicate that fiber fabric with catalytic activity and a high surface area obtained by ESD can improve the performance of a CBM.     

Conformation of adsorbed layers of polyNIPAM on silica in a binary solvent

The conformation of poly( N-isopropylacrylamide) chains adsorbed at a silica interface was studied as a function of concentration in the methanol-water binary solvent mixture. Both water and methanol are good solvents for PNIPAM; however, in certain mixtures cononsolvency is induced by a lowering of the LCST. This led to a decrease in the extent of the PNIPAM layer away from the interface as measured using the colloidal probe technique in the poor solvent region. At low methanol concentrations but still in the good solvent region capillary bridging between the silica surfaces with adsorbed PNIPAM layers was observed due to the increased methanol concentration in this interfacial region over that of the bulk. Furthermore, adsorption measurements showed that PNIPAM adsorbed only weakly to the silica interface with a low surface excess on the order of 0.23 mg/m (2), which allowed study of the behavior of the immobilized PNIPAM chains under highly dilute conditions using the quartz crystal microbalance. As the concentration of methanol increased toward the phase transition boundary, a slight contraction followed by an expansion of the PNIPAM was observed, which is in agreement with previous predictions from theory for polymers in solution.     

Polymer Dynamics in a Polymer-Solid Interphase: Molecular Dynamics Simulations of 1,4-Polybutadiene At a Graphite Surface

A chemically realistic model of 1,4-polybutadiene confined by graphite walls in a thin film geometry was studied by molecular dynamics simulations. The chemically realistic approach allows for a quantitative determination of a variety of experimentally accessible relaxation functions (e.g., dielectric, NMR, or neutron scattering responses). The simulations yield these experimental observables. Additionally, the simulations can be resolved as a function of distance to the solid interface on a much finer scale than experimentally possible, providing a detailed mechanistic picture of the segmental and large scale motions of polymers in the interfacial region between bulk polymer melts and solid walls. Extending the study of 1,4-polybutadiene on graphite to temperatures close to the glass transition temperature, we also address the question to what extent growing length scales associated with the glass transition influence the melt dynamics in the interphase. It was found that there is an interplay of this intrinsic slowing down with the adsorption/desorption kinetics of the chains close to the wall. It is argued that the monomer density changes near the wall can overcome the effect of rotational barriers only in a region of about 2 nm next to the wall.     

Polymer blend membranes of sulfonated poly(arylene ether ketone) for direct methanol fuel cell

The blend membranes of sulfonated poly(arylene ether ketone) (sPAEK) (IEC = 1.0 mequiv./g)/Nafion^® and the blend membranes of sPAEK (IEC = 1.0 mequiv./g)/sPAEK (IEC = 1.7 mequiv./g) were prepared. sPAEK with low IEC was introduced to reduce the methanol permeability through the membrane. Morphology, water uptake, proton conductivity and methanol permeability of the blend membranes were investigated by SEM, AFM, AC impedance spectroscopy and permeability measuring instrument. The cross-sections of blend membranes showed phase-separated morphologies. The effect of phase-separated morphology on the properties of blend membranes was investigated. The properties like water uptake, proton conductivity, and methanol permeability of sPAEK/Nafion^® blend membranes showed similar values with sPAEK and properties of sPAEK/sPAEK blend membranes showed intermediate values of two polymers due to the difference in morphology of the blend membranes. sPAEK/sPAEK blend membranes showed relatively high proton conductivity and lowered methanol permeability compared to Nafion^®. sPAEK/sPAEK blend membranes could be a competent substitution for Nafion^®.     

Water at surfaces: What can we learn from vibrational spectroscopy?

Recent developments in the vibrational spectroscopy of thin films of water adsorbed on well defined metal surfaces under ultra-high vacuum (UHV) conditions will be discussed. New results will be presented for H₂O and D₂O adsorbed on Cu(110), measured using grazing incidence reflection-absorption infrared spectroscopy (RAIRS). These will be discussed in context with previous high-resolution electron energy loss spectroscopy (HREELS) measurements of H₂O on Pd(110). Both of these results are typical of measurements from other laboratories. Particular attention will be paid to the O-H stretching region of the spectrum. A detailed examination of this region of the spectrum is used to study the amorphous to crystalline phase transition in thin films, the temperature dependence of the sticking coefficient of water, and the structure of the first one or two layers of water directly at the solid interface. The spectroscopic signature observed for very thin films is found to be consistently different from that of crystalline ice, and the possible reasons for this difference are discussed.     

Theoretical study of the Fe(phen)(2)(NCS)(2) spin-crossover complex with reparametrized density functionals

The theoretical study of spin-crossover compounds is very challenging as those parts of the experimental findings that concern the electronic structure of these compounds can currently hardly be reproduced because of either technical limitations of highly accurate ab initio methods or because of inaccuracies of density functional methods in the prediction of low-spin/high-spin energy splitting. However, calculations with reparametrized density functionals on molecules of the thermal spin-crossover type can give improved results when compared with experiment for close-lying states of different spin and are therefore important for, e.g., transition metal catalysis. A classification of transition metal compounds within hybrid density functional theory is given to distinguish standard, critical, and complicated cases. From the class of complicated cases we choose the prominent spin-crossover compound Fe(phen)(2)(NCS)(2) and show in a first step how the electronic contribution to the energy splitting can be calculated. In a second step, the vibrational effects on the spin flip are investigated within the harmonic force-field approximation of the isolated-molecule approach. A main result of the study is the necessity of exact-exchange reduction in hybrid density functionals to arrive at reasonable electronic energy splittings. The study resolves problems that originated from the use of standard density functionals, which are not able to reproduce the electronic contribution to the low-spin/high-spin splitting correctly, and demonstrates to which extent reparametrized density functionals can be used for the prediction of the spin-crossover effect.     

Molecularly imprinted polymer membranes for substance-selective solid-phase extraction from water by surface photo-grafting polymerization

Hydrophilized polyvinylidene fluoride microfiltration membranes were surface-modified in the presence of a template (terbumeton) in methanol with a graft copolymer of a functional monomer (2-acrylamido-2-methyl-1-propane sulfonic acid, AMPS, methacrylic acid, MAA, or acrylic acid, AA) and a cross-linker (N,N'-methylene-bis-acrylamide) using UV irradiation and benzophenone as photoinitiator. As result, membranes covered with a thin layer of imprinted polymer selective to terbumeton were obtained. Blank membranes were prepared with the same monomer composition, but in the absence of the template. The membranes' capacity to adsorb terbumetone from aqueous solution was evaluated yielding information regarding the effect of polymer synthesis (type and concentration of functional monomer, concentration of cross-linker) on the resulting membranes' recognition properties. UV spectroscopic studies of the interactions with terbumetone revealed that AMPS forms a stronger complex than MAA and AA. In agreement with that finding, imprinting with AMPS gave higher affinities than with MAA and AA. The terbumeton-imprinted membranes showed significantly higher sorption capability to this herbicide than to similar compounds (atrazine, desmetryn, metribuzine). With the novel surface modification technology, the low non-specific binding properties of the hydrophilized microfiltration membrane could successfully be combined with the receptor properties of molecular imprints, yielding substance-specific molecularly imprinted polymer composite membranes. The high affinity of these synthetic affinity membranes to triazine herbicides together with their straightforward and inexpensive preparation provides a good basis for the development of applications of imprinted polymers in separation processes such as solid-phase extraction.     

Air-Stable Mn doped CuCl/CuO Hybrid Triquetrous Nanoarrays as Bifunctional Electrocatalysts for Overall Water Splitting

The development of highly efficient non-precious metal catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is key for large-scale hydrogen evolution through water splitting technology. Here, we report an air-stable Cu-based nanostructure consisting of Mn doped CuCl and CuO (CuCl/CuO(Mn)-NF) as a dual functional electrocatalyst for water splitting. CuCl is identified as the main active component, together with Mn doping and the synergistic effect between CuCl and CuO are found to make responsibility for the excellent OER and HER catalytic activity and stability. The assembled electrolyzes also exhibit decent water splitting performance. This work not only provides a simple method for preparing Cu-based composite catalyst, but also demonstrates the great potential of Cu-based non-noble metal electrocatalysts for water splitting and other renewable energy conversion technologies.     

Optical switching of azobenzene sidechain molecules observed by surface plasmon spectroscopy

The use of surface plasmons is reported for the optical characterization of thin organic films, in particular thin polymer films at a metal dielectric interface. The basic properties of PSP are presented, including excitation and the technique of surface plasmon microscopy, which allows to obtain an image. As an example studies are presented on the trans-cis photoisomerization of azobenzene sidechain polymers in ultra thin films, prepared by the Langmuir-Blodgett-Kuhn technique. The transition from the trans to the cis state induces a change in the refractive index of the film. These changes were detected and their kinetics measured by a surface plasmon spectroscopy technique. A refractive index pattern could be written into the films and the areas of different refractive indices have been detected by surface plasmon microscopy.     

Monolayers and membranes from amphiphilic polymers

Nanometer thin, elastomeric membranes with considerable application potential in micro mechanics and materials science can be prepared by transferring monomolecular layers of polymers with ionic head groups from the water surface to solid substrates with holes. If monolayers of liquid polymers are transferred to substrates with openings they initially cover the openings, but finally rupture within a couple of minutes after transfer. However, if the polymer monolayers are stabilised by vitrification, chemical or physical cross-linking, they can be transferred to cover openings in solids substrates as stable membranes. Especially if monolayers of low glass transition polymers are cross-linked, elastomeric membranes are obtained, which might find application in micro mechanical devices like membrane valves and pumps. Incorporation of either a second, incompatible polymer or hydrophobised colloids leads to laterally structured and porous membranes.     

Dielectric relaxation on the intermediate layer in a bipolar membrane under the water splitting phenomenon. II. Double dielectric relaxation and identification of phase parameters

In this study, we investigated the impedance spectra of bipolar membranes. Under the application of a reverse-biased voltage, the spectra showed a double dielectric relaxation profile due to the heterogeneous structure and it was analyzed in accordance with the three-layered dielectric model. It is defined that one of the compositions of the heterogeneous structure is situated at the membrane interface region between the negatively and the positively charged membrane with a thickness of less than several micrometers, which has an extraordinarily large electric capacity with a magnitude of sub-microfarads. It is concluded that this layer is identified with the intermediate layer in which the water splitting phenomenon occurs on the bipolar membrane.     

Blend membranes of Nafion/sulfonated poly(aryl ether ketone) for direct methanol fuel cell

Sulfonated poly(aryl ether ketone) (sPAEK) synthesized by LG Chem. was confirmed by FT-IR. To estimate the thermal stability, glass transition temperature and decomposition temperature were investigated. They showed that sPAEK had good thermal properties. The proton conductivity, methanol permeability and water uptake of sPAEK were also measured. Nafion/sulfonated poly(aryl ether ketone) composite membranes were prepared by blending two materials. The blend ratios of sPAEK and Nafion were 2:1, 3:1, 5:1, and 7:1. The blend membranes showed phase separated morphology since they became immiscible during the solvent evaporation process. Due to the differences in specific gravity and solvent concentration profile during the solvent evaporation process, the upper region had lower Nafion volume fraction with smaller domains and the lower region had higher Nafion volume fraction with larger domains. Mechanical properties such as the stress at break, yield stress, Young's modulus, and elongation at break were measured. The sPAEK had better mechanical properties than Nafion. The mechanical properties increased with increasing sPAEK content. Proton conductivity and methanol permeability of the blend membranes were lower than those of Nafion. Both decreased with decreasing Nafion content. Since the methanol permeability of sPAEK was lower than that of Nafion, sPAEK acted as the methanol barrier. Water uptake of sPAEK was higher than that of Nafion.     

Morphological Characterization of Electrospun Nano-Fibrous Membranes of Biodegradable Poly(L-lactide) and Poly(lactide-co-glycolide)

Hydrophobic biodegradable polyesters, poly(L-lactide) (PLLA) and poly(lactide-co-glycolide) (PLGA), were electrospun on different types of collectors to induce morphological changes in the nanofibrous membrane. On the metal collector smooth nonwoven membranes were obtained for both PLLA and PLGA, while on the water reservoir the surface of the membranes became rough due to shrinkage and slow charge dissipation. When NaCl was added to water to enhance the conductivity, the roughness of the membrane surface was changed, yet the shrinkage remained relatively unchanged. The crystallization of PLLA electospun material on the metal plate was suppressed because of the rapid solvent evaporation, however, upon annealing above the glass transition temperature for 24 hr the PLLA membrane became crystallized. When electrospun on the water reservoir, the PLLA membrane remained amorphous. Crystalline PLLA was obtained by electrospinning on the methanol reservoir due to the swelling of nanofibers by methanol.     

Permeation of water as a tool for characterizing the effect of solvent, film thickness and water solubility in cellulose acetate membranes

Cellulose acetate membranes have been used in many applications; of particular interest are reverse osmosis systems, and as a neutral matrix for incorporation of different polymers (e.g., conducting polymers), inorganic ions (e.g., lanthanides) and organic (e.g., pharmaceutical) compounds. The properties of the new polymers derived from cellulose acetate or blends depend on those of cellulose acetate. This work presents an attempt to find links between thermodynamic and kinetic properties of cellulose acetate membranes in equilibrium with water. Water diffusion coefficients in cellulose acetate membranes are reported, measured with a simple water permeation technique. The comparison of these values with the percentage of water uptake and polymer thickness leads to interesting conclusions related with different polymer properties.     

Thermal degradation behaviour of some metal chelate polymer compounds with bis(bidentate) ligand by TG/DTG/DTA

Seven novel divalent transitional metal chelate polymers compounds (commonly known as chelate compounds or metal coordination complexes or polymer complexes) have been characterized by thermogravimetry (TG), differential thermal gravimetry (DTG) and differential thermal analysis (DTA) methods. Thermal decomposition behaviour of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) polymers with terphthaoyl-bis(p-methoxyphenylcarbamide) has been investigated by thermogravimetric analysis (TGA) at heating rate 10 °C min^?1 under nitrogen atmosphere. TG/DTA of chelate compounds were shown to be a stable compound against thermal decomposition which was measured on the basis of final decomposing temperature, but it is observed in some curves that decomposition takes place at low temperature due to the lattice water, which is always placed at outer coordination sphere of the central metal ion. The presence of both lattice and coordinated water were noteworthy investigated in Co(II), Ni(II) and Cu(II) chelate polymer compounds, whereas lattice water found in Zn(II), Cd(II) and Hg(II). However, Mn(II) showed only coordinated water. Thermal stabilities for release of lattice water, coordinated water and organic moiety that occur in sequential decomposition of chelate compounds are explained on the basis of ionic size effect and electronegativity. The processes of thermal degradation taking place in seven chelate polymers were studied comparatively by TG/DTG/DTA curves which indicating the difference in the thermal decomposition. Coats–Redfern integral method is used to determine the kinetic parameters for the successive steps in the decomposition sequence of TG curves. Scanning electron microscope images of some chelate polymers were shown in previous publication revealed that particle sizes of chelate polymers were found to be of nanomaterial level therefore, resulting chelate compounds might be called as nanomaterial.     

Role of metals and metal-deactivators in polymer degradation

The interaction between metals or metallic compounds and polymers is inevitable in the practical use of polymeric articles, and the stability of the polymers is often modified by these materials. Furthermore, the effect of the metallic compounds on the degradation of the polymers is extremely complicated, and is influenced by various factors.

This contribution deals with the possible role of metals or metallic compounds in the degradation of polymers, and this is followed by some typical examples of degradation by metallic compounds, mostly commercial pigments and transition metal compounds of stearic acid and acetylacetone, in typical commercial polymers. Recent studies of the inhibition of the copper-catalyzed thermo-oxidative degradation of polyolefins by deactivators, both commercial reagents and novel products, are discussed.     

Control of the metal-support interface of NiO-loaded photocatalysts via cold plasma treatment

NiO-loaded semiconductors have been extensively used as the photocatalysts for water splitting. The metal-support interface is an important factor affecting the efficiency. In the present work, the pretreatment methods were studied to produce a more desirable metal-support interface using Ta2O5 and ZrO2 as the support. The traditional method includes a thermal decomposition, reduction at 773 K, and oxidation at 473 K (R773-O473). The thermal decomposition of Ni(NO3)2 makes the Ni atoms migrate into the bulk of the supports, resulting in a diffused interfacial region. Alternatively, a cold plasma treatment was used to replace the thermal decomposition. Metal salts are quickly decomposed by glow discharge plasma treatment at room temperature, avoiding the thermal diffusion of Ni atoms. With the sequent R773-O473 treatment, a clean metal-support interface is produced. Moreover, the metal particles have optimal shapes with a larger surface. In photocatalysis, the clean metal-support interface is more favorable for the charge separation and transfer, and the increased metal surface provides more active sites. NiO/Ta2O5 and NiO/ZrO2 prepared with the plasma treatment exhibit higher activity for photocatalytic hydrogen generation from pure water and methanol solution, respectively. This work shows the potential of cold plasma treatment in the preparation of metal-loaded catalysts and nanostructured materials.     

New types of self-organizing interfacial alginate membranes

In this publication we describe a new self-association process, which leads to the formation of ultra-thin alginate layers at the interface between oil and water. The water phase contains a highly dilute solution of sodium alginate. These macromolecules are negatively charged and they are not surface active. The oil phase contains a small concentration of positively charged surfactants. At the interface between oil and water, the cationic surfactants tend to form complexes with the negatively charged alginate polyelectrolytes in the aqueous solutions. This leads to striking adsorption processes of the solved polysaccharide molecules at the oil-water interface. Upon the addition of calcium ions, a cross-linking process sets in and one obtains the thin viscoelastic membranes, which are anchored at the interface between oil and water. The thickness of these membranes is of the order of 0.2 mm. Similar structures can also be formed by solving positively charged Gemini surfactants in the oil phase. In this case, the cationic surfactant molecules induce the adsorption processes of alginate macromolecules, and they also act as cross-linking compounds. In a series of experiments, we measured the surface rheological properties of these ultra-thin alginate membranes. The results of these investigations point to the presence of electrostatically stabilized membranes. Special interest was given to the influence of the guluronate content of the alginates, which is important for the cross-linking mechanism according to the egg-box model. Finally, this article finishes with the discussion of the proposed building mechanisms of these membranes.     

Spectroscopic analysis of liquid/liquid interfaces in multiphase microflows

Microscopic quasi-elastic laser scattering (muQELS) spectroscopy has been developed for analysis of interfacial phenomena at laminar multiphase microflow in a microchannel. Transport phenomena of a metal chelate through a water/toluene interface were measured, and transient adsorption of the chelate in the initial step of the transport was measured. A water/methanol miscible interface was also measured, and the interfacial free energy of a miscible interface was determined for the first time. The muQELS is expected to be very effective not only for physicochemical investigations of transport and mixing, but also for elemental process analysis of heterogeneous reactions.     

Effects of an amphipathic alpha-helical peptide on lateral pressure and water penetration in phosphatidylcholine and monoolein mixed membranes

The physicochemical properties of mixed membranes of 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) and a nonlamellar-forming lipid, 1-monoolein (MO), and the effects of an amphipathic alpha-helical peptide, 18A (DWLKAFYDKVAEKLKEAF), on the membranes were investigated by fluorescence measurements and 31P NMR. The intramolecular excimer formation of dipyrenylphosphatidylcholines showed that the increased lateral pressure near the bilayer center by MO is reduced by the lamellar-cubic phase transition at an MO mole fraction of 0.7, while the lateral pressure near the polar-apolar interface increases even through the phase transition. The fluorescence lifetime of 2-(9-anthroyloxy)stearic acid revealed that water penetration into the interface region increases with the MO fraction. The insertion of the 18A peptide into the membrane interface region decreased both the lateral pressure near the interface and water penetration, and shifted the lamellar-cubic phase transition to a higher MO fraction. This suggests that 18A induces a positive curvature strain and lowers the lateral pressure and water penetration. Furthermore, the increase in the MO fraction in POPC/MO LUV promoted partitioning of 18A to the membranes. This preferential binding to the MO-containing membranes is presumably ascribed to the propensity of 18A to reduce the membrane strain.