On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells

Organic–inorganic hybrid materials do not represent only a creative alternative to design new materials and compounds for academic research, but their improved or unusual features allow the development of innovative industrial applications. Nowadays, most of the hybrid materials that have already entered the market are synthesised and processed by using conventional soft chemistry based routes developed in the eighties. These processes are based on: a) the copolymerisation of functional organosilanes, macromonomers, and metal alkoxides, b) the encapsulation of organic components within sol–gel derived silica or metallic oxides, c) the organic functionalisation of nanofillers, nanoclays or other compounds with lamellar structures, etc. The chemical strategies (self-assembly, nanobuilding block approaches, hybrid MOF (Metal Organic Frameworks), integrative synthesis, coupled processes, bio-inspired strategies, etc.) offered nowadays by academic research allow, through an intelligent tuned coding, the development of a new vectorial chemistry, able to direct the assembling of a large variety of structurally well defined nano-objects into complex hybrid architectures hierarchically organised in terms of structure and functions. Looking to the future, there is no doubt that these new generations of hybrid materials, born from the very fruitful activities in this research field, will open a land of promising applications in many areas: optics, electronics, ionics, mechanics, energy, environment, biology, medicine for example as membranes and separation devices, functional smart coatings, fuel and solar cells, catalysts, sensors, etc.

Applications of hybrid organic–inorganic nanocomposites

Surface modification of inorganic nanoparticles for development of organic–inorganic nanocomposites—A review

Leu-M

The state-of-the-art of polymer electrolyte membrane fuel cell (PEMFC) technology is based on perfluorosulfonic acid (PFSA) polymer membranes operating at a typical temperature of 80 °C. Some of the key issues and shortcomings of the PFSA-based PEMFC technology are briefly discussed. These include water management, CO poisoning, hydrogen, reformate and methanol as fuels, cooling, and heat recovery. As a means to solve these shortcomings, high-temperature polymer electrolyte membranes for operation above 100 °C are under active development. This treatise is devoted to a review of the area encompassing modified PFSA membranes, alternative sulfonated polymer and their composite membranes, and acid−base complex membranes. PFSA membranes have been modified by swelling with nonvolatile solvents and preparing composites with hydrophilic oxides and solid proton conductors. DMFC and H2/O2(air) cells based on modified PFSA membranes have been successfully operated at temperatures up to 120 °C under ambient pressure...

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Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C

Organic–inorganic membranes prepared from polyether diamine and epoxy silane

In this study, polysiloxane networks prepared by hydrosilylation or hydrolysis/condensation reactions were considered to be potential precursors for Si–C–O systems. Different precursors had different pyrolytic properties, which was essentially due to their molecular architecture. The kinetics parameters, such as the activation energy, E (kJ/mol) involved in the polymer-to-ceramic conversion, were investigated by thermogravimetry using a multiple heating rate kinetic method. The relationships between the molecular architecture and the precursor composition were compared to that of a linear poly(dimethylsiloxane) precursor. Solid-state 29 Si nuclear magnetic resonance, infrared spectroscopies, density measurements, and X-ray diffraction measurements were made on the final samples. These products were typically amorphous, with a molecular structure formed by a random distribution of different silicon sites and variable amounts of free carbon residue.

Investigation on kinetics of thermal decomposition in polysiloxane networks used as precursors of silicon oxycarbide glasses

The research herewith aims at obtaining cellulose nanocrystals with a reduced hydrophilic surface character using a silane with isocyanate groups (isocyanatepropyltriethoxysilane), which are very reactive to hydroxyl groups and thus, are readily able to react with the low quantity of free hydroxyl groups present in the cellulose nanocrystal surfaces, therefore, promoting surface modification. Cellulose nanocrystals were obtained by hydrochloric acid hydrolysis of cotton fiber and were characterized by X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and solid state 29Si nuclear magnetic resonance (NMR) and their morphologies were investigated by scanning and transmission electron microscopy techniques. The nanocrystals presented a needle-like geometry with a 10 nm approximate diameter and a 166 nm average length. FTIR, 29Si NMR and silicon mapping images showed that nanocrystal surface chemical modification was successfully achieved. Also, the results confirm that the chemical modification occurred mainly at the nanocrystal surface, keeping the morphological integrity of the nanocrystals. The applied methodology for surface modification of the cellulose nanocrystals provided nanofillers with more appropriate surface characteristics that allow the dispersion in polymeric matrices and the adhesion at filler-matrix interface to be obtained. This may result in a better performance of these nanocrystals as reinforcing agents of hydrophobic polymer matrices.

Surface modification of cotton nanocrystals with a silane agent

Rubbers resulting from the hydrosilylation reaction between poly(methylsiloxane), and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcycletetrasiloxane, have been pyrolyzed to silicon oxycarbide ceramics, with ceramic yield varying as a function of the mixture composition. The rubber–ceramic conversion process was investigated by 13C and 29Si nuclear magnetic resonance and infrared spectroscopies, thermogravimetric analysis and density measurements. The composition of the ceramic products was determined by elemental and X-ray fluorescence analyses and their structural characterization was done by 29Si solid-state magic angle spinning nuclear magnetic resonance. The structure of the ceramic products is, actually, a mixture of SiO4, SiCO3, SiC2O2, SiC3O, SiC4 sites randomly distributed in the bulk. The C–C/SiCxO4−x composites were prepared by infiltration of the siloxane mixture into the bidirectionally reinforced carbon plate. The composites obtained after pyrolysis showed an improved resistance to oxidation in relation to untreated carbon plates.

Inez Valéria Pagotto Yoshida

Papers

Organic–inorganic membranes prepared from polyether diamine and epoxy silane

Investigation on kinetics of thermal decomposition in polysiloxane networks used as precursors of silicon oxycarbide glasses

Surface modification of cotton nanocrystals with a silane agent

Silicon oxycarbide glasses from silicone networks

Hybrids of perfluorosulfonic acid ionomer and silicon oxide by sol-gel reaction from solution: Morphology and thermal analysis