Membrane interfaces, nanoparticle

The next question is which of the above-discussed scenarios is most Kkely to be found at the catalyst/hydrated membrane interface. It is generally accepted that the proton conductivity of the membrane depends on the characteristics of ionic clusters formed surrounding the polymer hydrophilic sites, both within the bulk polymeric structure and at the interface with the catalyst [79]. The ionic clusters located at the membrane/catalyst interface are the ones that close the circuit of this electrochemical system. That is, these ionic clusters act as bridges through which protons and other hydrophilic reactants and products may pass from the membrane to the catalyst surface and vice versa during fuel cell operation. To get some insights into the possible formation of ionic clusters, we have analyzed the conformation of a hydrated model nation membrane over Pt nanoparticles deposited on a carbon substrate via classical MD simulations [80] at various degrees of hydration. 

A new variation of interfacial polymerization was developed by Russell and Emrick in which functionalized nanoparticles or premade oligomers self-assemble at the interface of droplets, stabilizing them against coalescence. The functional groups are then crosslinked, forming permanent capsule shells around the droplets to make water-in-oil (Lin et al. 2003 Skaff et al. 2005) and oil-in-water (Breitenkamp and Emrick 2003 Glogowski et al. 2007) microcapsules with elastic membranes. 

Interfacial Polymerization Interfacial polymerization is a process whereby very thin films or membranes, on the order of nanometer thickness, are produced by reacting two monomers at the interface between two immiscible solutions [199], Nanoparticles [200] and aqueous core capsules with very thin membranes have been produced using this method for drug delivery applications. 

PEM fuel cells use a solid proton-conducting polymer as the electrolyte at 50-125 °C. The cathode catalysts are based on Pt alone, but because of the required tolerance to CO a combination of Pt and Ru is preferred for the anode [8]. For low-temperature (80 °C) polymer membrane fuel cells (PEMFC) colloidal Pt/Ru catalysts are currently under broad investigation. These have also been proposed for use in the direct methanol fuel cells (DMFC) or in PEMFC, which are fed with CO-contaminated hydrogen produced in on-board methanol reformers. The ultimate dispersion state of the metals is essential for CO-tolerant PEMFC, and truly alloyed Pt/Ru colloid particles of less than 2-nm size seem to fulfill these requirements [4a,b,d,8a,c,66j. Alternatively, bimetallic Pt/Ru PEM catalysts have been developed for the same purpose, where nonalloyed Pt nanoparticles <2nm and Ru particles <1 nm are dispersed on the carbon support [8c]. From the results it can be concluded that a Pt/Ru interface is essential for the CO tolerance of the catalyst regardless of whether the precious metals are alloyed. For the manufacture of DMFC catalysts, in... 

Besides the basic interest in the parameters governing particle interfacial assembly, there is also considerable technological potential associated with the structures formed at liquid-liquid interfaces. For example, nanoparticles could serve as building blocks for capsules and membranes with nanoscopic pores for filtering or encapsulation and for delivery purposes. 

Fig. 8 Rhodamine B dye (RhB, red solution) diffusing across a membrane of crosslinked nanoparticles (dotted line). The bold arrows point to the interface in each tube. The two right-hand images represent a time frame of about 15 min. Subsequent addition of water to the RhB/water droplet replaces the CdSe/toluene solution leading to a RhB/water-water interface separated by the nanoparticle membrane. Reprinted with permission from Journal of the American Chemical Society [47]. Copyright (2003) American Chemical Society...

The addition of superacid metal (IV) phosphonates is particularly suitable for the preparation of hybrid membranes. The proton conductivity in some cases reaches values even higher than 0.1S cm. The presence of nanoparticles of metal phosphonates in the electrode interface Nalion/Pt already improves the electrochemical characteristics of fuel cells in the temperature range 80-130°C [36]. 

The internal resistance of the polymer electrolyte membrane depends on the water content of the membrane. The water ionizes add moieties providing mobile protons, like protons in water [1-3]. Absorbed water also swells the membrane, which may affect the interface between the polymer electrolyte and the electrodes. Nafion, a Teflon/perfluorosulfonic acid copolymer, is the most popular polymer electrolyte because it is chemically robust to oxidation and strongly acidic. The electrodes are commonly Pt nanoparticles supported on a nanoporous carbon support and coated onto a microporous carbon cloth or paper. These structures provide high three-phase interface between the electrolyte/catalyst/reactant gas at both the anode and cathode. 

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