Self-organized layering

Fig. 6 Schematics of the proposed layer self-organization of PFs in MCH. Reprinted with permission from [32]. (2007) by the American Chemical Society...

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

CavaUini M, Facchini M, Albonetti C, Biscarini F, Innocent M, Loglio F, Salvietti E, Pezzatini G, Forest ML (2007) Two-dimensional self-organization of CdS ultra thin films by confined electrochemical atomic layer epitaxy growth. J Phys Chem C Lett 111 1061-1064... 

Successive H-bond urea self-assembly of 4 and sol-gel transcription steps yield preferential conduction pathways within the hybrid membrane materials. Crystallographic, microscopic and transport data confirm the formation of self-organized molecular channels transcribed in solid dense thin-layer membranes. The ionic transport across the organized domains illustrates the power of the supramolecular approach for the design of continual hydrophilic transport devices in hybrid membrane materials by self-organization (Figure 10.8) [42-44]. 

At the mesoscopic scale, interactions between molecular components in membranes and catalyst layers control the self-organization into nanophase-segregated media, structural correlations, and adhesion properties of phase domains. Such complex processes can be studied by various theoretical tools and simulation techniques (e.g., by coarse-grained molecular dynamics simulations). Complex morphologies of the emerging media can be related to effective physicochemical properties that characterize transport and reaction at the macroscopic scale, using concepts from the theory of random heterogeneous media and percolation theory. 

For typical catalyst layers impregnated with ionomer, sizes of hydrated ionomer domains that form during self-organization are of the order of 10 nm. The random distribution and tortuosity of ionomer domains and pores in catalyst layers require more complex approaches to account properly for bulk water transport and interfacial vaporization exchange. A useful approach for studying vaporization exchange in catalyst layers could be to exploit the analogy to electrical random resistor networks of... 

This section provides a comprehensive overview of recent efforts in physical theory, molecular modeling, and performance modeling of CLs in PEFCs. Our major focus will be on state-of-the-art CLs that contain Pt nanoparticle electrocatalysts, a porous carbonaceous substrate, and an embedded network of interconnected ionomer domains as the main constituents. The section starts with a general discussion of structure and processes in catalyst layers and how they transpire in the evaluation of performance. Thereafter, aspects related to self-organization phenomena in catalyst layer inks during fabrication will be discussed. These phenomena determine the effective properties for transport and electrocatalytic activity. Finally, physical models of catalyst layer operation will be reviewed that relate structure, processes, and operating conditions to performance. 

Mesoscale Simulations of Self-Organization in Catalyst Layers... 

Electrode surfaces can be modified by redox polyelectrolytes via a sol-gel process, yielding random redox hydrogels or by layer-by-layer self-assembly of different redox and nonredox polyelectrolytes by alternate electrostatic adsorption from solutions containing the polyelectrolytes to produce highly organized redox-active ultrathin multilayers. 

While for LB-layers, the molecules have to be organized by means of compression prior to deposition of the monolayer at the air-water interface, the self-organization process into SAMs follows similar pathways by itself This requires sufli-... 

These monolayers form themselves spontaneously by adsorption of suitable components from a diluted solution directly onto a surface. The formation of ordered and orientated monomolecular layers by spontaneous adsorption from a diluted solution is called self-assembling, the respective layers are called self-assembled monolayers (SAM) or self-organized monolayers. In the first part of this review, the coating of surfaces with functionalized SAMs will be examined. After that, some aspects of the attachment of the biomolecules onto these SAM-modified surfaces will be discussed. 

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