Templating, porous matrix

A second method that has been described as a means to deal with the limited accessibility issue involves a copolymerization route. In this approach, the porous matrix is copolymerized with the template. Burleigh and coworkers, for example, described the preparation of imprinted polysilsesquioxanes for the recognition of metal ions.79 Polysilsesquioxanes are hybrid porous materials synthesized from bridged alkoxide precursors such as shown in Figure 20.2.80 In this example, the bridged silsesquioxane precursors were copolymerized with the metal ion complex in the presence of surfactant. Once the surfactant and metal ion were removed, a porous network was formed that showed a high affinity for the metal ion.79... 

Model templated structures can be assembled from Monte Carlo simulations of binary mixtures of matrix and template particles [55-57]. Upon removal of the template from the quenched equihbrated structure, a porous matrix is recovered with an enhanced accessible void volume for adsorption. GCMC simulation studies have established that the largest enhancement of adsorption uptake occurs when the template particles used to fashion the porous matrix are the same size as the adsorbate molecules for which the adsorbent is intended [55]. The enhanced adsorption capacity of the templated material relative to a nontemplated matrix is noticeable even for modest template particle densities [55]. 

A adsorption model for a templated porous material may be posed in terms of seven replica Ornstein-Zernicke (ROZ) integral equations [58-60] that relate the direct and total correlation functions, c, (r) and hij (r), respectively, of the matrix-adsorbate system... 

Fig. 1. Illustration of porous matrix formed via templating. The initial configuration of particles shown in a is equilibrated at a high temperature without a template and then quenched to yield the structure shown in b. The initial configuration in a has the same density of matrix particles (small circles) as in a, but template particles (large circles) are also present in this system. The template particles are removed from the quenched equilibrated matrix + template system (a") to yield the structure shown in b. It is clear to the eye that the structure in b possesses a more open pore structure with more available void volume than the structure in b [55]. (Reproduced with permission from S. Ramalingam. D. Maroudas. and E. S. Aydil. Atomistic simulation study of the interactions of Sill radicals with silicon surfaces. Journal of Applied Physics, 1999 86 2872-28SS. Copyright 1999, American Institute of Physics.)...

Monodisperse latex spheres of a controlled size can be arranged into three-dimensional arrays and are used as templates to prepare well-defined cavities and structures once the latex sphere template has been removed. These latex spheres are identical to one another in size and shape and are often prepared from colloidal clusters resulting from the aggregation of sol-gel colloids (Section 5.6). The spherical polymer clusters can be fabricated by the slow addition of an aqueous solution into a reservoir of hydrophobic silicone liquid, forming emulsion droplets. This produces a highly structured porous matrix with a well-defined structure upon polymerisation. The size of the droplets is controlled by the concentration of the aqueous latex, the speed at which the suspension is stirred and the ratio between the silicone liquid and latex. As the concentration of the latex spheres increases to its critical concentration, i.e. the concentration at which the colloidal spheres start to order themselves into a close-packed structure, the balls are filtered off and are dried, ready to be used as templates. 

Synthetic methods include the use of silanes bearing a chiral group for silylating the surface of the porous sol-gel silica, the use of such silanes as monomers or co-monomers in the polycondensation, the physical entrapment of chiral molecules, the imprinting of SG materials with chiral templates and the creation of chiral pores, and the induction of chirality in the matrix skeleton itself 48... 

Fig. 9 Schematic representation of three approaches to generate nanoporous and meso-porous materials with block copolymers, a Block copolymer micelle templating for mesoporous inorganic materials. Block copolymer micelles form a hexagonal array. Silicate species then occupy the spaces between the cylinders. The final removal of micelle template leaves hollow cylinders, b Block copolymer matrix for nanoporous materials. Block copolymers form hexagonal cylinder phase in bulk or thin film state. Subsequent crosslinking fixes the matrix hollow channels are generated by removing the minor phase, c Rod-coil block copolymer for microporous materials. Solution-cast micellar films consisted of multilayers of hexagonally ordered arrays of spherical holes. (Adapted from [33])...

It should be mentioned that alternative possibilities to prepare similar membranes include the use of a porous alumina membrane as matrix, with the titania nanotubes grown in the channels. Nanoporous alumina membranes are commercial products, also synthesized by anodic oxidation. The commercial Whatman Corporation anodic membrane has holes of about 20-nm diameter at the top of the membrane and about 200-nm diameter at the bottom of membrane. Within these pores Ti02 nanotubes fabricated by template synthesis and water vapour hydrolysis could be grown, but non-uniform membrane characteristics are obtained due to the non-uniform pores of the commercial alumina... 

In an alternative approach, MIP membranes can be obtained by generating molec-ularly imprinted sites in a non-specific matrix of a synthetic or natural polymer material during polymer solidification. The recognition cavities are formed by the fixation of a polymer conformation adopted upon interaction with the template molecule. Phase inversion methods have used either the evaporation of polymer solvent (dry phase separation) or the precipitation of the pre-synthesised polymer (wet phase inversion process). The major difficulties of this method lay both in the appropriate process conditions allowing the formation of porous materials and recognition sites and in the stability of these sites after template removal due to the lack of chemical cross-linking. 

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