Hierarchically structured porous materials approach

The materials which have been mentioned here so far are predominantly shaped in planar films of hierarchical order. However, the synthesis of hierarchically structured particles is also highly desirable, as they might be further processed and used for the preparation of composite porous materials. Wu et al. showed the synthesis of raspberry-like hollow silica spheres with a hierarchically structured, porous shell, using individual PS particles as sacrificial template [134]. In another intriguing approach by Li et al. [135], mesoporous cubes and near-spherical particles (Fig. 10) were formed by controlled disassembly of a hierarchically structured colloidal crystal, which itself was fabricated via PMMA latex and nonionic surfactant templating. The two different particle types concurrently generated by this method derive from the shape of the octahedral and tetrahedral voids, which are present in the template crystal with fee lattice symmetry. 

The given discussion shows that rather universal and simple classification of porous materials equivalent to classification of crystals is absent. However, one can consider a system of interrelating classifications that take into account order, morphology and sizes at different hierarchical levels, degrees of integrity, structure, heterogeneity of a various type, etc. Such a systematic approach can be used as well for adequate modeling of various hierarchical levels of a porous material structure. 

Several approaches towards the synthesis of hierarchical meso- and macro-porous materials have been described. For instance, a mixture that comprised a block co-polymer and polymer latex spheres was utilized to obtain large pore silicas with a bimodal pore size distribution [84]. Rather than pre-organizing latex spheres into an ordered structure they were instead mixed with block-copolymer precursor sols and the resulting structures were disordered. A similar approach that utilized a latex colloidal crystal template was used to assemble a macroporous crystal with amesoporous silica framework [67]. 

Hierarchical porous materials are sohds that are ordered at different length scales. Materials with multiple porosities are of high interest for apphcations in catalysis and separation, because these apphcations can take advantages of different pore structures. For example, microporous mesoporous composites have shown superior catalytic activities by the combination of strong acidity from zeohtes with high reactant or product mobility due to large uniform mesopores. Several approaches have been reported on the design and synthesis of hierarchical porous materials, as discussed below. 

Sen T, Tiddy GJT, Casci JL, Anderson MW (2004) Synthesis and characterization of hierarchically ordered porous silica materials. Chem Mater 16 2044 Deng Y, Liu C, Yu T, Liu F, Zhang F, Wan Y, Zhang L, Wang C, Tu B, Webley PA, Wang H, Zhao D (2007) Facile synthesis of hierarchically porous carbons from dual colloidal crystal/block copolymer template approach. Chem Mater 19 3271 Luo Q, Li L, Yang B, Zhao D (2000) Three-dimensional ordered macroporous structures with mesoporous silica walls. Chem Lett 29 378... 

Route C mobilizes routes A and B to combine complex precursor systems (aerosol cocktails) in different ratios and yield multifunctional materials with hierarchically structured porosity [18-21]. For instance, latex beads can be combined with a diluted sol-gel surfactant dispersion that contains small inorganic nanoparticles of metallic oxides, metals, and so on. This approach then leack by EISA to micrometer-sized porous spheres with an independent control of dimensions at four levels of size. 

In view of catalytic potential applications, there is a need for a convenient means of characterization of the porosity of new catalyst materials in order to quickly target the potential industrial catalytic applications of the studied catalysts. The use of model test reactions is a characterization tool of first choice, since this method has been very successful with zeolites where it precisely reflects shape-selectivity effects imposed by the porous structure of tested materials. Adsorption of probe molecules is another attractive approach. Both types of approaches will be presented in this work. The methodology developed in this work on zeolites Beta, USY and silica-alumina may be appropriate for determination of accessible mesoporosity in other types of dealuminated zeolites as well as in hierarchical materials presenting combinations of various types of pores. 

The book collects contributions in the field of characterization of materials also, and these are reported in various chapters. In addition to this, a particular chapter is dedicated to interesting new calorimetric approaches to the study of soft-matter three-dimensional organization intended to demonstrate methods able to make a contribution to our understanding of hierarchical porous structures in which matter and void are organized in regular and controlled patterns. 

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