Hierarchical porous materials meso-/macroporous

Besides the biomaterials mentioned above, the cuttlebone [49] and chito-san [50] with unique structure have also been used as templates for the formation of hierarchically porous materials, which maintained the biological structure. Starch gel and dextran were also used to produce hierarchically sponge-like micro-, meso/macroporous monoliths of silicalite and meso/macro-porous metal oxides [51,52]. 

It is found that hierarchically meso/macroporous metal oxides can be synthesized even without the use of any external macrotemplate. In fact, great efforts have been made by scientists to promote development of hierarchically porous materials via the spontaneous self-formation phenomenon from metal alkoxides during the past decade. In this section, we will review the history of self-formation phenomenon to target hierarchically porous materials based on metal alkoxides. 

It is proved that the assisted conditions, such as surfactant molecules, pH values, organic solvent molecules, reaction temperature, and hydrothermal treatment, do not play a direct role in the creation of macroporosity. However, these assisted conditions can affect the resulting morphology of macroporous structure, meso-porosity, surface area, and so on. Furthermore, the resulting hierarchically porous materials have been apphed in many fields. Many efforts have been made on these parts of the subject, which will be described in detail in Section 32.2.3.4. 

It is proved that the surfactant molecules do not play a role in the creation of macroporosity via the self-formation phenomenon. However, some properties of the resulting hierarchically porous materials, such as the surface area, meso-porosity, morphology of the macroporous structure, degree of crystallinity of the nanoparticle, and stability of the porous structure, are tunable by using surfec-tant in the synthesis system. 

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]. 

Nb-based catalysts are among the investigated systems in total removal of -butanol due to the capacity of niobium to adopt variable oxidation states. Thus, Nb-doped hierarchically micro(meso) macroporous Ti02 (anatase phase) (Figure 17.10) synthesized via a self-formation procedure showed close performances with catalysts in which the same materials served as supports for noble metals [46]. The efficiency of these catalytic systems in the total oxidation of butan-l-ol was enhanced by the improved diffusion through the intrinsic macro-porous network. An effect of the niobium content was evidenced as welL... 

Based on the control of sol-gel deposition, hierarchically porous silica-based materials with a bimodal pore system (mesopores/large meso/macropores) and a diversity of dopant elements (Al, Ti, V, and Zr) could be prepared by using a one-pot surfactant-assisted procedure [78]. Another example includes the preparation of nonionically templated [Si]-MSU-X mesoporous silicas with bimodal pore systems by adding dilute electrolytes. 

In comparison with the materials synthesized in the presence of surfactants, the surface area of the hierarchically porous zirconium oxides obtained via the self-formation phenomenon is relatively lower. Furthermore, the synthesis temperature can affect the crystallinity of the final product [124,139]. Upon increase of the hydrothermal treatment temperature to 130 °C (generally reported to be 60-80 °C), thermally stable meso-macroporous zirconias with a nanocrystalline framework were prepared by using a mixture of amphiphilic block copolymer P123 and poly(ethylene oxide) surfactant Brij 56. 

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