Texture mesopore

Two different synthesis paths for making mesoporous silica possessing both framework-eonfined and textural mesoporosity has been presented. In the first synthesis path, adjustment of the reaction pH resulted in a gel-structure consisting of smaller particles and larger fraction of textural mesopores compared to ordinary MCM-41 materials. The lowest reaction pH resulted in the smallest particle size and highest amount of textural mesopores. In the second synthesis path, TEOS was allowed to prehydrolyze for different periods of time before surfactant addition. Longer prehydrolysis times resulted in a higher fraction of textural porosity and thicker pore walls. 

Most of the microporous and mesoporous compounds require the use of structure-directing molecules under hydro(solvo)thermal conditions [14, 15, 171, 172]. A serious handicap is the application of high-temperature calcination to develop their porosity. It usually results in inferior textural and acidic properties, and even full structural collapse occurs in the case of open frameworks, (proto) zeolites containing small-crystalline domains, and mesostructures. These materials can show very interesting properties if their structure could be fully maintained. A principal question is, is there any alternative to calcination. There is a manifested interest to find alternatives to calcination to show the potential of new structures. 

The BET surface area values are also reported with the distribution of porosity between microporosity (pore diameter <1.8 nm) deduced from N2 adsorption isotherms (t-curves) and mesoporosity (pore diameter > 1.8 nm). The following trend is observed for high atomic M/HPA ratio used for the precipitation, the precipitates exhibited high surface area mainly due to microporosity. However, depending on the nature of the coxmter cation and also of the previous ratio values, the textural characteristics were not similar. In particular, it is interesting to note the presence of mesopores for (NH4)2.4P, CS2.9P, CS2.7P and Cs2.4Si samples. 

The most active samples for n-C4 isomerization, (NH4)2.4P and Csi.gP, showed opposite reactivities in liquid alkylation. The first one gave rise to a high production of TMP while the second one was only initially slightly active. The main difference between these two samples concerned their porosity (NH4)2.4P was mesoporous while Csi.gP was mainly microporous. Then, one may suggest that the presence of mesoporosity is essential for the accessibility of the reactants to the acid sites and the desorption of the products. As a consequence the catalytic activity seems more governed by the textural features than by the acidity. As a general trend, the samples which were, at the same time, active and stable for the alkylation reaction, exhibited a mesoporosity equivalent to about 40 m. g-i. 

G.J. de A. Soler-Illia, C. Sanchez, B. Lebeau, J. Patari, Chemical strategies to design textured materials from microporous and mesoporous oxides to nanonetworks and hierarchical structures. Chem. Rev. 102 (2002) 4093. 

In conclusion, although the porous texture of these materials is of limited interest for getting high capacitance values, it allows to clearly demonstrate the beneficial effect of mesopores on the capacitor performance. 

Varying KOH ratio in the mixture is a very effective way of controlling porosity development in resultant activated carbons. The trend in the pore volume and BET surface area increase seems to be similar for various precursors (Fig. la). It is interesting to note, however, a sharp widening of pores, resulting in clearly mesoporous texture, when a large excess of KOH is used in reaction with coal semi-coke (Fig. lb). Increase in the reaction temperature within 600-900°C results in a strong development... 

Structural and textural characterisation of pure SBA-15 and hybrid GFP/SBA-15 Pure SBA-15 and GFP/SBA-15 hybrid were characterised by X-ray powder diffraction, HRTEM and volumetric analysis. Calcined SBA-15 (Fig. 1, curve A) show the typical XRD pattern of an ordered hexagonal network of mesopores with (10), (11) and (20) reflections. The presence of well resolved (11) and (20) peaks indicate that the calcined material used for the preparation of the hybrid materials have a long-range order. The hexagonal XRD pattern was still clearly observed in the hybrid material (GFP/SBA-15), as all the three main reflections were found (Fig. 1, curve B), indicating that the sonication and the GFP physical adsorption does not affect the framework integrity of the material. 

Figure 1 shows that the catalysts maintain their mesoporous structure with type IV isotherm. It can be observed a reduction in surface area, pore volume and pore diameter and slight increase in textural porosity as the concentration of aluminum increases (Table 1), due to the increase in the wall thickness in the mesoporous material as we have found previously [3],... 

At 9 hours of immersion, instead, isotherms do not show the pore filling associated with mesopores, which in turn appears again between 25 and 26 hours. After 28 hours of soaking, no mesopore filling is observed (figure 3). The DFT pore size distributions also confirm the presence of mesopores (around 2.2 nm) only at 2 hours of immersion and between 25 and 26 hours. The peak at around 5 nm is probably due to the textural interparticles porosity (figure 3 inset). 

Tabakova, Idakiev, Andreeva, and coworkers—Zr a highly efficient support for supported, well-dispersed Au textural effects and mesoporous support preparation. 

Pores are found in many solids and the term porosity is often used quite arbitrarily to describe many different properties of such materials. Occasionally, it is used to indicate the mere presence of pores in a material, sometimes as a measure for the size of the pores, and often as a measure for the amount of pores present in a material. The latter is closest to its physical definition. The porosity of a material is defined as the ratio between the pore volume of a particle and its total volume (pore volume + volume of solid) [1]. A certain porosity is a common feature of most heterogeneous catalysts. The pores are either formed by voids between small aggregated particles (textural porosity) or they are intrinsic structural features of the materials (structural porosity). According to the IUPAC notation, porous materials are classified with respect to their sizes into three groups microporous, mesoporous, and macroporous materials [2], Microporous materials have pores with diameters < 2 nm, mesoporous materials have pore diameters between 2 and 50 nm, and macroporous materials have pore diameters > 50 nm. Nowadays, some authors use the term nanoporosity which, however, has no clear definition but is typically used in combination with nanotechnology and nanochemistry for materials with pore sizes in the nanometer range, i.e., 0.1 to 100 nm. Nanoporous could thus mean everything from microporous to macroporous. 

Textural mesoporosity is a feature that is quite frequently found in materials consisting of particles with sizes on the nanometer scale. For such materials, the voids in between the particles form a quasi-pore system. The dimensions of the voids are in the nanometer range. However, the particles themselves are typically dense bodies without an intrinsic porosity. This type of material is quite frequently found in catalysis, e.g., oxidic catalyst supports, but will not be dealt with in the present chapter. Here, we will learn that some materials possess a structural porosity with pore sizes in the mesopore range (2 to 50 nm). The pore sizes of these materials are tunable and the pore size distribution of a given material is typically uniform and very narrow. The dimensions of the pores and the easy control of their pore sizes make these materials very promising candidates for catalytic applications. The present chapter will describe these rather novel classes of mesoporous silica and carbon materials, and discuss their structural and catalytic properties. 

Figure 9.1 Examples of texture of the materials formed on a short range from amorphous Si02 (a) silica gel (b) hydrothermally treated silica gel (c) porous glass (d) mesoporous mesophases type of MCM-41 and (e) opal.

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