Macroporous materials

Ordered macroporous materials with pore sizes of more than 50 nm appeared in the late 1990s with the development of a method using colloidal crystals of monodisperse spheres as a new template.The walls of macroporous materials are larger than those of mesoporous materials, and a number of well-ordered macroporous crystalline transition metal oxides have been prepared.The preparation method 

In order to produce a three-dimensionally ordered macroporous structure, the metal precursor solution should fulfil the following criteria (1) Sufficient metal should be present in the voids to form a macroporous wall, and the metal concentration should therefore be high. (2) Reactivity of the metal precursor should be mild so that it can infiltrate the voids. If the metal precursor reacts with a functional group on the surface of the template or moisture in the air before it infiltrates the voids, an ordered porous structure cannot be obtained. (3) The metal precursor should be solidified in the voids before the template is removed and the produced 

ORDERED POROUS CRYSTALLINE TRANSITION METAL OXIDES 

Inverse opal structures have been classified into three structures, the so-called residual volume structure , shell structure and skeleton structure . The residual volume structure is a perfect inverse opal structure, which can be produced if the whole space among the opal spheres is completely filled by the product materials. If the space is incompletely filled, the surface of the sphere template is covered by the product materials, and a shell structure is generated. Most amorphous compounds tend to form a shell structure. On the other hand, crystalline compounds tend to form a skeleton structure. 

Tetrah dn void Tetfahedral vertex 8-coordinated square prism vertex 

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Pore volumes are determined by forcing N2 (for micro- and mesoporous materials) or Hg (macroporous materials) under pressure into the pores. The quantity of N2 or Hg entering the catalyst is directly related to the pressure and the radius of the pores. The Kelvin equation describes this ... 

The tube has been first characterised just after the hydrothermal treatment step (i.e. before the calcination) The N2 isotherm is typical of macroporous materials (Figure 3, curve 1) and the tube is gas-tight. 

Compared with microporous and mesoporous materials, the larger, interconnected voids in macroporous materials potentially provide easier molecule transportation through the materials. This is of particular interest for the transport of large biomolecules (e.g., proteins and cells). The pore sizes in macroporous materials are usually from tens to hundreds of nanometers, and the pores are typically... 

Macroporous materials with various shapes such as particles, tubes, rods, fibers, membranes, and 3DOM have been designed to cater for different applications. Three... 

Macroporous substrates with interconnected voids can be used as platforms for biomacromolecule separation and enzyme immobilization. These assemblies are likely to find application in biocatalysis and bioassays. The inorganic framework can provide a robust substrate, while their large and abundant pores allow the transportation of biomolecules. The availability of various morphologies for macroporous materials provides another level of control over the function of the hybrids. 

Imhof, A. and Pine D.J. (1997) Ordered macroporous materials by emulsion templating. Nature, 389, 948-951. 

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. 

The material properties of PS offer new ways of making electronic devices. For the manufacture of cold cathodes, for example, oxidized microporous polysilicon has been found to be a promising material. The application of basic semiconductor processing steps such as doping, oxidation and CVD to a macroporous material enable us to fabricate silicon-based capacitors of high specific capacitance. Both devices will be discussed below. 

Terms such as symmetric and asymmetric, as well as microporous, meso-porous and macroporous materials will be introduced. Symmetric membranes are systems with a homogeneous structure throughout the membrane. Examples can be found in capillary glass membranes or anodized alumina membranes. Asymmetric membranes have a gradual change in structure throughout the membrane. In most cases these are composite membranes... 

In gas separation applications, polymeric hollow fibers (diameter X 100 fim) are used (e.g. PAN) with a dense skin. In the skin the micropores develop during pyrolyzation. This is also the case in the macroporous material but is not of great importance from gas permeability considerations. Depending on the pyrolysis temperature, the carbon membrane top layer (skin) may or may not be permeable for small molecules. Such a membrane system is activated by oxidation at temperatures of 400-450 C. The process parameters in this step determine the suitability of the asymmetric carbon membrane in a given application (Table 2.8). 

With hysteresis loops of Type HI, the two branches are almost vertical and nearly parallel. Such loops are often associated with porous materials which are known to have very narrow pore size distributions or agglomerates of approximately uniform spheres in fairly regular array. More common are loops of Type H2, where the pore size distribution and shape are not well defined. This is attributed to the difference in adsorption and desorption mechanisms occurring in ink-bottle pores, and network effects. The Type H3 hysteresis loop does not show any limiting adsorption at high relative pressures and is observed in aggregates and macroporous materials. Loops of Type H4 are often associated with narrow... 

As discussed in Section 1.4.2.1, the critical condensation pressure in mesopores as a function of pore radius is described by the Kelvin equation. Capillary condensation always follows after multilayer adsorption, and is therefore responsible for the second upwards trend in the S-shaped Type II or IV isotherms (Fig. 1.14). If it can be completed, i.e. all pores are filled below a relative pressure of 1, the isotherm reaches a plateau as in Type IV (mesoporous polymer support). Incomplete filling occurs with macroporous materials containing even larger pores, resulting in a Type II isotherm (macroporous polymer support), usually accompanied by a H3 hysteresis loop. Thus, the upper limit of pore size where capillary condensation can occur is determined by the vapor pressure of the adsorptive. Above this pressure, complete bulk condensation would occur. Pores greater than about 50-100 nm in diameter (macropores) cannot be measured by nitrogen adsorption. 

The first monolithic materials initially emerged in the 1960s, but it is during the last 20 years that monoliths have been intensively developed in a variety of fields and particularly in analytical chemistry for separation techniques. Nowadays, these macroporous materials are widely used and have found numerous applications in different chromatographic modes such as liquid chromatography (LC) or CEC, as indicated by several reviews [150, 151]. Less commonly, monolithic materials can also be applied, for example, to solid-phase extraction, combinatorial synthesis and for enzyme immobilisation. 

Figure 7.42 Types of gas sorption isotherm - microporous solids are characterised by a type I isotherm. Type II corresponds to macroporous materials with point B being the point at which monolayer coverage is complete. Type III is similar to type II but with adsorbate-adsorbate interactions playing an important role. Type IV corresponds to mesoporous industrial materials with the hysteresis arising from capillary condensation. The limiting adsorption at high P/P0 is a characteristic feature. Type V is uncommon. It is related to type III with weak adsorbent-adsorbate interactions. Type VI represents multilayer adsorption onto a uniform, non-porous surface with each step size representing the layer capacity (reproduced by permission of IUPAC).

PGC sorbents have even more highly homogeneous hydrophobic surfaces than GCB sorbents. PGCs are macroporous materials composed of flat, two-dimensional layers of carbon atoms arranged in graphitic structure. The flat, homogeneous surface of PGC arranged in layers of carbons with delocalized n electrons makes it uniquely capable of selective fractionation between planar and nonplanar analytes such as the polychlorinated biphenyls [92,94,95],... 

According to the IUPAC definition, porous materials ate divided into three different classes, depending on their pore sizes. Mesoporous materials are described as materials whose pore diameters lie in the range between 2 and 50 nm. Solids with a pore diameter below 2 nm or above 50 nm belong to the class of micro- and macroporous materials, respectively. 

Silica is one of the most abundant chemical substances on earth. It can be both crystalline or amorphous. The crystalline forms of silica are quartz, cristobalite, and tridymite [51,52]. The amorphous forms, which are normally porous [149] are precipitated silica, silica gel, colloidal silica sols, and pyrogenic silica [150-156], According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous materials can be classified as follows microporous materials are those with pore diameters from 3 to 20 A mesoporous materials are those that have pore diameters between 20 and 500 A and macroporous materials are those with pores bigger than 500 A [149],... 

The fractal concept is based on the assumption of reproduction of the general elements of structure of porous materials at all levels—from microscopic to macroscopic ones. This assumption is valid for numerous macroporous materials, while it is too difficult to check its validity for microporous ones. However, based on general thermodynamic considerations, one may assume that fractal concepts also apply to some of microporous materials. As it is shown below, the main condition of the applicability of the fractal approach to microporous materials consists in their homogeneity. However, one has to take into account that this strict analysis does not allow the assumption of homogeneity of any microporous system, not least, because the subsystem micropore-wall of micropore is obviously heterogeneous. Therefore, the fractal concept is probably not applicable to very narrow micropores (ultramicropores, according to Dubinin s classification). 

L C dc Menorval, A Julbe, H Jobic, J-A Dalmon, C Guizard, MRS Proc Series "Microporous and Macroporous Materials , 1996, 431, 159 164... 

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