Porosity mesopores

Fig. 2 In vitro biodegradation of an 83 % porosity mesoporous silicon membrane...

Fig. 4 In vivo biodegradation of a 30 % porosity mesoporous silicon layer in the subeutaneous site of the guinea pig. Plan view HREM images of porosified silicon disc surfaces (a) prior to implantation, (b) after 4 weeks in vivo, and (c) after 12 weeks in vivo...

High porosity mesoporous silicon is a complex nanostrueture whose optoeleetronie properties and morphology have received intense continuous study over the last 25 years, following the publieation of its dramatic luminescence properties in 1990. There are a series of reviews that historieally ehart progress in understanding and exploitation of its lumineseent, optieal, and eleetrieal properties (Fauchet et al. 1995 Hamilton 1995 Cullis et al. 1997 Bisi et al. 2000 Boarino et al. 2009 Torres-Costa and Martin-Palma 2010 Chao 2011 Golovan and Timoshenko 2013 Paeholski 2013). 

High porosity mesoporous silicon is a fascinating nanostructure with low dimensionality that has a number of novel properties. It also can possess ehemieal instability, meehanieal weakness, and low thermal transport. These latter properties can necessitate very careful characterization in order to avoid data misinterpretation and unwanted ehanges to the nanostractured material. 

Zhang L, Coffer JL, Gnade BE, DaXue X, Pinizzotto RF (1995) Effects of local ambient atmosphere on the stability of electroluminescent porous silicon diodes. J Appl Phys 77 5936 Zimin SP (2000) Classification of electrical properties of porous silicon. Semiconductors 34 353 Zimin SP (2006) Hopping conductivity in low-porosity mesoporous silicon formed on p -Si -B. Semiconductors 40(11) 1350... 

Volumetric shrinkage %) Dry gel porosity (%) Mesopore volume (cm g- ) Macropore volume (cm g" )... 

We showed that these mesoporous silica materials, with variable pore sizes and susceptible surface areas for functionalization, can be utilized as good separation devices and immobilization for biomolecules, where the ones are sequestered and released depending on their size and charge, within the channels. Mesoporous silica with large-pore-size stmctures, are best suited for this purpose, since more molecules can be immobilized and the large porosity of the materials provide better access for the substrates to the immobilized molecules. The mechanism of bimolecular adsorption in the mesopore channels was suggested to be ionic interaction. On the first stage on the way of creation of chemical sensors on the basis of functionalized mesoporous silica materials for selective determination of herbicide in an environment was conducted research of sorption activity number of such materials in relation to 2,4-D. 

At this point we should also recall another application of the already mentioned Bernal model of amorphous surface. Namely, Cascarini de Torre and Bottani [106] have used it to generate a mesoporous amorphous carbonaceous surface, with the help of computer simulation and for further application to the computer simulation study of adsorption. They have added a new component to the usual Bernal model by introducing the possibility of the deletion of atoms, or rather groups of atoms, from the surface according to some rules. Depending on the particular choice of those rules, surfaces of different porosity and structure can be obtained. In particular, they have shown examples of mono- as well as pohdispersed porous surfaces... 

Figure 2.2 Classification of different types of porous materials, (a) A purely microporous zeolite is considered as a non-hierarchical system according to the single level of porosity, (b) Fragmentation of the zeolite into nanocrystals engenders a network of mesopores constituting the intercrystalline space, leading to an interconnected hierarchical system. Intraconnected...

The previous sections have shown that desihcation of ZSM-5 zeohtes results in combined micro- and mesoporous materials with a high degree of tunable porosity and fuUy preserved Bronsted acidic properties. In contrast, dealumination hardly induces any mesoporosityin ZSM-5 zeolites, due to the relatively low concentration of framework aluminum that can be extracted, but obviously impacts on the acidic properties. Combination of both treatments enables an independent tailoring of the porous and acidic properties providing a refined flexibility in zeolite catalyst design. Indeed, desihcation followed by a steam treatment to induce dealumination creates mesoporous zeolites with extra-framework aluminum species providing Lewis acidic functions [56]. 

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. 

Kokufuta, E Jinbo, E, A Hydrogel Capable of Facilitating Polymer Diffusion through the Gel Porosity and Its Application in Enzyme Immobilization, Macromolecules 25, 3549, 1992. Kresge, CT Leonowicz, ME Roth, WJ Vartuli, JC Beck, JS, Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Template Mechanism, Nature 359, 710, 1992. 

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. 

Bhattacharya and Gedanken [11] have reported a template-free sonochemical route to synthesize hexagonal-shaped ZnO nanocrystals (6.3 1.2 nm) with a combined micro and mesoporous structure (Fig. 8.1) under Ar gas atmosphere. The higher porosity with Ar gas has been attributed to the higher average specific heat ratio of the Ar which leads to higher bubble collapse temperatures. With an intense bubble collapse temperature, more disorder is created in the product due to the incompleteness of the surface structure that led to greater porosity. Importance of gas atmosphere has been noted when the same process was carried out in the presence of air which results in the formation of ZnO without any porosity. 

Pal U, Kim CW, Jadhav NA, Kang YS (2009) Ultrasound-assisted synthesis of mesoporous ZnO nanostructures of different porosities. J Phys Chem C 113(33) 14676-14680... 

A rather limited range of mesopores in terms of size and volume were observed in the skeletons of polymer monoliths. The porosity of the polymer monolith seems to be lower than that of silica monolith. The total porosity of these monoliths is in the range of 0.61-0.73, whereas interstitial (through-pore) porosity and mesopore porosity are 0.28-0.70 and 0.03-0.24, respectively. In the case of poly(butyl methacrylate-co-ethylene dimethacrylate), the observed porosity is around 0.61-0.71, resulting in permeability 0.15-8.43 x 10 14 m2, whereas the observed porosity of silica monoliths prepared in a capillary is 0.86-0.96 and the permeability is 7-120 x 10 14 m2. Higher permeability will be advantageous for 2D applications, as mentioned later. 

High porosity carbons ranging from typically microporous solids of narrow pore size distribution to materials with over 30% of mesopore contribution were produced by the treatment of various polymeric-type (coal) and carbonaceous (mesophase, semi-cokes, commercial active carbon) precursors with an excess of KOH. The effects related to parent material nature, KOH/precursor ratio and reaction temperature and time on the porosity characteristics and surface chemistry is described. The results are discussed in terms of suitability of produced carbons as an electrode material in electric double-layer capacitors. 

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... 

A sharp increase in bum-off above 800°C is associated with a limited enhancement of porosity. Pore widening (reflected by a slight but continuous increase in the mesopore ratio and micropore width), seems to be most characteristic effect of increasing reaction temperature (Fig. 2b). 

The soak time seems to have a less pronounced effect on porosity development during treatment at 800°C. A considerable porosity (VT = 1.04 cm3/g and Sbet = 2570 m2/g) is created within the early period of reaction and a limited change of the parameters occurs with prolonged heating to 3 h (Fig. 3a). Again, the widening of pores, as evidenced by an increase of both the mesopore ratio and the micropore width, is the most noticeable result of extended reaction time (Fig. 3b). 

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],... 

Acidic micro- and mesoporous materials, and in particular USY type zeolites, are widely used in petroleum refinery and petrochemical industry. Dealumination treatment of Y type zeolites referred to as ultrastabilisation is carried out to tune acidity, porosity and stability of these materials [1]. Dealumination by high temperature treatment in presence of steam creates a secondary mesoporous network inside individual zeolite crystals. In view of catalytic applications, it is essential to characterize those mesopores and to distinguish mesopores connected to the external surface of the zeolite crystal from mesopores present as cavities accessible via micropores only [2]. Externally accessible mesopores increase catalytic effectiveness by lifting diffusion limitation and facilitating desorption of reaction products [3], The aim of this paper is to characterize those mesopores by means of catalytic test reaction and liquid phase breakthrough experiments. 

The studied solids exhibit great differences in term of porosity (purely microporous, micro-mesoporous and mesoporous). As it is well known, mesoporosity of USY (CBV series) increases as the aluminum content decreases. Large part of mesoporosity is in the range 2-3.6 nm according to the difference between mesoporous volume obtained by N2 or Hg measurements. Pore size estimation gave similar results whatever the technique. 

For n-decane isomerization, when a good balance between the metal phase and the acidic phase of the catalysts is reached, the isomerization and cracking yield curves of the catalysts are a unique function of the conversion, meaning that these yields do not depends on the porosity nor the acidity of large pore materials. Formation of the most bulky isomers, such as 4-propylheptane and 3-ethyl-3-methylheptane was favored in mesoporous solids (figure 1). Criteria based on the formation of these particular isomers are linked with mesoporosity and could be useful to discriminate between zeolites catalysts with and without mesopores. 

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