Porous mesoporous carbons

IUPAC classification, mesoporous materials are defined as porous materials with diameters in the range 2-50 nm, which is rather dose to the dimensions of functional biomolecules such as proteins. Therefore, unexplored phenomena and functions could be observed for biomolecules confined in mesopore channels due to their restricted motion and orientation. In this chapter, we briefly introduce recent developments on the immobilization of biomolecules in mesoporous media, where the use of mesoporous silica and mesoporous carbon are mainly discussed. 

Recent reports describe the use of various porous carbon materials for protein adsorption. For example, Hyeon and coworkers summarized the recent development of porous carbon materials in their review [163], where the successful use of mesoporous carbons as adsorbents for bulky pollutants, as electrodes for supercapacitors and fuel cells, and as hosts for protein immobilization are described. Gogotsi and coworkers synthesized novel mesoporous carbon materials using ternary MAX-phase carbides that can be optimized for efficient adsorption of large inflammatory proteins [164]. The synthesized carbons possess tunable pore size with a large volume of slit-shaped mesopores. They demonstrated that not only micropores (0.4—2 nm) but also mesopores (2-50 nm) can be tuned in a controlled way by extraction of metals from carbides, providing a mechanism for the optimization of adsorption systems for selective adsorption of a large variety of biomolecules. Furthermore, Vinu and coworkers have successfully developed the synthesis of... 

Nowadays synthesis of mesoporous materials with zeolite character has been suggested to overcome the problems of week catalytic activity and poor hydrothermal stability of highly silicious materials. So different approaches for the synthesis of this new generation of bimodal porous materials have been described in the literature like dealumination [4] or desilication [5], use of various carbon forms as templates like carbon black, carbon aerosols, mesoporous carbon or carbon replicas [6] have been applied. These mesoporous zeolites potentially improve the efficiency of zeolitic catalysis via increase in external surface area, accessibility of large molecules due to the mesoporosity and hydrothermal stability due to zeolitic crystalline walls. During past few years various research groups emphasized the importance of the synthesis of siliceous materials with micro- and mesoporosity [7-9]. Microwave synthesis had... 

Among the inorganic templates, zeolite produces more regulated pores as compared to the silica template. If nano-channels in zeolite are completely filled with carbonaceous precursor and then the carbon materials are extracted from the zeolite framework, one can obtain the porous carbon of which structure reflects the porosity of the original zeolite template. The ordered mesoporous silica templates, e.g., MCM-4 838,39,47 and SBA-1547 have been employed to prepare the ordered porous carbons by the procedures involving the pore filling of the silica template with carbonaceous precursor followed by carbonization and silica dissolution. The resulting pore sizes of the ordered mesoporous carbons are smaller than about 10 nm. 

Air diffusion electrodes In fuel cells and in air-breathing batteries, a mesoporous carbon electrode is made up of two layers an outer layer composed of carbon powder and a hydrophobic (nonwettable) binder, typically PTFE. This enables the access of gas to the inner layer, where the binder is selected to be both a hydrophilic (wettable) and an ion-conducting ionomer, to support (rather than impair if the binder was nonconducting) the ionic conductivity of the porous electrode. The catalyst particles are dispersed in-between the carbon particles. Thus, a very tortuous interface between the two layers is formed. The reacting gas approaches this interface, forming three phase points of contact providing a high active surface area. See also - air electrode. 

Ryoo et al. reported the first ordered mesoporous carbon, CMK-1, using cubic MCM-48 as template and sucrose as carbon source. CMK-1 exhibited a highly ordered cubic structure, as confirmed by transmission electron microscopy (TEM). However, x-ray powder diffraction patterns indicated that CMK-1 underwent a structural transformation upon the silica removal due to the two disconnected porous systems separated by the silica wall. ... 

Different porous materials, including oxides (a-AlaO. , Si02, Ti02), zeolites (Na-ZSM-5, H-ZSM-5, H-beta, Na-Y, and H-USY), carbon (activated carbon, Norit, and mesoporous carbon (Novacarb from MAST Carbon Ltd.)), cement-like materials (end and tras, with low and high lime content, respectively), and catalysts (1 wt.% Pt/ALOs, 5 wt.% Pt/AbOs, and 16 wt.% Ni/AbOa) were used, as well as home-made samples (AbOs, MCM-41, and SBA-15). 

For the accurate characterization of the adsorption phenomena, it is necessary to obtain accurate information on pore stmctures. However, most of ordinary microporous carbons and mesoporous carbons are obtained with amorphous stmctures that are characterized by irregular arrangements of non-uniform pores. X-ray (or electron) diffraction (XRD) techniques are not useful for such carbons because there are no well-defined stmctural factors to correlate with the adsorption behavior. Moreover, porous carbons exhibit wide varieties of the surface functional groups and the thickness of the pore walls, depending on the details of the synthesis conditions. The lack of distinct XRD lines makes it difficult to distinguish stmctural differences between samples which causes many works to depend empirically on specific samples. 

As can be seen from Figure 2 the adsorption branch of this isotherm exhibits two distinct steps that reflect the capillary condensation inside smaller or larger mesopores at relative pressures about 0.79 and 0.9, respectively. The condensation in the relative pressure range of 0.9S-0.99S reflects condensation in secondary mesopores or small macropores, which resulted from the imprinting of agglomerates of colloidal particles. To our knowledge, this kind of isotherm has not been reported for porous carbon materials. The pore size distribution for this mesoporous carbon shown in Figure 3 exhibits two distinct peaks located about 11 nm and 24 nm, which correspond to the particle size of Bindzil 30/360 and Ludox AS-40 colloidal silicas, respectively. 

Radhakrishnan and co-workers [6] also studied the freezing of CCI4 in activated carbon fibers (ACF) of uniform nano-scale structures, using Monte Carlo simulation and differential scanning calorimetry (DSC), klicro-porous activated carbon fibers serve as highly attractive adsorbents for simple non-polar molecules. The DSC experiments verified the predictions about the increase in T/. and the molecular results were consistent with equation (1) for pore widths in the mesoporous range they also explained the deviation from the linear behavior in the case of micropores. 

We will not discuss here models for pores in carbons, as this topic is treated in Chapter 5, and elsewhere in specialist [15] or general reviews [106, 107]. For similar reasons, we will not discuss porosity control [44, 108] in detail. However, porous carbons prepared by the template technique, especially the ordered ones, deserve special attention. Ordered mesoporous carbons have been known to scientists since 1989 when two Korean groups independendy reported their synthesis using mesoporous silicas as templates [109, 110]. Further achievements have been described in more recent reports [111, 112]. One might have expected that the nanotexture of these materials would merely reflect the nature of the precursor used, namely phenol-formaldehyde [109] or sucrose [110] in the two first ordered mesoporous carbon syntheses (as is well known, these two precursors would have yielded randomly oriented, isotropic carbon had they been pyrolyzed/activated under more conventional conditions). However, the mesopore walls in some ordered mesoporous carbons exhibited a graphite-like, polyaromatic character [113, 114], as described in Chapter 18. This information was obtained by nitrogen adsorption at low relative pressures, as in classical... 

Lately, a fascinating strategy has been successfully developed for the preparation of ordered mesoporous carbons. The synthesis procedure of these advanced carbons consists in the infiltration of an organic precursor into the pores of silica or aluminosilicate templates, followed by the subsequent pyrolysis of the precursor and dissolution of the template framework by HF [9—12]. In another process, carbon is directly introduced in the template by a CVD method [86]. The method gives a highly ordered and interconnected network of meso- and micropores [87], where the size of carbon mesopores is defined by the walls thickness of the pristine silica matrix. Such materials are very suitable for better understanding the relationships between the porous characteristics and the supercapacitors performance [88, 89]. 

The next two chapters deal mainly with the use of adsorption to characterize porous solids. In the case of activated carbon fibers (Chapter 17), methods to characterize microporosity, and particularly ultramicroporosity, by physical adsorption are of particular relevance for understanding the behavior of these adsorbents and extending the range of their applications. Moreover, in Chapter 18 the pore structure of ordered mesoporous carbons is shown to differ greatly from that of conventional activated carbons for which most of the available data treatment methods have been developed. Therefore, suitable procedures for correctiy analyzing the pore structure of these novel carbons are proposed in this chapter. 

High surface areas are normally obtained by using porous materials, and the pore sizes may condition the accessibility of the reactants to the active sites, especially in the case of microporous materials such as activated carbons. Pore diffusion limitations become more important as the pore sizes decrease in addition, the smaller pores may be more easily blocked (e.g., by coke deposition). Therefore, deactivation and diffusion phenomena will in general affect more strongly the performance of microporous carbons. As a result, there has been a drive to develop mesoporous carbon catalysts (such as aerogels, xerogels, and templated carbons) for some applications, especially in the liquid phase. 

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