6
Communications [12] M. J. San JosØ, M. Olazar, F. J. Peæas, J. Bilbao, Ind. Eng. Chem. Res. 1994, 33, 1838. [13] P. N. Rowe, A. W. Nienow, A. J.Agbim, Trans. Inst. Chem. Engrs. 1972, 50, 324. [14] N. Epstein, J. R. Grace, J. R., Handbook of Powder Science and Technology , Van Nostrand Reinhold, New York 1984, 507. [15] M. Olazar, M. J. San JosØ, R. Llamosas, S. Alvarez, J. Bilbao, Ind. Eng. Chem. Res. 1995, 34, 4033. [16] F. J. Peæas, Ph.D. Thesis, University of the Basque Country, Bilbao 1993. [17] K. B. Mathur, K. B. Epstein, Adv. Chem. Eng. 1974, 9, 111. [18] G. Rovero, N. Piccinini, A. Lupo, Entropie 1985, 124, 43. [19] Y. L. He, S. Z. Qin, C. J. Lim, J.R. Grace, Can. J. Chem. Eng. 1994, 72, 561. [20] A. Kmiec, Chem. Eng. J. 1980, 19, 189. [21] O. Uemaki, T. Tsuji, Can. J. Chem. Eng. 1992, 70, 925. [22] B. Thorley, J. B. Saunby, K. B. Mathur, G. L. Osberg, Can. J. Chem. Eng. 1959, 37, 184. [23] G. A. Lefroy, J. F. Davidson, Trans. Instn. Chem. Engrs. 1969, 47, 120. [24] D. S. Scott, S. R. Czernik, J. Piskorz, A. G.Radlein, Energy Fuels 1990 4, 411. [25] W. Kaminsky, Adv. Polym. Technol. 1995, 14, 337. [26] U. Arena, M. Mastellone, Chem. Eng. Sci. 2000, 55, 2849. [27] M. Olazar, M. J. San JosØ, S. Alvarez, A. Morales, J. Bilbao, Ind. Eng. Chem. Res. 1998, 37, 4520. Microporous Solid Characterization: Use of Classical and ªNewº Techniques By D. Lozano-Castelló, D. Cazorla-Amorós , and A. Linares-Solano* Gas adsorption techniques constitute the most common approach for the characterization of the pore structure of porous materials, and undoubtedly, N 2 adsorption at 77 K is the most used. However, N 2 adsorption has some limitations. Therefore, to achieve the correct assessment of the micropo- rosity, the use of other adsorptives has been proposed. In this sense, it has been demonstrated that CO 2 adsorption at 273 K, at sub-atmospheric pressures, is necessary for the correct characterization of this narrow microporosity. In this keynote, the usefulness of the adsorption of gases to characterize different type of microporous solids will be reviewed. Small Angle Scattering (SAS) techniques represent an alternative to gas adsorption methods. A review of the first experiments performed with single activated carbon fibers with the micro-SAXS technique available at the ESRF (synchrotron facilities) will also be reviewed. 1 Introduction Activated carbons (ACs) and activated carbon fibers (ACFs) are materials widely used in many applications. A feature of particular interest, that controls their usefulness, is their porous texture (pore volume, pore size distribution, etc). Thus, porous texture characterization is an essential task to predict and understand the performance of an adsorbent in a given application. The objective of this work is to present different ways of characterizing microporous solids, paying special attention to the characterization of the narrow microporosity (pore sizes less than 0.8 nm, approximately). These ways include the use of classical techniques, such as gas adsorption, and new techniques such as the lSAXS (microbeam Small Angle X-Ray Scattering) technique. Physical adsorption of gases is the technique most employed for the characterization of porous solids [1,2]. Different adsorptives, like N 2 , CO 2 , Ar, He, CH 4 , benzene, nonane, etc., can be used for this purpose [1±5]. Among the gases, N 2 adsorption at 77 K is the most widely used. The advantage of N 2 adsorption is that it covers relative pressures from 10 ±8 ±1, which results in adsorption in the whole range of porosity. The main disadvantage of N 2 adsorption at 77 K is that when used for the characterization of microporous solids, diffusional problems of the molecules inside the narrow porosity range (size < 0.7 nm) occur [3]. Moreover, there is an additional experimental difficulty in the adsorption of subcritical nitrogen, because very low relative pressures (10 ±8 ±10 ±4 ) are required to extend the range of porosity studied to narrow microporosity. To overcome this problem, the use of other adsorptives has been proposed. CO 2 adsorption, either at 273 K or 298 K [3, 6±9] is an easy alternative to N 2 adsorption for the assessment of the narrow microporosity. Though the critical dimension of the CO 2 molecule is similar to that of N 2 , the higher temperature of adsorption used for CO 2 results in larger kinetic energy of the molecules, which are consequently able to enter into the narrow porosity. In the first two parts of this work, some examples of the usefulness of CO 2 adsorption at 273 K to achieve a complete characterization of the porous texture of microporous carbons will be presented. In addition to gas adsorption techniques, the Small Angle X-Ray Scattering (SAXS) technique represents an alternative to gas adsorption methods. This technique can provide structural details of porous materials on a scale covering a range from a few to about 2000 . SAXS techniques offer a number of advantages for the characterization of porous materials [10±13]: (i) it is sensitive to both closed and open porosity; (ii) SAXS intensity profiles are sensitive to both shape and orientation of the scattering objects; (iii) it can be used to investigate samples that are saturated with liquids; and (iv) it can be used to investigate the pore structures of materials under operating conditions. However, the equip- ment required for SAXS experiments is not as widely available as other laboratory techniques. In previous work [14,15], it has been shown that lSAXS technique (SAXS technique with X-ray microbeams with sizes down to 2 lm) is a suitable technique to study single activated carbon fibers (ACFs), instead of bundles of fibers, as it is usually done in SAXS experiments. In the third part of this work, the usefulness of lSAXS technique to characterize the ªclosedº or inaccessible porosity in a carbon fiber and ACFs will be discussed. 852 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ceat.200300007 Chem. Eng. Technol. 26 (2003) 8 ± [*] D. Lozano-Castelló, D. Cazorla-Amorós, A. Linares-Solano (author to whom correspondence should be addressed, e-mail: [email protected]), Departamento de Química Inorgµnica, Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain.

Microporous Solid Characterization: Use of Classical and “New” Techniques

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