Brunauer-Emmett-Teller isotherm method

Specific surface area (SSA), total pore volume and average pore diameter were measured by N2 adsorption-desorption isotherms at 77K using Micromeritics ASAP 2020. The pore size was calculated on the adsorption branch of the isotherms using Barrett-Joyner-Helenda (BJH) method and the SSA was calculated using the Brunauer-Emmett-Teller (BET) method. 

Nitrogen adsorption was performed at -196 °C in a Micromeritics ASAP 2010 volumetric instrument. The samples were outgassed at 80 °C prior to the adsorption measurement until a 3.10 3 Torr static vacuum was reached. The surface area was calculated by the Brunauer-Emmett-Teller (BET) method. Micropore volume and external surface area were evaluated by the alpha-S method using a standard isotherm measured on Aerosil 200 fumed silica [8]. Powder X-ray diffraction (XRD) patterns of samples dried at 80 °C were collected at room temperature on a Broker AXS D-8 diffractometer with Cu Ka radiation. Thermogravimetric analysis was carried out in air flow with heating rate 10 °C min"1 up to 900 °C in a Netzsch TG 209 C thermal balance. SEM micrographs were recorded on a Hitachi S4500 microscope. 

The most common method used for the determination of surface area and pore size distribution is physical gas adsorption (also see 1.4.1). Nitrogen, krypton, and argon are some of the typically used adsorptives. The amount of gas adsorbed is generally determined by a volumetric technique. A gravimetric technique may be used if changes in the mass of the adsorbent itself need to be measured at the same time. The nature of the adsorption process and the shape of the equilibrium adsorption isotherm depend on the nature of the solid and its internal structure. The Brunauer-Emmett-Teller (BET) method is generally used for the analysis of the surface area based on monolayer coverage, and the Kelvin equation is used for calculation of pore size distribution. 

In principle, isotherms at low partial pressures of the sorbate may be used to determine specific surface areas by the Brunauer-Emmett-Teller (BET) method (G64). In this method, it is assumed that molecules of the sorbate are adsorbed on surfaces that can include the walls of pores, provided that the distance between molecules on opposing walls is large compared with molecular dimensions. From a plot derived from the isotherm, and given the effective cross-sectional area of the sorbate molecule, the specific surface area of the sorbent and the net heat of adsorption are obtained. Using water as sorbate, specific surface areas of about 200 m per g of D-dried paste have typically been obtained for mature cement pastes of normal w/c ratios... 

We now cite the types of experimental data in the literature, by which an analysis of surface adsorption effects is carried out. One common experiment involves measuring adsorption isotherms. By weighing or by volumetric techniques one determines as a function of equilibrium gas pressure the amount of gas held on a given surface at a specified temperature. Usually this quantity varies sigmoidally with rising pressure P, as sketched in Fig. 5.2.1 for a variety of temperatures 7). By standard methods that rely on the Brunauer, Emmett, Teller isotherm equa-tion one can determine the point on the isotherms at which monolayer coverage of the surface is complete it is usually is located fairly close to the knee of the isotherm. From the cross sectional area of the adsorbate molecules and from the amount needed for monolayer coverage one may then ascertain more or less quantitatively the surface area of the adsorbent. As-... 

The nitrogen adsorption-desorption isotherms for specific surface area and porosity assessment were recorded at -196 C in a Gemini instrument from Micromeritics. The specific surface areas were determined by the Brunauer-Emmett-Teller (BET) method. The pore size distributions were obtained from the desorption branch, and the micropore volume was determined by the t-plot method, using literature software [14]. 

Gelb LV, Gubbins KE. Characterization of porous glasses simulation studies, adsorption isotherms, and the Brunauer-Emmett-Teller analysis method. Langmuir 1998 14 ... 

In physical gas adsorption, when an inert gas (such as nitiogen or argon) is used as an absorbent gas, the adsorption isotherm indicates the surface area and/or the pore size distribution of the objective material by applying experimental data to the theoretical adsorption isotherm for gas adsorption on the polymer surface (eg, Brunauer— Emmett—Teller (BET)" method). 

From the isotherms in Figure 11.8 a range of information can be obtained. The first important piece of information is the total surface area of the porous material, which can be calculated using the Brunauer-Emmett-Teller (BET) method. This derives a relationship between the volume and relative pressure, based on how the molecular layers of adsorbate build up on the surface of the porous material [36]. The BET equation is as follows ... 

The area is an important surface parameter for catalytic studies. It is needed to evaluate the rate constant of the surface reaction from the kinetics as well as to allow a fair comparison to be made of the effectiveness of different catalysts. Areas are commonly determined by nitrogen or krypton gas adsorption interpreted by the Brunauer-Emmett Teller (BET) isotherm [30, 32], A number of other methods has been proposed and utilised including microscopy, isotopic exchange, chromatography, gas permeability, adsorption from solution, and negative adsorption (desorption) of co-ions [30, 33]. 

Gas adsorption is a suitable method for a fractal analysis because it is sensitive to the fine structure of the pores and has negligible adverse affects on the pore system. The results are usually analyzed by using fractal generalizations of the Brunauer-Emmett-Teller (BET) isotherm (30) or of the Frenkel-nalsey-TfiU (FHH) isotherm (31). The latter may also be seen as a fractal generalization of the Kelvin equation and is therefore also applicable in the capillary condensation regime (32). It has been claimed that the fractal BET theory is more appropriate for mass fractals (see sect. Fractals ), whereas surface fractals are to be analyzed using the fractal FHH theory (33). These methods have been applied to cellulose powders (34) and tablets (35). 

The point-R method of estimating surface areas was frequently used prior to the development of the Brunauer-Emmett-Teller approach. It entailed choosing from an absorption diagram such as Fig. 8-3 the point at which the central linear section begins. This procedure worked well for some systems, but it was extremely difficult, if not impossible, to select a reliable point B on an isotherm such as that shown for n-butane in Fig. 8-3. In contrast, the Brunauer-Emmett-Teller method was found to be reasonably satisfactory for this type of isotherm. 

Determination of surface areas by Brunauer-Emmett-Teller (BET) isotherms is also an important method for the characterization of amorphous catalysts. For example, the effects of different pretreatments have been followed by measuring BET surface areas (37, 38, 43). BET measurements revealed a dramatic increase in surface areas concomitant with a substantial increase in catalytic activities for Zr-containing amorphous alloys (48, 53-56) during the early period of hydrogenation of CO. 

The BET surface area of powder samples was determined by applying the standard Brunauer-Emmett-Teller method to the nitrogen adsorption isotherm obtained at -196°C using a Quantachrome, Nova 2000e (Boynton Beach, FL) instrument... 

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