Characterization of Heterogeneous Catalysts

Both the physical and the chemical structure of a catalyst must be known if relationships between the
material structure of the catalyst and activity, selectivity, and lifetime are to be revealed. The available
methods include classical procedures and state-of-the-art techniques for studying the physics and
chemistry of surfaces.

The physical properties of pore volume, pore distribution, and BET surface area are nowadays routinely
monitored in the production and use of industrial catalysts. In contrast, the chemical characterization of
catalysts and microstructural investigations, especially of the catalyst surface, are far more laborious and
are rarely carried out in industry.

As we have already seen in many examples, the upper atomic layers often have a different composition
to that in the catalyst pellet. Promoters, inhibitors, and catalyst poisons can also be deposited. Therefore,
in order to understand heterogeneous catalysis, information about the nature and structure of the upper
atomic layers is required. Up to about 35 years ago, chemisorption processes were the only methods
available for the indirect characterization of the catalyst surface. Only in the 1970s did instruments for
the analysis of surfaces become commercially available, opening up new possibilities for fundamental
catalyst research.

In this section we will encounter some methods for characterizing catalysts and discuss their capabilities
and limitations. Most chemical engineers working in catalyst development are not experts in complex
industrial analytical chemistry, and only a few major companies and research institutes can afford surface
analysis equipment. For these reasons we shall dispense with the details of methods and apparatus and
concentrate on practical applications.

Figure 1. gives an overview of the common methods of catalyst investigation.

Figure 1. Instruments of catalyst investigation

Physical Characterization

The main terms for describing physical catalyst properties are as follows:

▪ Morphology: steric conditions and topology of the surface

▪ Porosity: share of the hollow space (pore volume) of a catalyst pellet
▪ Texture: generally, refers to the pore structure of the particles (pore size, pore size distribution,
pore shape)

An important property of catalysts is the distribution of pores across the inner and outer surfaces. The
most widely used method for determining the pore distribution in solids is mercury porosimetry, which
allows both mesopores (pore radius 1–25 nm) and macropores (pore radius > 25 nm) to be determined.
The pore size distribution is determined by measuring the volume of mercury that enters the pores under
pressure. The measurement is based on Equation:

p = pressure
σ = surface tension of adsorbate
α = contact angle Hg/solid
rP = radius of cylindrical pores

Pressures of 0.1 to 200 MPa allow pore sizes in the range 3.75–7500 nm to be determined. Since the pores
are not exactly cylindrical, as assumed in Equation, the calculated pore sizes and pore size distributions
can differ considerably from the true values, which can be determined by electron microscopy.

Mercury porosimetry is advantageously used for characterizing various shaped industrial catalysts in
which diffusion processes play a role. The macropore distribution is of major importance for the turnover
and lifetime of industrial catalysts and is decisively influenced by the production conditions.

For the actual catalytic reaction, the distribution of meso- and micropores is of greater importance. The
specific pore volume, pore size, and pore size distribution of microporous materials are determined by
gas adsorption measurements at relatively low pressures (low values of p/p0 = pressure/saturation
pressure). The method is based on the pressure dependence of capillary condensation on the diameter of
the pores in which this condensation takes place. To calculate the pore size distribution, the desorption
isotherm is also determined. Thus, a distinction can be made between true adsorption and capillary
condensation. The latter is described by the Kelvin equation.

Micropores occur in particular in zeolites and activated carbons. They can lead to false values of BET
surface areas due to capillary condensation.

The specific surface area (in m2/g) of a catalyst or a support material can be determined by the proven
BET method. The volume of a gas (usually N 2) that gives monomolecular coverage is measured, allowing
the total surface area to be calculated. The equilibrium isotherms are of the form shown in Figure 2.
 Figure 2. Typical isotherm for physisorption

In Figure 2 the adsorbed volume is plotted against p/p0 (p = pressure, p0 = saturation pressure). At low
pressures monolayer adsorption obeys the Langmuir equation:

However, above about p/p0 = 0.1, multilayer adsorption becomes important. A theoretical model for
describing such adsorption processes was developed by Brunauer, Emmett, and Teller, who formulated
the familiar BET equation:

c includes the heat of adsorption and condensation and is constant for a particular class of compounds
(i.e., oxides, metals) with values of over 100.

Equation BET applies up to p/p0 = 0.3, above which capillary condensation begins, initially in the smallest
micropores and finally in the mesopores when p/p0 approaches unity. The determination of VM by means
of BET Equation is impractical, and a much better method was developed by transforming BET Equation
into a linear equation:
Then VM can easily be determined from the slope m and the ordinate intersection y. From the difference
between the BET surface area and the surface area measured by mercury porisometry, the micropore
fraction of materials such as zeolites and activated carbons can be determined.

The nest table lists typical surface areas of catalysts and supports.

Table 1. Specific surface areas of catalysts and support materials.

Industrial Catalysis: A Practical Approach, Third Edition, Jens Hagen, Wiley-VCH, 2015.