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Temperature-Programmed Desorption (TPD) Methods

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Calorimetry and Thermal Methods in Catalysis

Part of the book series: Springer Series in Materials Science ((SSMATERIALS,volume 154))

Abstract

This chapter presents the fundamentals, the experimental setups and the applications of temperature-programmed desorption (TPD), method used to investigate the events that take place at the surface of solid material while its temperature is changed in a controlled manner. At the beginning, fundamental principles of adsorption and desorption phenomena, as well as the data concerning first experimental setups are given. Further, important information related to the construction of nowadays used equipment and the organization of common experiments are underlined. The significance of data directly obtained from temperature-programmed experiment—TPD profile, which are the area under it and the position of peak maximum, are highlighted. Particular attention is given to the results that can be derived from these data—characterization of active sites that can be found on the surface of solid material and determination of kinetic and thermodynamic parameters of desorption process. In this regard, the influence of important experimental parameters on derived values is explained. Besides, the distinctions between TPD experiments performed in ultra-high vacuum and in the flow systems (differences in experimental setups and in the derivation of kinetic and thermodynamic parameters) are explained. Also, the modification of temperature-programmed techniques, known as temperature-programmed oxidation and temperature-programmed reduction are shortly explained and compared with temperature-programmed desorption method. In the end, a brief comparison of the TPD and adsorption calorimetry, two most widely used techniques for the study of acid/base properties of catalysts, is given.

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Notes

  1. 1.

    Significant difference in heating rates makes main distinction between “flash desorption”, where the heating rate is very high (the desired temperature is reached in seconds) and temperature-programmed desorption (where the sample is heated in minutes or even hours).

  2. 2.

    TPD is perhaps the most often used for estimation of acid/base properties of solid catalysts.

  3. 3.

    Dissociative chemisorption of a diatomic molecule can also happen through the dissociation in a gas phase and a creation of two gas phase atoms; these two atomic species can be then adsorbed on the surface (this way is almost always non-activated). If the curves describing molecular and atomic adsorption intersect at or below the zero potential energy line, then the precursor physisorbed molecule can experience non-activated dissociation, followed by chemisorption (Fig. 4.1a). In contrast, if the energetic for these two pathways are such that the intersection occurs above the zero energy plane, then chemisorption will be activated with activation energy, E\(_{ad}\), as indicated in Fig. 4.1b.

  4. 4.

    Instead to define equilibrium by constant surface coverage, it is possible to keep constant pressure at the surface; in that case the equilibrium heat of adsorption \(q_{eq}\) is incorporated in Clausius-Clapeyron equation.

  5. 5.

    In those cases, the consumption of either reductive or oxidative gas by the catalyst is derived from the change in thermal conductivity of the gas mixture.

  6. 6.

    If catharometer is used as detector, it is very important to remove traces of water or any other impurities from the gas flows, because they would affect the thermal conductivity measurements.

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Authors and Affiliations

  1. University of Belgrade, Nemanjina 6, 11080 , Zemun, Serbia

    Vesna Rakić

  2. University of Belgrade, Studentski trg 12-16, 11000 , Belgrade, Serbia

    Ljiljana Damjanović

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  1. Vesna Rakić
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  2. Ljiljana Damjanović
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Correspondence to Vesna Rakić .

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  1. Lyon (IRCELYON), Institut de Recherches sur la Catalyse et l’Environnement de, Villeurbanne CX, France

    Aline Auroux

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Rakić, V., Damjanović, L. (2013). Temperature-Programmed Desorption (TPD) Methods. In: Auroux, A. (eds) Calorimetry and Thermal Methods in Catalysis. Springer Series in Materials Science, vol 154. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-11954-5_4

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