Abstract
The focus of this chapter is single-crystal adsorption calorimetry, which is used for the direct measurement of adsorption energies on well-defined surfaces, both single- and poly-crystalline. The method was pioneered in the 1990s mainly by D.A. King and C.T. Campbell and is based on earlier work by S. Černy. Especially in recent years, the technique has seen increasing proliferation and development. In contrast to desorption-based methods, such as temperature-programmed desorption and isosteric measurements, calorimetry is also well suited for irreversible reactions. The systems studied range from simple adsorption of small molecules, such as CO and NO, to surface reconstructions, reaction intermediates, hydroxyl group formation, metal adsorption and diffusion into polymers, particle-size dependent adsorption energies on model catalysts and even electrochemical reactions on electrode surfaces in the liquid phase.
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