Activated carbons are widely used as commercial adsorbents. Thermal or chemical activation creates a pore system and functional groups on the inner surface which may significantly change adsorption properties. Therefore, in addition to knowledge of the structural properties, a sound understanding of surface chemistry is indispensable. This paper summarizes the state of art as well as new developments in both fields. Standardized methods for characterizing structural properties are volumetric measurements and mercury porosimetry. To get a more detailed insight into the region of micropores, a probe molecule method was developed. For characterization of surface chemistry, methods such as IR spectroscopy, temperature‐programmed desorption, and Boehm titration are subject of research. Novel methods were developed such as measuring of excess isotherms and calorimetric measurement of heat of adsorption, which are presented and discussed in greater detail in this paper. As each single method can only provide limited information, a better description of surface chemistry requires combination and careful interpretation of complementary information from different methods.

In addition to the adsorption mechanism, the heat released during exothermic adsorption influences the chemical reactions that follow during heterogeneous catalysis. Both steps depend on the structure and surface chemistry of the catalyst. An example of a typical catalyst is the faujasite zeolite. For faujasite zeolites, the influence of the Si/Al ratio and the number of Na⁺ and Ca²⁺ cations on the heat of adsorption was therefore investigated in a systematic study. A comparison between a NaX (Sodium type X faujasite) and a NaY (Sodium type Y faujasite) zeolite reveals that a higher Si/Al ratio and therefore a smaller number of the cations in faujasite zeolites leads to lower loadings and heats. The exchange of Na⁺ cations for Ca²⁺ cations also has an influence on the adsorption process. Loadings and heats first decrease slightly at a low degree of exchange and increase significantly with higher calcium contents. If stronger interactions are required for heterogeneous catalysis, then the CaNaX zeolites must have a degree of exchange above 53%. The energetic contributions show that the highest-quality adsorption sites III and III’ make a contribution to the load-dependent heat of adsorption, which is about 1.4 times (site III) and about 1.8 times (site III’) larger than that of adsorption site II.

The aim of this study is to unravel the influence of single, double and triple bonds in hydrocarbons on the mechanisms of adsorption on zeolites. Therefore, the adsorption of the C2 hydrocarbons ethane, ethene and ethyne on different adsorbents is studied by adsorption calorimetry. As adsorbents pure sodium LTA (NaA) and FAU (NaX) zeolites and calcium exchanged CaNaA and CaNaX zeolites are used. Based on experimental loadings and heat of adsorption, the influence of the number and distribution of cations on different cation positions are discussed in detail. With increasing degree of exchange the increasing number of Ca²⁺-cations introduce energetically more valuable adsorption sites into the zeolites. On the other hand, the decreasing total number of cations has a negative effect on saturation loading. The impact of these opposing effects and the different occupation of cation positions on the interactions and mechanisms occurring are discussed. The loading increases from ethane to ethene to ethyne and shows higher values on FAU compared to LTA. In terms of interactions, due to the single bond, in ethane only dispersion and induction interactions are formed. In ethene and ethyne due to the double and triple bonds, respectively, additional quadrupole cation and π-interactions occur. In this study, for the first time the formation of a π-complex with Ca²⁺-cations at position I in LTA and at positions II, III, and III’ in FAU is demonstrated. For ethyne, additional π-complex formation with Na⁺-cations on the identical positions is also detected, which was previously unknown in literature.