Ferrocene Adsorbed on Silica and Activated Carbon Surfaces: A Solid-State NMR Study of Molecular Dynamics and Surface Interactions

Ferrocene has been adsorbed on the surface of silica and activated carbon within the pores by dry grinding in the absence of a solvent at room temperature. While the dry adsorption and translational mobility of ferrocene within the pores are already established on the centimeter scale, there is little systematic understanding of the surface site-to-site motions of the ferrocene molecules and their orientation with respect to the surface. In this paper, silica and activated carbon, both widely applied in academia and industry as adsorbents, are used as support materials. Using variable-temperature 13C and 2H solid-state NMR and T 1 relaxation time measurements, the dynamics of ferrocene on the surfaces of silica and activated carbon within the pores has been quantitatively characterized on the molecular scale. The obtained data indicate that ferrocene molecules show a liquid-like behavior on the surface. Fast exchange between isotropically moving molecules and surface-attached molecular states of ferrocene has been found in samples with submonolayer surface coverages. The surface-attached molecular states have been characterized by the free energies ΔG ⧧ of 6.1 kcal/mol for silica and ΔG ⧧ of 6.2 kcal/mol for activated carbon at 223 and 263 K, respectively. The horizontally oriented ferrocene molecules are the most thermodynamically stable states on the surfaces of both materials. These molecules exhibit fast C5 rotation of the Cp rings, as established by low-temperature 13C and 2H NMR. The interactions of ferrocene with the pore surfaces have been characterized by adsorption enthalpies measured as −8.4 to −7.0 kcal/mol and −6.7 kcal/mol for activated carbon and silica, respectively. It has been suggested that the ferrocene–surface interactions for both support materials have a polar character.