The molecular orientation and structure of adsorbates at oxide interfaces is driven by surface-molecule and molecule-molecule interactions and is useful for predicting reactivity and product selectivity in heterogeneous chemical reactions, including those important in catalytic processes. Using broadband vibrational sum-frequency generation spectroscopy, we probed cyclic and acyclic alkanes and olefins at buried vapor/solid and liquid/solid interfaces of the α-alumina (0001) surface under ambient conditions. The spectroscopic signatures of the adsorbates were measured and compared with bulk phase spectra and spectra of model surfaces containing hydrocarbons covalently linked to glass slides using silane chemistry. By utilizing appropriate polarization combinations, the orientations of hydrocarbons adsorbed from the vapor were evaluated and compared to the hydrocarbon orientations at the liquid/solid interface. The data support a proposed orientation for n-alkanes and cycloalkanes at the liquid/solid interface in which the hydrocarbons lie with the planes of their carbon backbones parallel to the surface, whereas at the vapor/solid interface, the adsorbates are oriented with their carbon backbones in an orientation neither parallel nor perpendicular to the surface. The surface vibrational spectra of olefins at both types of interfaces indicate that their orientations differ from saturated counterparts, and their unique spectral signatures allow differentiation of adsorbed olefins from alkanes.
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films