Attenuated total reflection infrared spectroscopy for studying adsorbates on planar model catalysts : CO adsorption on silica supported Rh nanoparticles

A sensitive method is presented for studying adsorption of gaseous species on metal surfaces in vacuum by attenuated total internal reflection Fourier transform IR spectroscopy (ATR). The method is illustrated by CO adsorption expts. on silica supported Rh nanoparticles. An exptl. setup and a procedure are described in detail to obtain a sensitivity of reflectance change of .apprx.5 * 10-5 absorbance units. Here, a silicon ATR crystal with a 50 nm layer of hydroxylated silica acts as the support for the Rh nanoparticles. These particles are easily prepd. by spincoat impregnation from a RhCl3 soln. followed by H2 redn. XPS before and after redn. shows that rhodium is reduced to Rh0 and that all chlorine is removed. At. force microscope images the distribution of the particles, which are 3-4 nm in height. When the crystal is exposed to pressures up to 1 mbar of CO, a gas which is inert to the silica support, the stretch vibration of linearly adsorbed CO on the Rh nanoparticles is detected at 2023 cm-1, while no bridged CO or geminal dicarbonyl species can be distinguished. The min. detectable coverage is estd. .apprx.0.005 CO per nm2 substrate area or .apprx.5 * 10-4 ML. [on SciFinder (R)

Anomalous dispersion effects in the IR-ATR spectroscopy of water

The distortion of band shapes seen in infrared attenuated total reflection (IR-ATR) spectroscopy of strongly absorbing materials such as water, relative to transmission sampling, is shown here to be due to the anomalous dispersion (AD) of water. This distortion occurs in addition to the normal 1/v dependence, and, contrary to previous reports, is shown to not be due to chemical changes of water at the interface between the optical element and bulk solution. IR-ATR spectra of water were modeled with approximation-free calculations, The modeled spectra are compared with experimental ATR spectra for different internal reflection elements, and the results are discussed in terms of the AD optical effect