Comparative study by infrared spectroscopy and microcalorimetry of the CO adsorption over supported palladium catalysts

The adsorption of CO on Al(2)O(3), ZrO(2), ZrO(2)-SiO(2), and ZrO(2)-La(2)O(3) supported Pd catalysts was studied by adsorption microcalorimetry and infrared (TR) spectroscopy. Some interesting and new correlations between the results of microcalorimetry and IR spectroscopy have been found. The CO is adsorbed on palladium catalysts in three different modes: multibonded (3-fold), bridged (2-fold), both on Pd(lll) and (100) planes, and linear (1-fold) adsorbed species. The corresponding differential adsorption heats lie in the field of high (210-170 kJ/mol), medium (140-120 kJ/mol), and low (95-60 kJ/mol) values, respectively. The nature of the support, the reduction temperature, and the pretreatment conditions affect the surface structure of the Pd catalysts, resulting in variations in the site energy distribution, i.e., changes in the fraction of sites adsorbing CO with specific heats of adsorption. Moreover, the CeO(2); promoter addition weakens the adsorption strength of CO on palladium. Based on the exposed results, a correctness factor, which considers the percentages of various CO adsorption states, must be introduced when one calculates the Pd dispersion using CO adsorption data.

Photofragment translational spectroscopy of p-bromotoluene at 266 nm

Photodissociation of p-bromotoluene at 266 nm has been investigated on the universal crossed molecular beam machine, and translational energy distribution P(E-t) as well as the anisotropy parameter beta have been obtained. Photofragment translational energy distribution P(E-t) reveals that similar to 38.5% of the available energy is partitioned into translational energy. The anisotropy parameter beta is determined to be -0.4 +/- 0.2. From P(E-t) and beta, we deduce that p-bromotoluene photodissociation is a fast process and the perpendicular transition plays a central role at this wavelength. The possible mechanism has been discussed and comparison of p-bromotoluene with bromobenzene, o-bromotoluene has also been made. (C) 1999 Elsevier Science B.V. All rights reserved.

Photofragment translational spectroscopy of iodobenzene at 266 nm

The photofragmentation of C6H5I at 266 nn is investigated on the universal crossed molecular beam ma chine, and the translational spectroscopy as well as the angular distribution of I atom is measured. The results reveal that under the laser intensity of 10(R) W/cm(2) the single-photon dissociation competes with multi-photon processes. In single-photon dissociation the anisotropy parameter beta is 0.4 and the average translational energy is only 1.04 kcal/mol, which indicates that this process is a slow predissociation. In two-photon photofragmentation the average translational energy is 51.64 kcal/mol, which accounts for about 35% of the available energy. Another photofragmentation channel is even more faster, whose peak in time-of-flight spectra corresponds to four or five photon absorptions. The branching ratio of these three channels is determined to he about 3:3:4.

Characterization of iron atoms in the framework of MFI-type zeolites by UV resonance Raman spectroscopy

Silicalite-I, ZSM-5, and Fe-ZSM-5 zeolites prepared from two different silicon sources are characterized by UV resonance Raman (UVRR) spectroscopy, X-ray diffraction (XRD), electron spin resonance (ESR), and UV/visible diffuse reflectance spectroscopy (UV/Vis DRS). A new technique for investigating zeolitic structure, UV resonance Raman spectroscopy selectively enhances the Raman bands associated with framework iron atoms incorporated into MFI-type zeolites, and it is very sensitive in identifying the iron atoms in the framework of zeolites, while other techniques such as XRD, ESR, and UV/Vis DRS have failed in uncovering trace amounts of iron atoms in the framework of zeolites. (C) 2000 Academic Press.