Alumina support surface structure

In situ dynamic surface structural changes of catalyst particles in response to variations in gas environments were examined by ETEM by Gai et al. (78,97). In studies of copper catalysts on alumina, which are of interest for the water gas shift reaction, bulk diffusion of metal particles through the support in oxygen atmospheres was shown (78). The discovery of this new catalyst diffusion process required a radical revision of the understanding of regeneration processes in catalysis. 

The total surface areas determined by the N2 BET method for the calcined, supported catalysts are listed in Table II. The X-ray diffraction (XRD) results showed diffraction peaks from a cubic lattice with a unit cell distance of 6.1 A were present on all of the calcined catalysts. Both C03O4 and C0AI2O4 have structures consistent with that lattice spacing, making assignment of the type of crystalline cobalt species present on the alumina supports difficult. 

Shimizu, K Takamatsu, M Nishi, K Yoshida, H Satsuma, A Tanaka, T Yoshida, S Hattori, T. Alumina-supported gallium oxide catalysts for NO selective reduction Influence of the local structure of surface gallium oxide species on the catalytic activity, J. Phys. Chem., B, 1999, Volume 103, Issue 9, 1542-1549. 

Supported Cu-Pd catalysts have the potential to provide new alternatives to conventional commercial methanol synthesis catalysts (based on the Cu-ZnO-alumina system). Cu-Pd catalysts are also of industrial interest in hydrogenolysis and CO oxidation (Bulatov 1995). To interpret the catalyst behaviour and selectivity, including CO hydrogenation, a fundamental understanding of the structure, surface structure and stability of the phases in this system is required. The Cu-Pd phase diagram indicates that at temperatures greater than 600 °C, Cu... 

The literature of the vibrational spectra of adsorbed alkynes (acetylene and alkyl-substituted acetylenes) is very much in favor of single-crystal studies, with fewer reported investigations of adsorption on oxide-supported metal catalysts. Fewer studies still have been made of the particulate metals under the more advantageous experimental conditions for spectral interpretation, namely, at low temperatures and on alumina as the support. (The latter has a wide transmittance range down to ca. 1100 cm-1.) A similar number of different single-crystal metal surfaces have been studied for ethyne as for ethene adsorption. We shall review in more detail the low-temperature work which usually leads to HCCH nondissociatively adsorbed surface structures. Only salient features will be discussed for higher temperature ethyne adsorption that often leads to dissociative chemisorption. Many of the latter species are those already identified in Part I from the decomposition of adsorbed ethene. 

The alumina or silica-alumina supports used in bifunctional catalysts have been shown to be acidic in nature. The acidic properties are readily demonstrated by the affinity of these solids for adsorption of basic compounds such as ammonia, trimethylamine, re-butylamine, pyridine, and quinoline (01, R5). Furthermore, adsorption of certain acid-base indicators such as butter yellow gives a coloration similar to that observed in acid media (B3, B4). With regard to the origin of the acidity, Tamele (Tl) has suggested in the case of silica-alumina that aluminum atoms replace silicon atoms in the surface of the silica structure, giving rise to surface sites of the form... 

The surface structure and acid sites of alumina-supported molybdenum nitride catalysts have been studied using temperature-programed desorption (TPD), and reduction (TPR), diffuse reflectance infrared spectroscopy, and X-ray diffraction (XRD) analysis. The nitride catalysts were prepared by the temperature-programmed reaction of alumina-supported molybdenum oxide (12.5% and 97.1%) with NH3 at temperatures of 773, 973, and 1173 K. TPR and XRD analyses showed that y-Mo2N was already formed at 973 K. On the basis of NH3-TPD measurements and IR spectroscopy, it was found that Lewis acid sites were predominant over Bronsted acid sites on the surface of Mo2N/A1203. 

Although the synthesis and catalytic activity of unsupported and alumina-supported molybdenum nitride have been studied extensively, much less attention has been given to examining the surface structure and... 

Due to the high density of Rh atoms, no species of the form Rh(C0)2 were formed, however. This is expected to be the case on the (111) surface as well. Weak absorptions between 400 and 575 cm"l were seen and are indicative of metal-absorbate stretching and bending vibrations. Inelastic electron tunneling spectroscopic (IETS) measurements on alumina supported rhodium particles (47, 48, 49) add little new structural information... 

Molybdenum oxide - alumina systems have been studied in detail (4-8). Several authors have pointed out that a molybdate surface layer is formed, due to an interaction between molybdenum oxide and the alumina support (9-11). Richardson (12) studied the structural form of cobalt in several oxidic cobalt-molybdenum-alumina catalysts. The presence of an active cobalt-molybdate complex was concluded from magnetic susceptibility measurements. Moreover cobalt aluminate and cobalt oxide were found. Only the active cobalt molybdate complex would contribute to the activity and be characterized by octahedrally coordinated cobalt. Lipsch and Schuit (10) studied a commercial oxidic hydrodesulfurization catalyst, containing 12 wt% M0O3 and 4 wt% CoO. They concluded that a cobalt aluminate phase was present and could not find indications for an active cobalt molybdate complex. Recent magnetic susceptibility studies of the same type of catalyst (13) confirmed the conclusion of Lipsch and Schuit. 

Application of Raman spectroscopy to a study of catalyst surfaces is increasing. Until recently, this technique had been limited to observing distortions in adsorbed organic molecules by the appearance of forbidden Raman bands and giant Raman effects of silver surfaces with chemisorbed species. However, the development of laser Raman instrumentation and modern computerization techniques for control and data reduction have expanded these applications to studies of acid sites and oxide structures. For example The oxidation-reduction cycle occurring in bismuth molybdate catalysts for oxidation of ammonia and propylene to acrylonitrile has been studied in situ by this technique. And new and valuable information on the interaction of oxides, such as tungsten oxide and cerium oxide, with the surface of an alumina support, has been obtained. 

Even if the tin does not actually form a species corresponding to a surface tin aluminate compound, the oxidized tin is widely dispersed, the anion associated with it must be an oxide anion, or possibly a chloride ion if the catalyst still contains this element, and the oxidized tin interacts strongly with the alumina support. Thus, even if the tin is not present in a specific tin aluminate compound containing either Sn2+ or Sn4+, the actual structure will resemble a tin aluminate widely dispersed over the surface. Thus, we only consider two states for tin a surface species for the oxidized tin that is or resembles a tin aluminate and Sn° that is essentially all present as PtSn =1 1 alloy. Thus,... 

These results led to questioning of the presumed similar performance of polymeric and isolated surface species. Raman spectroscopy and UV-vis DRS investigations of zirconia- and alumina-supported vanadia showed that the oxidation state of the surface vanadium oxide species was determined by the propane-to-C>2 ratio in the feed (Garcra-Cortez and Banares, 2002). The combination of two spectroscopic techniques provided more detail about the structural state of the supported species during moderate reduction under reaction conditions (Gao et al., 2002). 

The interaction of cupric ions with alumina supports has subsequently been studied more extensively as a function of the support surface area, metal loading, and calcination temperature (93,279) by means of EXAFS and X-ray absorption-edge shifts, in conjunction with XRD, EPR, XPS, and optical reflectance spectroscopy. These techniques, each sensitive to certain structural and electronic aspects, allow a unified picture of the phases present and the cation site location. Four Cu2 + ion sites are distinguished in the catalysts. In low concentrations (typically below about 4 wt. % Cu/100 m2/g support surface area) Cu2 + ions enter the defect spinel lattice of the A1203 support. The well-dispersed surface copper aluminate has Cu2+ ions predominantly occupying tetragonally (Jahn-Teller) distorted octahedral sites, although... 

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