Aluminas have been used extensively as adsorbenu and active catalysrs and catalyst supponsm the pas. Already in 1197 the aluminadyzed dehydration of ettllnoi was dtscavered by Dutch chermsts: and S;rbatier [3] remewed the use of dumlnas as active cazaiysrs far vanous reacttons UI the second decade of thu century. She that time the applicazions of aluuuas m dycic pmcesses have mcreased tremendously. In tndustrral cualytic pmcesses, alumuus are mostiy used as catalyst suppons [4]. Oxides a d mued oxides ap well as tracuuion mauls and noble meare supported oa alumma. Thuscb. romaa-elumana catalysts are ktng used for the conversion of parafdns to olailnrc hydrocarbons, 10 hydrodealkplation of aromatics. and to a lesser exzm in catalyzic reforming. The larter process LS also caralyzed by molybdena-alumina, a cavlyst system whid is also active for malang toluene and ocher aromatics from satwed hydrocarc bons. It also dyzes the Isomerhation of pm. Great efions are presently be-made to nudy the surface c...

Catalytic Aluminas: Surface Models and Characterization of Surface Sites

Infrared spectrometric studies of the surface basicity of metal oxides and zeolites using adsorbed probe molecules

The review is a summary and analysis of the data characterizing CO adsorption on surface cationic sites of oxides including supported materials and microporous and mesoporous materials. The contributions of various types of CO bonding to the IR frequency shifts of carbon-bonded molecules are analyzed, namely, the increase of the CO stretching frequency in cases of electrostatic and σ bonding and the decrease of the frequency with π bonding. Polycarbonyls, bridging CO, oxygen-bonded CO, and tilted CO are also considered. The main part of the review is a collection of the experimental results characterizing carbonyls of individual metal ions. The spectral behavior of CO bonded to metal atoms is also assessed in the cases when the metal ions are easily reduced to metal (Cu, Ag, Au, Pd, or Pt) or cationic carbonyls are produced after CO adsorption on supported metals (Ru, Rh, Ir, and Os). The interaction of CO with surface OH groups is also considered. It is demonstrated that IR spectroscopy of adsorbed CO is an efficient methodology to characterize cationic surface sites in terms of their nature, oxidation states, coordination environment and coordinative unsaturation, and location at faces, edges or corners of microcrystallites. When applied to materials with surface hydroxyl groups CO undergoes hydrogen bonding and information can be collected on the proton acid strength.

Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule

beta-oxidation of fatty acids in mitochondria, peroxisomes, and bacteria: a century of continued progress.

The zeolite imidazolate framework ZIF-8 is shown for the first time to be able to catalyze transesterification of vegetable oil with significant activity. Rationalization of this behavior at the atomic scale is provided by combining CO adsorption monitored by FTIR and DFT calculations (clusters and periodic models). We demonstrate that the acido-basic sites are located at the external surface of the material or at defects, but not in the microporosity of ZIF-8. A great variety of sites are found the surface: OH and NH groups, hydrogenocarbonates, low-coordinated Zn atoms, and free N(-) moieties belonging to linkers. Their proportions depend on the operating conditions (temperature and pressure). The acido-basicity of the surface is then probed by adsorption of CO at low temperature. In parallel, the species present are mapped by DFT calculations combined with a thermodynamic model. An assignment of the CO region of the FTIR spectra can thus be proposed. The complex infrared spectrum is attributed to the coexistence of classical C-adducts of CO with acid sites and other modes on basic sites (O-adducts and side-on adducts). Adsorption energies and CO frequency shifts show that some strong Lewis sites exist (in particular Zn(II) species), as well as strong Bronsted acid sites (NH groups), together with basic sites (OH groups and N(-) moieties). By calculating the co-adsorption of a model ester (methyl acetate) and methanol, we show the prevailing role of Zn(II) species as acid sites, combined with N(-) moieties and OH groups as basic ones, in determining the catalytic properties of ZIF-8. This work opens new perspectives on the use of MOFs in catalysis and, more generally, on the properties of their external surface.

Catalysis of transesterification by a nonfunctionalized metal-organic framework: acido-basicity at the external surface of ZIF-8 probed by FTIR and ab initio calculations.

Surface-supported metal cluster carbonyls. I. Decarbonylation and aggregation reactions of rhodium clusters on alumina

Evidence for production of surface formate upon direct reaction of CO with alumina and magnesia

Characterization of supported iridium catalysts prepared from Ir4(CO)12

Interactions of cobalt carbonyls with oxide surfaces. 2. Dicobalt octacarbonyl and tetracobalt dodecacarbonyl on silicas and aluminas

The resonance Raman (RR) spectra of FMN, FAD, FAD in D2O, and 7,8-dimethyl-1, 10-ethyleneisoalloxazinium perchlorate have been obtained by employing KI as a collisional fluorescence-quenching agent. The spectra are very similar to those obtained recently by using the CARS technique to eliminate fluorescence. Spectra have also been obtained for several species in which flavin is known to fluoresce only weakly. We report RR spectra of protonated FMN, FMN semiquinone cation, the general fatty acyl-CoA dehydrogenase, and two "charge-transfer" complexes of fatty acyl-CoA dehydrogenase. Tentative assignment of several vibrational bands can be made on the basis of our flavin spectra. RR spectra of fatty acyl-CoA and its complexes are consistent with the previous hypothesis that visible spectral shifts observed during formation of acetoacetyl-CoA and crotonyl-CoA complexes of fatty acyl-CoA dehydrogenase result from charge-transfer interactions in which the ground state is essentially nonbonding as opposed to interactions in which complete electron transfer occurs to form FAD semiquinone. The only significant change in the RR spectrum of FAD on binding to enzyme occurs in the 1250-cm-1 region of the spectrum, a region associated with delta N--H of N-3. The position of this band in fatty acyl-CoA dehydrogenase and the other flavoproteins studied to date is discussed in terms of hydrogen bonding between flavin and protein.

Kenneth L. Watters

Papers

Surface-supported metal cluster carbonyls. I. Decarbonylation and aggregation reactions of rhodium clusters on alumina

Evidence for production of surface formate upon direct reaction of CO with alumina and magnesia

Characterization of supported iridium catalysts prepared from Ir4(CO)12

Interactions of cobalt carbonyls with oxide surfaces. 2. Dicobalt octacarbonyl and tetracobalt dodecacarbonyl on silicas and aluminas

Resonance Raman study of flavins and the flavoprotein fatty acyl coenzyme A dehydrogenase.