Characterization of supported Pd-Pt catalysts by chemical probes

The temperature programmed (palladium) hydride decomposition appeared very effective method for diagnosing the extent of alloying in Pd-Pt/SiO₂ catalysts. Introduction of Pt to Pd catalysts moves the TPHD peak gradually towards lower temperatures and the shift in hydride decomposition peak is accompanied by a decrease in the amount of released hydrogen. The catalysts prepared the direct redox method showed much better alloy homogeneity than the samples prepared by coimpregnation. The results of probing with other techniques, i.e. catalytic probing with hydrodechlorination of CCl₂F₂ and XRD, were in line with TPHD data. The catalytic probing showed the presence of synergistic effect, a clear indication of Pd-Pt mixing. XRD data of post-reaction samples showed carbon incorporation into Pd-rich phase, whereas separate Pt-rich phase did not experience any bulk carbiding.     

Influence of water and ammonia on hydrotreating catalysts and activity for tetralin hydrogenation

The effects of H₂O and NH₃ on the kinetics of the liquid phase hydrogenation of tetralin to decalin at 6.9 MPa and 330°C over commercial P---Ni---Mo/alumina catalysts in the presence of H₂S have been investigated. H₂O functioned as a mild kinetic inhibitor to an extent sensitive to the H₂S level. Quasi in situ XPS was used to investigate the catalyst structure after exposure to H₂0/H₂S.     

Preparation of nickel-tungstate catalysts by a novel impregnation method

Nickel-tungstate/γ-alumina (NiW) catalysts were prepared by an incipient wetness impregnation method using citric acid as a complexing agent. Citric acid has been used by our research group in preparing cobalt-molybdate and nickel -molybdate catalysts. The extended X-ray absorption fine structure (EXAFS) data of the impregnating solutions indicated that citric acid contributes to the formation of polytungstate anions that are smaller than the dodecatungstate ions formed when conventional ammoniacal solutions are used. Sulfided NiW catalysts prepared by using citric acid showed higher hydrogenation activity and hydrogenation selectivity than NiW catalysts prepared using the conventional ammoniacal solutions.     

Adaptation of the microscopic properties of redox catalysts to the type of gas-solid reactor

Catalysts of selective oxidation usually work in a simultaneous redox mode in reactant/air cofed reactors. The solid must provide selective lattice oxygen according to a kinetic mechanism depending on operating conditions that differ from one reactor to another. Better catalytic performance can be obtained in a recirculating solids reactor because it allows separate optimization of the reduction and oxidation steps. Among the microscopic properties of the catalyst, the crystal morphology is to be taken into account because it influences its reactivity on stream. These considerations lead to a new approach of the catalyst-reaction-reactor trio.     

Spatially resolved infrared spectroscopy: a novel technique for in situ study of spatial surface coverage during CO oxidation on supported catalysts

A spatially resolved infrared (IR) imaging technique to monitor the linear adsorbed CO coverage on supported catalyst surface combining an IR bandpass filter and an IR thermography camera has been developed. Images acquired during the CO adsorption/desorption and ignition indicate that the technique provides an excellent method to image the change of surface coverage with a spatial resolution. It is expected that the combination of infrared thermography with spatially resolved imaging of surface coverage will provide a deeper insight in the dynamics of spatio-temporal patterns on heterogeneous catalysts.     

Ammoxidation of methylaromatics over vanadium phosphate catalysts II. Catalyst formation, active sites and reaction mechanism

The interactions of VOHPO₄· 0.5H₂O and (VO)₂P₂O₇ with the ammoxidation feed and the single components such as ammonia, oxygen, water and component mixtures were studied in detail using XRD and temperature-programmed reaction spectroscopy. The aim of this work was to improve the knowledge of the formation of the active phases or active sites of the catalysts from their precursors under the condition of the ammoxidation reaction. Similar catalytic properties of various applied VPO materials were discussed in terms of the presence of similar structure elements (domains of adjacent edge-sharing VO₆ octahedra-units and P-O-NH₄ groups).     

Aromatics saturation by sulfided Nickel---Molybdenum hydrotreating catalysts

The effect of H₂S on the rates of toluene hydrogenation of sulfided Mo, Ni, Ni---Mo and Ni---Mo---P/alumina catalysts has been determined at 6 MPa, 350°C over a large range of H₂S partial pressure. In those conditions, Ni/alumina is nearly inactive. For the three other catalysts, similar trends are found with in particular no effect of H₂S at high partial pressure. In the presence of NH₃, the effect of H₂S remains globally the same.     

Nitrogen dioxide effect in the reduction of nitric oxide by propane in oxidizing atmosphere

The role of nitrogen dioxide in the selective reduction of NO by propane over a Cu-MFI zeolite is investigated. NO₂ and NO reductions were carried out under similar conditions of reaction. In the presence of oxygen, the reduction of NO by C₃H₈ does not differ significantly from that of NO₂. In the absence of oxygen, the reduction of NO₂ by propane occurs with a partial decomposition of the nitric dioxide molecule. Such a decomposition leads to the formation of oxygen, which is responsible for the increase in catalytic activity by comparison with the same reaction performed with NO. NO₂ formed and released in the gas phase during the reduction of NO by propane in the presence of oxygen does not play a predominant role in the catalytic process.     

Partial oxidation of methane towards hydrogen production over a promising class of catalysts: Rh supported on Ti-modified MgO

The partial oxidation of methane over the supported Rh (0.8 wt.%) catalysts was investigated. Two kinds of supports were used, MgO and Ti-modified MgO (prepared by grafting technique). Among the Ti-modified MgO supports, two different compounds were used as source of Ti: inorganic (chloride) and organic (alkoxide). The catalytic performance of Rh-supported catalysts depends on the support and varies in the sequence: Ti-MgO/I > Ti-MgO/O > MgO. Ti-containing catalysts exhibited higher activity and selectivity compared to MgO, which is especially noticeable at low temperature. Possible explanations for the phenomena observed were proposed on the basis of characterization results.     

IR spectroscopic study of Pt/Kl zeolites using adsorption of CO as a molecular probe

FTIR spectra of CO adsorbed on Pt/KL catalysts show that the relative band intensities and the total dispersion markedly depend on the catalyst preparation method (ion exchange, incipient wetness impregnation or co-impregnation with KCl). The CO stretching frequency of the dominant band for linear CO is shifted to higher wavenumbers, parallel with the proton concentration in the reduced catalyst, which is derived independently from the intensity of the IR bands of the OH groups. The results are in accordance with the model that electron-deficient platinum particles are platinum-proton adducts.On leave from: N.D. Zelinsky Institute of Organic Chemistry, Academy of Sciences, Moscow, USSR.