The Mechanism of Low-Temperature Ammonia Oxidation on Metal Oxides According to the Data of Spectrokinetic Measurements

Low temperature ammonia oxidation on MoO₃, Fe₂O₃, Cr₂O₃, and ZnO is studied by the spectrokinetic method. It is shown that the following adsorbed species are intermediates in this reaction: NH₃ and N₂O on Fe₂O₃ and ZnO; NH₃, N₂O, and NO on Cr₂O₃. All of the detected intermediates are used to construct the mechanism of the process. In the framework of the proposed mechanism, stationary and nonstationary spectral and kinetic data are quantitatively processed. The dependence of the rate constants of the same steps on different oxides on their physicochemical properties is discussed.     

Effect of the nanoparticle size of supported copper-containing catalysts on their activity in the selective oxidation of CO in an excess of H<Subscript>2</Subscript>

The catalytic properties of systems prepared by the supporting of CuO onto CeO₂, ZrO₂, and Zr_0.5Ce_0.5O₂ with particle sizes of 15–25 nm (nitrate pyrolysis (p)) and 5–6 nm (microemulsion method (me)) in the reaction of CO oxidation in an excess of H₂ were studied. In the latter case, the supports had an almost homogeneous surface and a small number of defects. The catalytic activity of (me) and (p) supports was low and almost the same, whereas the catalytic activity of CuO/(CeO₂, ZrO₂, and Zr_0.5Ce_0.5O₂)(me) samples was lower than that of CuO/(CeO₂ and ZrO₂)(p). The maximum CO conversion (∼100% at 125°C) was observed on 5% CuO/CeO₂ (p). The CO and CO₂ adsorption species on (p) and (me) catalysts were studied by TPD. Differences in the compositions of copper-containing centers on the surfaces of (p) and (me) systems were found using TPR. The nature of the active centers of CO oxidation and the effect of support crystallite size on the catalytic activity were considered.     

Reactivity of surface complexes in the selective catalytic reduction of NO x on supported heteropoly compounds

The reactivity of surface complexes in the selective catalytic reduction of NO _x on supported heteropoly compounds has been investigated by in situ IR spectroscopy. The best performance is shown by CeO₂-supported catalysts. The conversion rate of the intermediate nitrate complexes obeys a zeroth-order equation, like the formation rate of the propylene activation products, namely, surface acetate and formate complexes. The conversion rate of the surface nitrate complexes is determined by the propylene oxidation selectivity, which, in turn, is related to the composition of the heteropoly compound. Among the heteropoly compounds examined, the most appropriate ones are those in which vanadium ions are in both anionic and cationic positions. These pair sites serve to activate propylene, and the activation product reacts efficiently with the nitrate complexes.     

Study of the mobility of lattice oxygen in complex oxide catalysts for partial oxidation of propylene to acrolein

The amount of oxygen in the lattice of solids that participates in the elementary stages of partial propylene oxidation is determined for two types of Co-Mo-Bi-Fe-Sb-K-O catalysts (I, II) differing in the method of introduction of antimony and potassium. Two independent methods are used: (1) on the basis of the yield of the oxygen-containing products of propylene oxidation by oxygen of the catalyst in a pulse regime and (2) with the use of Möessbauer spectroscopy. Coincidence of the results obtained by both methods indicates that the active oxygen of the catalyst lattice is formed during redox transformations of iron(III) molybdate entering the composition of the catalysts. Data on the reduction of the catalysts in a pulse regime at various temperatures, which were processed in the framework of the diffusion model, allowed the estimation of the rate constants for diffusion of the lattice oxygen. An increase in the mobility of the lattice oxygen in catalyst I, which is modified with a small amount of antimony as compared to catalyst II, results in an increase in the overall productivity of the sample and in a decrease in the selectivity of propylene oxidation to acrolein. This correlates with the increase in the total amount of the lattice oxygen participating in the process.     

CO oxidation with oxygen of the catalyst and gas-phase oxygen over (0.5−15)%СоО/СеО<Subscript>2</Subscript>

The CO adsorption species on Co₃O₄ and (0.5-15%)CoO/CeO₂ catalysts have been investigated by temperature-programmed desorption and IR spectroscopy. At 20°C, the largest amount of CO is adsorbed on the 5%CoO/CeO₂ sample to form, on Co_m²⁺O_n²⁺ clusters, hydrogen-containing, bidentate, and monodentate carbonate complexes, whose decomposition is accompanied by CO₂ desorption at 300 and 450°C (1.1 × 10²⁰ g^–1). The formation of the carbonates is accompanied by the formation of Co⁺ cations and Co⁰, on which carbonyls form. The latter decompose at 20, 90, and 170°C to release CO (2.7 × 10¹⁹ g^–1). Part of the carbonyls oxidizes to CO₂ upon oxygen adsorption, and the CO₂ undergoes desorption at 20°C. Adsorbed oxygen decreases the decomposition temperature of the H-containing and bidentate carbonates from 300 to 100-170°C and maintains the sample in the oxidized state, which is active in subsequent CO adsorption and oxidation. CO oxidation by oxygen of the catalyst diminishes the activity of the sample in these processes and increases the decomposition temperature of the carbonate complexes. Taking into account the properties of the adsorption complexes, we concluded that the H-containing and bidentate carbonates are involved in CO oxidation by oxygen of the catalyst at ~170°C under isothermal conditions. The rate limiting step is the decomposition of the carbonates, a process whose activation energy is 65-74 kJ/mol.     

The mechanism of selective NOx reduction by hydrocarbons in excess oxygen on oxide catalysts: V. Adsorption properties of a commercial Ni-Cr oxide catalyst

According to X-ray diffraction analysis data, the test catalyst was a Ni-Cr spinel with an impurity of NiO. With the use of in situ IR spectroscopy, it was found that nitrite, nitrate, and acetate surface complexes occurred under the reaction conditions of the selective catalytic reduction of nitrogen oxides by propane in the presence of oxygen on the nickel-chromium catalyst. As the temperature was increased, the nitrite complexes were converted into nitrate species. The molar absorption coefficient of surface nitrate complexes was determined. According to IR-spectroscopic and TPD data, the nitrate complexes were bound relatively weakly to the surface. The temperature region of their existence was 50–200°C. The temperature region of existence of the surface acetate complexes was 200–400°C. The individual adsorption of oxygen was not observed; however, oxygen-containing surface sites (Cr⁵⁺=O) participated in the formation of the surface complexes of reactants.     

Time-resolved chemically induced dynamic nuclear polarization studies of structure and reactivity of methionine radical cations in aqueous solution as a function of pH

Using time-resolved chemically induced dynamic nuclear polarization (CIDNP) techniques, we have studied the mechanism of the photoreactions of triplet excited 4-carboxybenzophenone (CBP) with l-methionine (Met) and 3-(methylthio)propylamine (MTPA) in aqueous solution and the details of the formation of CIDNP at pH from 6.7 to 13.6. At a pH below the pKa of the nitrogen atom of Met, the CIDNP is strongly affected by degenerate electron exchange between the S-S cationic radical dimer and the zwitterionic form of Met with the rate constant kex = 3.4 x 10(8) s(-1) providing an exhaustive explanation of the pH dependence of steady-state CIDNP that was previously interpreted as a manifestation of fast interconversion among three different methionine radical species (Goez, M.; Rozwadowski, J. J. Phys. Chem. A 1998, 102, 7945-7953). By analyzing the polarization of different protons formed in geminate recombination as a function of the pH, we obtained the branching ratio between two reaction pathways for oxidative quenching of (T)CBP via electron transfer from the sulfur and nitrogen atoms of Met and MTPA. Nuclear spin-lattice relaxation times were determined in the dimeric cation radical of Met (T1,S = 8.5 micros). In the cyclic radical cation of MTPA with a three-electron two-center S-N bond, the estimated paramagnetic relaxation is comparatively slow for all protons. Fast deprotonation of the primary aminium radical cation of MTPA and Met in strongly basic solution takes place on the submicrosecond time scale leading to efficient formation of CIDNP in the neutral aminyl radical.     

IR luminescence of bismuth-containing centers in materials prepared by impregnation and thermal treatment of porous glasses

The properties of bismuth-containing luminescent materials prepared by impregnating a porous glass with an aqueous solution of bismuth and aluminum salts followed by thermal treatment are studied. The formation of a variety of bismuth-containing centers luminescent in the near infrared range of the spectrum is revealed, one of which is the Bi⁺ monocation. At high temperatures, along with it, bismuth-containing cluster-type luminescent centers are apparently formed.