NO – oxygen scavenger or reaction intermediate in the decomposition of N2O?

Nitric oxide and nitrogen dioxide were found during the thermal desorption of surface species left on Fe-ferrierites after the decomposition of nitrous oxide. This demonstrates the formation of surface NOx species during N₂O decomposition. Repeated decomposition and subsequent desorption of surface species confirm the active role of surface NOx species. Addition of NO up to a fraction of 0.1 times the amount of N₂O increased the decomposition of nitrous oxide as well as the amount of surface NOx species. The use of nitrous oxide labeled with ¹⁸O demonstrated that the zeolite oxygens participate in the reaction and that the presence of NO enhances this participation.     

Semi-Empirical Calculations on the Stability and Reactivity of NH x Species on Metal Surfaces

The semi-empirical method of interacting bonds was used to elucidate the mechanism of oscillation phenomena in the NO + H₂ reaction on metal surfaces. Basic single-crystal planes of Pt, Rh, Ir, Fe, Ru, and Re were examined with respect to the stability of adsorbed NH _n species (n = 0, 1, 2, 3); to the reactivity of NH _n (n = 0, 1, 2) species toward adsorbed hydrogen atoms; and to the possibility of combination reactions between two NH or two NH₂ species resulting in the formation of gaseous N₂ molecules. All studied surfaces were found to form readily stable NH species. The principal difference between Pt, Rh, and Ir single-crystal planes exhibiting reaction rate oscillations, and Fe, Ru, and Re surfaces, which do not show an oscillatory behavior, is that the combination reaction of NH species can easily proceed in the former case, whereas this reaction is not allowed thermodynamically in the latter. This result is consistent with an earlier suggested model that attributes the oscillatory surface wave propagation to the intermediate formation of NH species.Stable NH₂ species can be formed on Ru, Re, and Fe surfaces, whereas the noble metal surfaces of Pt, Rh, and Ir can only form weakly stable NH₂ species at the very edge of their existence region. The combination reaction between two NH₂ species is endothermic in all cases.     

An overview: Comparative kinetic behaviour of Pt, Rh and Pd in the NO + CO and NO + H2 reactions

This paper reports a comparative kinetic investigation of the overall reduction of NO in the presence of CO or H₂ over supported Pt-, Rh- and Pd-based catalysts. Different activity sequences have been established for the NO+H₂ reaction Pt/Al₂O₃>Pd/Al₂O₃>Rh/Al₂O₃ and for the NO+CO reaction Rh/Al₂O₃>Pd/Al₂O₃> Pt/Al₂O₃. It was found that both reactions differ from the rate determining step usually ascribed to the dissociation of chemisorbed NO molecules. The rate enhancement observed for the NO+H₂ reaction has been mainly related to the involvement of a dissociation step of chemisorbed NO molecules assisted by adjacent chemisorbed H atoms. The calculation of the kinetic and thermodynamic constants from steady-state rate measurements and subsequent comparisons show that Pd and Rh are predominantly covered by chemisorbed NO molecules in our operating conditions which could explain either changes in activity or in selectivity with the lack of ammonia formation on Rh/Al₂O₃ during the NO+H₂ reaction. Interestingly, Pd and Rh exhibit similar selectivity behaviour towards the production of nitrous oxide (N₂O) irrespective of the nature of the reducing agent (CO or H₂). A weak partial pressure dependency of the selectivity is observed which can be related to the predominant formation of N₂ via a reaction between chemisorbed NO molecules and N atoms, while over Pt-based catalysts the associative desorption of two adjacent N atoms would occur simultaneously. Such tendencies are still observed under lean conditions in the presence of an excess of oxygen. However, a detrimental effect is observed on the selectivity with an enhancement of the competitive H₂+O₂ reaction, and on the activity behaviour with a strong oxygen inhibiting effect on the rate of NO conversion, particularly on Rh.     

Steady‐state N2O decomposition on Pt and Rh surfaces using a free‐jet molecular‐beam excited by nozzle heating

Steady‐state N₂O decomposition reaction on polycrystalline Pt and Rh surfaces has been studied using a supersonic free‐jet molecular beam (2.1 × 10¹⁸ molecules/cm² s). The energy of the incident N₂O beam was controlled by a nozzle heating technique in conjunction with a seeding technique. The decomposition rate shows both translational and vibrational energy dependence on the Pt surface. However, there is also the surface temperature dependence of the decomposition rate even varying the incident beam energy, indicating precursor‐mediated dissociation of N₂O on the Pt surface. On the other hand, no energy dependence was observed on the Rh surface, suggesting that the decomposition dynamics are different between Pt and Rh surfaces. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adsorbate-assisted NO decomposition in NO reduction by C3H6 over Pt/Al2O3 catalysts under lean-burn conditions

The rates and product selectivities of the C₃H₆-NO-O₂ and NO-H₂ reactions over a Pt/Al₂O₃ catalyst, and of the straight, NO decomposition reaction over the reduced catalyst have been compared at 240C. The rate of NO decomposition over the reduced catalyst is seven times greater than the rate of NO decomposition in the C₃H₆-NO-O₂ reaction. This is consistent with a mechanism in which NO decomposition occurs on Pt sites reduced by the hydrocarbon, provided only that at steady state in the lean NO _x reaction about 14% of the Pt sites are in the reduced form. However, the (extrapolated) rate of the NO-H₂ reaction at 240C is about 10⁴ times faster than the rate of the NO decomposition reaction thus raising the possibility that NO decomposition in the former reaction is assisted by H_ads. It is suggested that adsorbate-assisted NO decomposition in the C₃H₆-NO-O₂ reaction could be very important. This would mean that the proportion of reduced Pt sites required in the steady state would be extremely small. The NO decomposition and the NO-H₂ reactions produce no N₂O, unlike the C₃H₆-NO-O₂ reaction, suggesting that adsorbed NO is completely dissociated in the first two cases, but only partially dissociated in the latter case. It is possible that some of the associatively adsorbed NO present during the C₃H₆-NO-O₂ reaction may be adsorbed on oxidised Pt sites.     

Role of Zeolitic Oxygens During the Decomposition of 15N 2 18 O Over Fe-ferrierite

Isotopic species of dioxygen released during the decomposition of ¹⁵N₂¹⁸O over Fe-ferrierite show that the zeolite oxygens participate in the reaction. While Fe-ferrierite alone does not exchange its oxygens with ¹⁸O₂ below 400 °C, this exchange is very rapid in the mixture of ¹⁸O₂+N₂O. The amount of participating zeolite oxygen (ca. 1–6 per iron atom) is practically the same in the latter case as in the decomposition of ¹⁵N₂¹⁸O. The time dependence of individual dioxygen isotope species released during the ¹⁵N₂¹⁸O decomposition points to the primary release of ¹⁸O₂ which is very rapidly exchanged for the zeolite oxygen by a single-step mechanism.     

The positive effect of hydrogen on the reaction of nitric oxide with carbon monoxide over platinum and rhodium catalysts

The effect of adding 330–4930 ppm hydrogen to a reaction mixture of NO and CO (2000 ppm each) over platinum and rhodium catalysts has been investigated at temperatures around 200–250°C. Hydrogen causes large increases in the conversion of NO and, surprisingly, also of CO. Oxygen atoms from the additional NO converted are eventually combined with CO to give CO₂ rather than react with hydrogen to form water. This reaction is described by CO + NO +3/2H₂ CO₂ + NH₃ and accounts for 50–100% of the CO₂ formed with Pt/Al₂O₃ and 20–50% with Rh/Al₂O₃. With the latter catalyst a substantial amount of NO converted produces nitrous oxide. Comparison with a known study of unsupported noble metals suggests that isocyanic acid (HNCO) might be an important intermediate in a reaction system with NO, CO and H₂ present.     

High Efficiency of Noble Metal and Metal Oxide Catalyst Systems for the Selective Reduction of NO with Propene in Lean Exhaust Gas

An investigation was conducted of noble metal and metal oxide catalysts deposited on Al₂O₃. The noble metals Pt, Pd, Rh the metal oxides CuO, SnO₂, CoO, Ag₂O, In₂O₃, catalysts were examined. Also investigated were noble metal Pt, Pd, Rh-doped In₂O₃/Al₂O₃ catalysts prepared by single sol–gel method. Both were studied for their capability to reduce NO by propene under lean conditions. In order to improve the catalytic activity and the temperature window, the intermediate addition propene between a Pt/Al₂O₃ oxidation and metal oxide combined catalyst system was also studied. Pt/Al₂O₃ and In₂O₃/Al₂O₃ combined catalyst showed high NO reduction activity in a wider temperature window, and more than 60% NO conversion was observed in the temperature range of 300–550 °C.     

Nitrous Oxide Reduction with Ammonia and Methane Over Mesoporous Silica Materials Modified with Transition Metal Oxides

Transition metal oxides (Cu, Cr and Fe) were deposited on various mesoporous silicas (MCM-48, SBA-15, MCF and x-MSU) by an impregnation method. Electron microprobe analysis, BET, UV-VIS-DRS and temperature programmed desorption of NH₃ were used for the characterization of the samples. The modified mesoporous silicas were tested as catalysts of the N₂O decomposition and the N₂O reduction using ammonia and methane. The Cu-containing samples presented the highest catalytic activity in the N₂O decomposition, while the Cr- and Fe-modified materials were more active in the reduction of nitrous oxide with NH₃ and CH₄. The type of the silica support strongly influenced the catalytic performance of the studied materials.     

Catalytic Performance and Sulfur Dioxide Resistance of One-Pot Synthesized Fe-MCM-22 in Selective Catalytic Reduction of Nitrogen Oxides with Ammonia (NH3-SCR)—The Effect of Iron Content

The catalytic performance of Fe-catalysts in selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR) strongly depends on the nature of iron sites. Therefore, we aimed to prepare and investigate the catalytic potential of Fe-MCM-22 with various Si/Fe molar ratios in NH₃-SCR. The samples were prepared by the one-pot synthesis method to provide high dispersion of iron and reduce the number of synthesis steps. We have found that the sample with the lowest concentration of Fe exhibited the highest catalytic activity of ca. 100% at 175 °C, due to the abundance of well-dispersed isolated iron species. The decrease of Si/Fe limited the formation of microporous structure and resulted in partial amorphization, formation of iron oxide clusters, and emission of N₂O during the catalytic reaction. However, an optimal concentration of Fe_xO_y oligomers contributed to the decomposition of nitrous oxide within 250–400 °C. Moreover, the acidic character of the catalysts was not a key factor determining the high conversion of NO. Additionally, we conducted NH₃-SCR catalytic tests over the samples after poisoning with sulfur dioxide (SO₂). We observed that SO₂ affected the catalytic performance mainly in the low-temperature region, due to the deposition of thermally unstable ammonium sulfates.     

Catalytic decomposition of N2O over supported rhodium catalysts: high activities of Rh/USY and Rh/Al2O3 and the effect of Rh precursors

The catalytic decomposition of nitrous oxide to nitrogen and oxygen has been studied over Al₂O₃-supported and zeolite-supported Rh catalysts. The activities of Rh/Al₂O₃ and Rh/USY (ultrastable Y zeolite) catalysts prepared from Rh(NO₃)₃ were higher than those of Rh/ZSM-5 and Rh/ZnO reported in the literature, while the activity of a Rh/Al₂O₃ catalyst prepared from RhCl₃ was suppressed severely in spite of the high H/Rh and CO/Rh values. The catalytic activity of N₂O decomposition was sensitive not only to the Rh dispersion but also to the preparation variables such as the Rh precursors and the supports used. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic activity of Fe ions in iron-based crystalline and amorphous systems: role of dispersion,coordinative unsaturation and Al content

Different Fe-based materials, where iron ions are anchored on crystalline and amorphous siliceous supports are studied by FTIR spectroscopy of adsorbed NO and in the N₂O decomposition reaction test. The influence of Al concentration is also considered. We show that the coordination state of Fe dramatically changes when Fe is anchored on crystalline or amorphous matrices. In crystalline Fe-ZSM-5 and Fe-silicalite samples highly coordinatively unsaturated and isolated Fe sites are present, which form Fe²⁺(NO)₂ and Fe²⁺(NO)₃ complexes upon NO contact. The presence of oxidic clusters, forming Fe²⁺(NO) complexes, whose relative concentration strictly depends upon the presence of Al and the concentration of Fe, is also evidenced. Fe-ZSM-5 sample (Si/Fe = 1120) mainly contains isolated Fe²⁺ ions characterised by high coordinative unsaturation. This sample also shows the highest activity in N₂O decomposition, indicating that isolated and coordinatively unsaturated Fe sites are the most active precursors for the catalytic reaction. It is thought that adsorbed oxygen is formed, upon N₂O decomposition, on both isolated and oxidic clusters, forming ferryl groups in the former case and bridged structures in the latter.     

Chemically resolved dynamical imaging of catalytic reactions on composite surfaces

The catalytic reduction of NO by hydrogen is investigated at (T = 650 K and (p≈10^-6 mbar on a microstructured Rh/Pt(100) surface consisting of Pt(100) domains surrounded by a 600 Åthick Rh film. Synchrotron radiation scanning photoemission microscopy (SPEM), using photons focused into a spot of less than 0.2 μm diameter, is employed as a spatially and chemically resolving in situ technique. The chemical waves which arise in the bistable system NO+H₂/Rh are imaged with SPEM monitoring the N 1s and O 1s photoelectrons. The reaction fronts initiate transitions from an inactive oxygen-covered surface (Θ_O≈0.25 ML) to a reactive nitrogen-covered surface (Θ_N≈0.06 ML). At the Pt/Rh interface, synergetic effects can be observed: the chemical waves on the Rh film nucleate preferentially at the Pt/Rh interface. This nucleation is poisoned by carbon contamination on the Pt area but is prevented in the vicinity of the Pt/Rh interface by the adjacent clean Rh film. No segregation of Pt to the surface was observed for the 600 Å thick Rh film.     

Synthesis gas formation by direct oxidation of methane over Rh monoliths

The production of H₂ and CO by catalytic partial oxidation of CH₄ in air or O₂ at atmospheric pressure has been examined over Rh-coated monoliths at residence times between 10^–4 and 10^–2 s and compared to previously reported results for Pt-coated monoliths. Using O₂, selectivities for H₂ ( ) as high as 90% and CO selectivities (S _CO) of 96% can be obtained with Rh catalysts. With room temperature feeds using air, Rh catalysts give of about 70% compared to only about 40% for Pt catalysts. The optimal selectivities for either Pt or Rh can be improved by increasing the adiabatic reaction temperature by preheating the reactant gases or using O₂ instead of air. The superiority of Rh over Pt for H₂ generation can be explained by a methane pyrolysis surface reaction mechanism of oxidation at high temperatures on these noble metals. Because of the higher activation energy for OH formation on Rh (20 kcal/mol) than on Pt (2.5 kcal/mol), H adatoms are more likely to combine and desorb as H₂ than on Pt, on which the O+ H OH reaction is much faster.This research was partially supported by DOE under Grant No. DE-FG02-88ER13878-AO2.     

Denitrification in aqueous FeEDTA solutions

The biological reduction of nitric oxide (NO) in aqueous solutions of FeEDTA is an important key reaction within the BioDeNOx process, a combined physico‐chemical and biological technique for the removal of NO_x from industrial flue gasses. To explore the reduction of nitrogen oxide analogues, this study investigated the full denitrification pathway in aqueous FeEDTA solutions, ie the reduction of NO₃^?, NO₂^?, NO via N₂O to N₂ in this unusual medium. This was done in batch experiments at 30 °C with 25 mmol dm^?3 FeEDTA solutions (pH 7.2 ± 0.2). Also Ca²⁺ (2 and 10 mmol dm^?3) and Mg²⁺ (2 mmol dm^?3) were added in excess to prevent free, uncomplexed EDTA. Nitrate reduction in aqueous solutions of Fe(III)EDTA is accompanied by the biological reduction of Fe(III) to Fe(II), for which ethanol, methanol and also acetate are suitable electron donors. Fe(II)EDTA can serve as electron donor for the biological reduction of nitrate to nitrite, with the concomitant oxidation of Fe(II)EDTA to Fe(III)EDTA. Moreover, Fe(II)EDTA can also serve as electron donor for the chemical reduction of nitrite to NO, with the concomitant formation of the nitrosyl‐complex Fe(II)EDTA–NO. The reduction of NO in Fe(II)EDTA was found to be catalysed biologically and occurred about three times faster at 55 °C than NO reduction at 30 °C. This study showed that the nitrogen and iron cycles are strongly coupled and that FeEDTA has an electron‐mediating role during the subsequent reduction of nitrate, nitrite, nitric oxide and nitrous oxide to dinitrogen gas. Copyright © 2004 Society of Chemical Industry     

Behavior of Active Oxygen During the Decomposition of Nitrous Oxide Over Fe-FER

Isotope exchange (I.E) of ¹⁸O₂ for oxygen captured in Fe-FER after decomposition of nitrous oxide proceeds readily even at room temperature, provided that the amount of surface NO _x species, formed as a secondary product of the N₂O decomposition, is relatively low. If ¹⁸O₂ is present during the decomposition of nitrous oxide above 250 °C, or if nitrous oxide labeled with ¹⁸O is employed, ¹⁸O appears also in NO _x species, and I.E easily occurs with zeolite framework oxygens.     

Effect of Pt addition on vanadium-incorporated TiO2 catalysts for photodecomposition of ammonia

This study investigated the effect of adding Pt components to V-TiO₂ for highly concentrated ammonia photodecomposition. Pt components were introduced to the V-TiO₂ photocatalysts by using two method types: the common sol-gel (Pt-V-TiO₂) and impregnation (Pt/V-TiO₂) methods. The observed X-ray diffraction (XRD) peaks were assigned to V₂O₅ at 19.5, 27.5 and 30.20° in V-TiO₂, and to Pt metals at 39.80° (111) in Pt/V-TiO₂. The Pt component of Pt-V-TiO₂ was identified at Pt²⁺ from the Pt4f_7/2 and Pt4f_5/2 bands at 73.6 and 77.4 eV in XPS bands, respectively, but the band was shifted to a lower binding energy in Pt/V-TiO₂. The H₂ temperature-programmed reduction (TPR) curves showed that the temperature of reduction from Ti³⁺ to Ti⁰ was decreased by Pt addition and that the area was larger in Pt-V-TiO₂ than in Pt/V-TiO₂. The NH₃ decomposition was slightly increased with vanadium addition compared to that of pure TiO₂, and the decomposition was further enhanced with Pt addition. Particularly, the NH₃ (1,000 ppm) decomposition reached 100% over Pt/V-TiO₂ after 120 min, although about 10–30% of the ammonia was converted into undesirable NO₂ and NO.     

Highly active and stable bimetallic Ir/Fe-USY catalysts for direct and NO-assisted N2O decomposition

The current research investigated N₂O decompositions over the catalysts Ir/Fe-USY, Fe-USY and Ir-USY under various conditions, and found that a trace amount of iridium (0.1 wt%) incorporated into Fe-USY significantly enhanced N₂O decomposition activity. The decomposition of N₂O over this catalyst (Ir/Fe-USY-0.1%) was also partly assisted by NO present in the gas mixture, in contrast to the negative effect of NO over noble metal catalysts. Moreover, Ir/Fe-USY-0.1% can decompose more than 90% at 400 °C (i.e. the normal exhaust temperature) under simulated conditions of a typical nitric acid plant, e.g. 5000 ppm N₂O, 5% O₂, 700 ppm NO and 2% H₂O in balance He, and such an activity can be kept for over 110 h under these strict conditions. The excellent properties of bimetallic Ir/Fe-USY-0.1% catalyst are presumably related to the good dispersion of Fe and Ir on the zeolite framework, the formation of framework Al–O–Fe species and the electronic synergy between the Ir and Fe sites. The reaction mechanism for N₂O decomposition has been further discussed on the temperature-programmed desorption profiles of O₂, N₂ and NO₂.     

Influence of the Oxidation State of Rhodium in Three-Way Catalysts on Their Catalytic Performances: An in situ FTIR and Catalytic Study

Simultaneous IR spectroscopic and catalytic measurements have been performed in order to investigate the nature of adsorbed species involved in the formation of N₂O on Rh/Al₂O₃ in the course of the CO + NO reaction. Only nitrosyl species have been isolated that could be involved in the formation of N₂ and N₂O in accordance with previous kinetic investigations [Granger et al. J. Catal. 175(1998) 194]. Sequential and simultaneous NO and CO exposures lead to the observation of different nitrosyl species that could act as intermediates in the formation of N₂ and N₂O. Correlations between the appearance/disappearance of Rh(NO) ⁺ species and an extra formation of N₂O have been established.     

Promoting Effect of Pt Addition to V2O5/ZrO2 Catalyst on Reduction of NO by C3H6

The effect of Pt addition to a V₂O₅/ZrO₂ catalyst on the reduction of NO by C₃H₆ has been studied by FTIR spectroscopy as well as by analysis of the reaction products. Pt loading promoted the catalytic activity remarkably. FTIR spectra of NO adsorbed on the catalysts doped with Pt show the presence of two different types of Pt sites, Pt oxide and Pt cluster, on the surface. The amount of these sites depends on Pt contents and the catalyst state. Pt atoms highly disperse on the surface as Pt oxide at low Pt content, being aggregated into Pt metal clusters by increasing Pt amount or reducing the catalysts. The spectral behavior of V=O bands on the surface also supports the formation of Pt clusters. It is concluded that Pt promotes the NO–C₃H₆ reaction through a reduction–oxidation cycle between its oxide and cluster form.