Direct decomposition of nitrous oxide in the presence of oxygen over iridium catalyst supported on alumina

Direct decomposition of nitrous oxide (N₂O) on noble metal catalysts supported on alumina was examined in the presence of oxygen. The iridium catalysts supported on alumina showed higher activities than the other noble metal catalysts. Although the catalyst activity was affected by oxygen formed by N₂O decomposition at lower temperatures, desorption of oxygen proceeded promptly at the temperature , and the catalytic activity was recovered by increasing the reaction temperature from 350 to . Therefore, the Ir/Al₂O₃ catalyst can be used for N₂O decomposition in the presence of oxygen at relatively higher temperatures.     

Isotopic Study of N2O Decomposition on an Ion-Exchanged Fe-Zeolite Catalyst: Mechanism of O2 Formation

N₂O decomposition on an ion-exchanged Fe-MFI catalyst has been studied using an ¹⁸O-tracer technique in order to reveal the reaction mechanism. N₂ ¹⁶O was pulsed onto an ¹⁸O₂-treated Fe-MFI catalyst at 693 K, and the O₂ molecules produced were monitored by means of mass spectrometry. The ¹⁸O fraction in the produced oxygen had almost half the value of that on the surface oxygen, and ¹⁸O¹⁸O was not detected. The result shows that O₂ formation proceeds via the Eley–Rideal mechanism (N₂ ¹⁶O + ¹⁸O(a) N₂ + ¹⁶O¹⁸O).     

FTIR study of the photoinduced dissociation of CO2 on titania-supported noble metals

The effect of illumination on the activation and dissociation of CO₂ was investigated at 190 and 300 K on titania-supported noble metals by means of Fourier transform infrared spectroscopy. The photoinduced dissociation of CO₂ (through the formation of resulting in CO_(a) occurred on Pt/TiO₂, Rh/TiO₂ and Ir/TiO₂; no CO_(a) formation, however, was observed on Pd/TiO₂ and Ru/TiO₂. It is assumed that the CO₂ on supported noble metals is bonded to the surface with both C (linked to a noble metal atom) and one of the O atoms (linked to the oxygen vacancy of the supports), and an extended charge transfer induced by illumination leads to the cleavage of a C–O bond. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic Conversion of N2O to N2 over Metal-Based Catalysts in the Presence of Hydrocarbons and Oxygen

The catalytic conversion of N₂O to N₂ in the presence or the absence of propene and oxygen was studied. The catalysts examined in this work were synthesized impregnating metals (Rh, Ru, Pd, Co, Cu, Fe, In) on different supports (Al₂O₃, SiO₂, TiO₂, ZrO₂ and calcined hydrotalcite MgAl₂(OH)₈·H₂O). The experimental results varied both with the type of the active site and with the type of the support. Rh and Ru impregnated on -alumina exhibited the highest activity. The performance of the above most promising catalysts was studied using various hydrocarbons (CH₄, C₃H₆, C₃H₈) as reducing agents. These experimental results showed that the type of reducing agent does not affect the reaction yield. The temperature where complete conversion of N₂O to N₂ was measured was independent of the reductant type. The activity of the most active catalysts was also measured in the presence of SO₂ and H₂O in the feed. A shift of the N₂O conversion versus temperature curve to higher temperatures was observed when SO₂ and H₂O were added, separately or simultaneously, to the feed. The inhibition caused by SO₂ was attributed to the formation of sulfates and that caused by water to the competitive chemisorption of H₂O and N₂O on the same active sites.     

Carbon dioxide absorption kinetics in potassium threonate

The absorption of carbon dioxide in potassium threonate aqueous solutions is studied at concentrations ranging from 0.1 to 3 M and temperatures from 293 to 313 K. This study includes experimental density, viscosity, solubility of N₂O and absorption kinetics of CO₂ (using a stirred cell reactor) data obtained for the various potassium threonate solutions. The diffusion coefficients of CO₂ and potassium threonate in the absorption solutions are estimated using a modified Stokes-Einstein relation. N₂O solubility is interpreted using the Schumpe [1993. The estimation of gas solubilities in salt-solutions. Chemical Engineering Science 48(1), 153-158] model and CO₂ physical solubility estimated. Physical absorption experiments were performed in the stirred cell in order to determine the physical mass transfer coefficients. The kinetics results are interpreted using both the pseudo-first-order and the DeCoursey approaches. It was concluded that CO₂ absorption in the aqueous potassium threonate solutions is well represented by

     

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.     

The photocatalytic reduction of nitrous oxide with propane on lead(II) ion-exchanged ZSM-5 catalysts

UV irradiation of the Pb²⁺/ZSM-5 catalyst prepared by an ion-exchange method in the presence of N₂O leads to the decomposition of N₂O into N₂. This reaction is found to be dramatically enhanced by the addition of propane to produce N₂ and oxygen-containing compounds such as ethanol or acetone. UV light effective for the reaction lies in wavelength regions shorter than 250 nm where the absorption band of the Pb²⁺ ion ([Xe] 4f¹⁴5d¹⁰6s² [Xe] 4f¹⁴5d¹⁰6s¹6p¹) exists, indicating that the excited state of the isolated Pb²⁺ ions plays a significant role in this decomposition of N₂O both in the absence and the presence of propane, and the role of propane is found to be a capture of oxygen atoms formed by the decomposition of N₂O.     

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

We have studied a reaction between the reduced form of titanocene dichloride (Cp₂TiCl₂) and a group of organic halides: benzyl derivatives (4-XC₆H₄CH₂Cl, X = H, NO₂, CH₃; 4-XC₆H₄CH₂Br, X = H, NO₂, PhC(O); 4-XC₆H₄CH₂SCN, X = H, NO₂) as well as three aryl halides (4-NO₂C₆H₄Hal, Hal = Cl, Br; 4-CH₃O-C₆H₄Cl). It has been shown that the electrochemical reduction of Cp₂TiCl₂ in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic CHal bond cleavage.The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.     

FTIR study of NO, C3H6 and O2 adsorption and interaction on gold modified MCM-41 materials

This paper is devoted to the detailed FTIR study of the adsorption, co-adsorption, and interaction of all the reagents used in NO HC-SCR process addressed to lean-burn engines with the surface of new gold catalysts based on ordered mesoporous materials. Gold was introduced into silicate and niobiosilicate matrices by the impregnation (Au/MCM-41 and Au/NbMCM-41, respectively) and via co-precipitation with siliceous and niobium sources (AuNbMCM-41). The in situ FTIR study allowed the estimation of the possible chemisorption of the reagents and their interaction towards intermediates, depending on the chemical composition of the catalyst and the way of gold introduction. It has been found that propene is chemisorbed, but not, NO, on gold species at room temperature. Chemisorbed C₃H₆ interacts with NO only in the presence of oxygen excess. Oxygen oxidizes NO to NO₂, the latter interacts with chemisorbed propene towards carboxylates (1570 cm⁻¹) and NO₂ is reduced to N₂O. At higher temperatures carboxylates interact with gaseous NO to carbonate, N₂O, CO and CO₂. The presence of niobium in the NbMCM-41 matrix enhances the oxidative properties of the catalysts and as a consequence the interaction between intermediates in NO reduction with propene in the oxygen excess. The co-precipitated AuNbMCM-41 exhibits higher NOx storage properties than the impregnated one.     

Nitrous oxide formation potential of various humid tropic soils of Malaysia: A laboratory study

Nitrous oxide (N₂O) is formed mainly during nitrification and denitrification. Inherent soil properties strongly influence the magnitude of N₂O formation and vary with soil types. A laboratory study was carried out using eight humid tropic soils of Malaysia to monitor NH₄ ⁺ and NO₃ ^– dynamics and N₂O production. The soils were treated with NH₄NO₃ (100 mg N kg^–1 soil) and incubated for 40 days at 60% water-filled pore space. The NH₄ ⁺ accumulation was predominant in the acid soils studied and NO₃ ^– accumulation/disappearance was either small or stable. However, the Munchong soil depicted the highest peak (238 g N₂O-N kg^–1 soil d^–1) at the beginning of the incubation, probably through a physical release. While the Tavy soil showed some NO₃ ^– accumulation at the end of the study with a maximum N₂O flux of 206 g N₂O-N kg^–1 soil d^–1, both belong to Oxisols. The other six soils, viz. Rengam, Selangor, Briah, Bungor, Serdang and Malacca series, formed smaller but maximum peaks in an decreasing order of 116 to 36 g N₂O-N kg^–1 soil d^–1. Liming the Oxisols and Ultisols raised the soil pH, resulting in NO₃ ^– accumulation and N₂O production to some extent. As such the highest N₂O flux of 130.2 and 77.4 g N₂O-N kg^–1 soil d^–1 was detected from the Bungor and Malacca soils, respectively. The Selangor soil, belonging to Inceptisol, did not respond to lime treatment. The respective total N₂O formations were 3.63, 1.92 and 1.69 mg N₂O-N kg^–1 soil from the Bungor, Malacca and Selangor soils, showing an increase by 49 and 99% over the former two non-limed soils. Under non-limed conditions, the indigenous soil properties, viz. Ca⁺⁺ content, %clay, %sand and pH of the soils collectively could have influenced the total N₂O formation.     

N2O decomposition over K-promoted Co-Al catalysts prepared from hydrotalcite-like precursors

N₂O decomposition was investigated over a series of K-promoted Co-Al catalysts. The activity tests showed that doping with K greatly enhanced the catalytic activity of the Co-Al catalyst, and the enhancement was critically dependent on the amount of K and the calcination temperature. When the catalyst had a K/Co atomic ratio of 0.04 and was calcined at 700–800 °C, a full N₂O conversion could be reached at a reaction temperature of 300 °C. Moreover, even under the simultaneous presence of 4% O₂ and 2.6% water vapor, such high-temperature treated K/Co-Al catalyst exhibited high reactivity and stability, with the N₂O conversion remaining at a constant value of 92% over 40 h run at 360 °C. In contrast, non-doped Co-Al catalyst showed a severe activity loss under such reaction conditions. A combination of characterization techniques was employed to reveal the promoting role of K and the effect of calcination temperature. The results suggest that doping with K increases the electron density of Co and weakens the Co–O bond, thus promoting the activation of N₂O on the Co sites and facilitating the desorption of oxygen from the catalyst surface. High-temperature calcinations made the desorption of O₂ proceed more readily.     

Reduction of NO by H2 on PdO-MoO3/γ-Al2O3 of low molybdena loading

The catalytic activity and selectivity of three PdO-MoO₃/-Al₂O₃ catalysts containing about 2% Pd and 2% Mo were studied for the reduction of NO by h₂ in the presence of varying amounts of oxygen at temperatures from 50 to 550 °C. The results are compared with those for PdO/-Al₂O₃, PdO-MoO₃/-Al₂O₃ containing 2% Pd and 20% Mo, and a commercial Pt-Rh catalyst. In the absence of oxygen, the conversion of NO to N₂ and N₂O is higher on the three catalysts than it is on PdO/-Al₂O₃ at 500 and 550 °C. In the presence of oxygen, the yields of N₂ and N₂O are generally lower on two of the PdO-MoO₃/-Al₂O₃ catalysts than on PdO/-Al₂O₃.     

Nitrous oxide emissions from paddy soil in three rice-based cropping systems in China

Rice-flooding fallow, rice-wheat, and double rice-wheat systems were adopted in pot experiment in an annual rotation to investigate the effects of cropping system on N₂O emission from rice-based cropping systems. The annual N₂O emission from the rice-wheat and the double rice-wheat cropping systems were 4.3 kg N ha^–1 and 3.9 kg N ha^–1, respectively, higher than that from rice-flooding fallow cropping system, 1.4 kg N ha^–1. The average N₂O flux was 115 and 118 g N m^–2 h^–1 for rice season in rice-wheat system and early rice season in double rice-wheat system, respectively, 68.6 and 35.3 g N m^–2 h^–1 for the late rice season in double rice-wheat system and rice season in rice-flooding fallow, respectively, and only 3.1–5.3 g N m^–2 h^–1 for winter wheat or flooding fallow season. Temporal variations of N₂O emission during rice growing seasons differed and high N₂O emission occurred when soil conditions changed from upland crop to flooded rice.     

Kinetic Investigation of the Photocatalytic Reduction of Nitric Oxide by Carbon Monoxide at Low Pressure on Silica-Supported Molybdenum Oxide

The kinetics of photoinduced reactions that occur upon UV irradiation (<360 nm) of a MoO₃/SiO₂ catalyst (2.5 wt% Mo) in CO-NO mixtures and CO alone are studied at gas pressures from 0.05 to 2 torr and for CO/NO ratios from 0.3 to 3.0 in the temperature interval 20-150C. The data obtained are consistent with a previously proposed two-stage redox mechanism. In the first stage NO is reduced to N₂O through the reaction CO+2NO CO₂+N₂O, while in the second stage the N₂O formed is further reduced to N₂ via the reaction CO+N₂O CO₂+N₂. The ratio of rate constants for quenching of a transient excited state (Mo⁵⁺-O^-)* by NO and CO molecules is found to be 2.8. The reaction rates decrease with increasing temperature, apparently because of a lower concentration of adsorbed species and/or a reduction of the steady-state concentration of (Mo⁵⁺-O^-)*.     

Isotope effect of H2/D2 and H2O/D2O for the PROX reaction of CO on the FeOx/Pt/TiO2 catalyst

The oxidation reaction of CO with O₂ on the FeOx/Pt/TiO₂ catalyst is markedly enhanced by H₂ and/or H₂O, but no such enhancement occurs on the Pt/TiO₂ catalyst. Isotope effects were studied by H₂/D₂ and H₂O/D₂O on the FeOx/Pt/TiO₂ catalyst, and almost the same magnitude of isotope effect of ca. 1.4 was observed for the enhancement of the CO conversion by H₂/D₂ as well as by H₂O/D₂O at 60 °C. This result suggests that the oxidation of CO with O₂ via such intermediates as formate or bicarbonate in the presence of H₂O, in which H₂O or D₂O acts as a molecular catalyst to promote the oxidation of CO as described below.      

Adsorption and oxidation of NH3 over V2O5/AC surface

V₂O₅/AC has been reported to be active for selective catalytic reduction (SCR) of NO with NH₃ at around 200 °C and resistant to SO₂ deactivation. To elucidate its SCR mechanism, adsorption and oxidation of NH₃ over V₂O₅/AC are studied in this paper using TG, MS and DRIFTS techniques. It is found that the adsorption and oxidation of NH₃ take place mainly at VO bond of V₂O₅. A higher V₂O₅ loading results in more NH₃ adsorption on the catalyst. V₂O₅ contains both Brnsted and Lewis acid sites; NH₄⁺ on Brnsted acid sites is less stable and easier to be oxidized than NH₃ on Lewis acid sites. Gaseous O₂ promotes interaction of NH₃ with AC and oxidation of NH₃ over V₂O₅/AC. NH₃ is oxidized into NH₂ and acylamide structures and then to isocyanate species, which is an intermediate for N₂ formation.     

An investigation into the effect of Cs promotion on the catalytic activity of NiO in the direct decomposition of N2O

A series of Cs promoted NiO catalysts have been prepared and tested for direct decomposition of N₂O. These catalysts are characterized by BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of N₂O (TPD-N₂O) and X-ray photo electron spectroscopy (XPS). The Cs promoted NiO catalysts exhibit higher activity for the decomposition of N₂O compared to bulk NiO. The catalyst with Cs/Ni ratio of 0.1 showed highest activity. The enhancement in catalytic activity of the Cs promoted catalysts is attributed to the change in the electronic properties of NiO. The characterization techniques suggest weakening of Ni–O bond thereby the desorption of oxygen becomes more facile during the reaction. The Cs promoted NiO catalyst is effective at low reaction temperature and also in the presence of oxygen and steam in the feed stream. IICT Communication No: 070523.     

Experimental and DFT studies of N2O decomposition over bare and Co-doped magnesium oxide—insights into the role of active sites topology in dry and wet conditions

Isothermal and TPSR studies of deN₂O reaction were performed over model MgO, and Co–MgO systems. Complementary experiments such as O₂-TPD, H₂O-TPD and IR, supported by DFT molecular modeling were carried out to elucidate the role of topological irregularities such as corners, steps, edges on the principal reaction events in dry and wet environment. The hydroxyl groups produced upon water adsorption were used for selective blocking of the active sites. Topological aspect of the surface reactivity was discussed in terms of the energetics of reaction steps and the relative stability and mobility of reaction intermediates (O₂²⁻) and inhibiting (OH⁻_surf) species. Whereas the most active corner sites are depleted by oxygen, produced in the course of N₂O decomposition, the edge and step sites could be eliminated only by more strongly adsorbed water. In steady state conditions the reaction turns over mainly on terrace sites and is moisture insensitive. Upon introduction of Co²⁺ ions to magnesium oxide the N₂O conversion curve is shifted by 200 °C towards lower temperatures, due to the change in the N₂O activation step (from anionic redox to cationic redox). However, at such thermal conditions the terrace sites remain still hydroxylated, and the overall reaction rate is clearly deteriorated by water present in the feed.     

Measurement of nitrous oxide emissions from two rice-based cropping systems in China

A field experiment was conducted to investigate the effects of winter management and N fertilization on N₂O emission from a double rice-based cropping system. A rice field was either cropped with milk vetch (plot V) or left fallow (plot F) during the winter between rice crops. The milk vetch was incorporated in situ when the plot was prepared for rice transplanting. Then the plots V and F were divided into two sub-plots, which were then fertilized with 276 kg urea-N ha^–1 (referred to as plot VN and plot FN) or not fertilized (referred to as plot VU and plot FU). N₂O emission was measured periodically during the winter season and double rice growing seasons. The average N₂O flux was 11.0 and 18.1 g N m^–2 h^–1 for plot V and plot F, respectively, during winter season. During the early rice growing period, N₂O emission from plot VN averaged 167 g N m^–2 h^–1, which was eight- to fifteen-fold higher than that from the other three treatments (17.8, 21.0 and 10.8 g N m^–2 h^–1 for plots VU, FN, and FU, respectively). During the late rice growing period, the mean N₂O flux was 14.5, 11.1, 12.1 and 9.9 g N m^–2 h^–1 for plots VN, VU, FN and FU, respectively. The annual N₂O emission rates from green manure-double rice and fallow-double rice cropping systems were 3.6 kg N ha^–1 and 1.3 kg N ha^–1, respectively, with synthetic N fertilizer, and were 0.99 kg N ha^–1 and 1.12 kg N ha^–1, respectively, without synthetic N fertilizer. Generally, both green manure N and synthetic fertilizer N contribute to N₂O emission during double rice season.