On the mechanism of NO decomposition on Cu-ZSM-5 catalysts

Decomposition of NO was studied on Cu-ZSM-5 catalysts prepared by solid state ion exchange using CuCl₂ (I), CuO (II) and by conventional liquid phase ion exchange with copper acetate (III). There was no difference in the catalytic activity among samples (I), (II) and (III) using the same copper loading. Treatment of the samples in argon, in air or in NO/Ar mixture at 700°C was necessary to develop optimum catalytic activity. Transient kinetic experiments using NO carried out under isothermal conditions, showed overshoots in the N₂ and O₂ concentration at the front and tail edge, respectively. Fourier transform-infrared studies indicated the formation of oxidized copper sites and adsorbed NO₂ species during the NO decomposition. In a proposed mechanism Cu²⁺(O)(NO)(NO₂) intermediate was suggested to play a key role in the NO decomposition.     

In situ XANES characterization of the Cu oxidation state in Cu-ZSM-5 during NO decomposition catalysis

The oxidation state of Cu in Cu-ZSM-5 has been investigated by the X-ray absorption near-edge structure (XANES) spectroscopic method during NO decomposition catalysis. We designed an in situ reactor system with which we can measure the relative NO decomposition rate while taking XANES spectra. We observed that the 1s4p electronic transition of Cu(I) in Cu-ZSM-5 appears as a narrow, intense peak which is an effective measure of changes in the population of copper oxidation states. This transition is quite intense after Cu-ZSM-5 is activated in inert gas flow. However, its intensity decreases but by no means disappears after the admission of a NO/N₂ gas mixture. We conducted the reaction in a temperature cycle around the optimum conversion temperature of 773 K and recorded the XANES at each temperature. We observed that the integrated intensity of the Cu(I) 1s4p transition, which is proportional to the cuprous ion concentration in Cu-ZSM-5, was well correlated with the NO decomposition rate. This finding supports the conjecture that Cu(I) participates in a redox mechanism during catalyzed NO decomposition in Cu-ZSM-5 at elevated temperature.     

NO2 formation over Cu-ZSM-5 and the selective catalytic reduction of NO

The extent of the selective catalytic reduction (SCR) of nitric oxide to dinitrogen in the presence of excess oxygen is enhanced by the oxygen on several zeolite-based catalysts and using different reductants. When the catalyst is Cu-ZSM-5 and the reductant is a hydrocarbon, an NO₂ intermediate has been suggested by several investigators. This work shows that at short residence times, with excess reductant and in the absence of oxygen, the NO₂ itself is reduced only back to NO. Thus, for the selective reduction of NO₂ to N₂ (N-pairing) strongly oxidizing conditions are required, same as for the complete reduction of NO. In the presence of excess oxygen the activity of Cu-ZSM-5 in the NO + O₂ reaction to form NO₂ parallels the SCR in every respect. It is higher over Cu-ZSM-5 than on Cu/Al₂O₃ or on H-ZSM-5. The coppercontaining zeolite is also active in the decomposition of NO₂ back to NO and O₂ while the other catalysts are much less active. The inhibiting effect of water on the NO + O₂ catalytic reaction is also parallel to the effect on SCR. This evidence strengthens the notion of an NO₂ intermediate.     

Dinitrogen formation over low-exchanged Cu-ZSM-5 in the selective reduction of NO by propane

The role of gaseous NO and C₃H₈ has been studied over low-exchanged Cu-ZSM-5 zeolite employing TPD, FTIR and pulse technique with the alternate introduction of NO or C₃H₈ onto the catalyst surface. The rate of the N₂ formation is directly proportional to the content of gaseous NO and the surface coverage with 2-nitrosopropane. There was no formation of N₂ during interaction of gaseous C₃H₈ with NO adsorbates. However, 2-nitrosopropane and its isomer acetone oxime were also formed in this reaction. This revised version was published online in November 2006 with corrections to the Cover Date.     

In situ FT-IR study of NH3 formation during the reduction of NOx with propane on H/Cu-ZSM-5 in excess oxygen

IR experiments under flow of NO and propane on H/Cu-ZSM-5 evidence at 623 K the appearance of bands at 2248, 2157 and 2047 cm⁻¹ tentatively assigned through the use of ¹⁵NO to nitrile, carbonyl (CO---Cu⁺) and isocyano species respectively. Addition of O₂ suggests conversion of isocyano to isocyanato species (2208 cm⁻¹) which by hydrolysis leads to NH₃ formation, revealed by IR bands at 3366, 3290, 3192 and 1610 cm⁻¹.     

Selective catalytic reduction of NOx with NH3 over Cu-ZSM-5—The effect of changing the gas composition

The selective catalytic reduction of nitrogen oxides (NO_x) with ammonia over ZSM-5 catalysts was studied with and without water vapor. The activity of H-, Na- and Cu-ZSM-5 was compared and the result showed that the activity was greatly enhanced by the introduction of copper ions. A comparison between Cu-ZSM-5 of different silica to alumina ratios was also performed. The highest NO conversion was observed over the sample with the lowest silica to alumina ratio and the highest copper content. Further studies were performed with the Cu-ZSM-5-27 (silica/alumina = 27) sample to investigate the effect of changes in the feed gas. Oxygen improves the activity at temperatures below 250 °C, but at higher temperatures O₂ decreases the activity. The presence of water enhances the NO reduction, especially at high temperature. It is important to use about equal amounts of nitrogen oxides and ammonia at 175 °C to avoid ammonia slip and a blocking effect, but also to have high enough concentration to reduce the NO_x. At high temperature higher NH₃ concentrations result in additional NO_x reduction since more NH₃ becomes available for the NO reduction. At these higher temperatures ammonia oxidation increases so that there is no ammonia slip. Exposing the catalyst to equimolecular amounts of NO and NO₂ increases the conversion of NO_x, but causes an increased formation of N₂O.     

Mechanistic aspects of lean NO2 reduction by propane over HZSM-5

This study focuses on the mechanism of lean NO₂ reduction by propane. In particular the role of isocyanate- and amine species has been studied in transient experiments by in situ Fourier Transform Infrared (FTIR) spectroscopy. The results imply that these species are possible reaction intermediates over acidic HZSM-5.     

Identification of adsorbed species on Cu-ZSM-5 under NH3 SCR conditions

The selective catalytic reduction of nitrogen oxides with ammonia as the reducing agent was studied using Fourier transform infrared (FTIR) spectroscopy. The adsorbed species found on a Cu-ZSM-5 powder during exposure to NO, NO₂ or NH₃ was compared to the adsorbed species identified during SCR conditions. A blocking effect caused by ammonia at 175 °C was investigated by a stepwise increase of the ammonia concentration, and the spectra indicated that the formation of nitrites or nitrates decreased as surface coverage of ammonia increased. No such effect was observed at 350 °C, since the oxidation of ammonia results in very low ammonia coverage. The effect of changes in the NO to NO₂ ratio was also studied at 350 °C, and the species identified during SCR reaction indicated that the enhanced activity at equimolecular amounts of NO and NO₂ possibly involves gas phase components as well as adsorbed species.     

The role of NO2 in the reduction of NO by hydrocarbon over Cu-ZrO2 and Cu-ZSM-5 catalysts

The reduction of NO _x with propene or propane in the presence of 1 or 4% O₂ was studied at low conversions over a 7.4 wt% Cu-ZrO₂ and a 3.2 wt% Cu-ZSM-5 catalyst. The rates of N₂ production were compared in experiments using only NO or a mixture of NO and NO₂ in the feed. They were also compared with the rates of NO₂ reduction to NO under the same conditions, and of NO oxidation to NO₂ in the absence of hydrocarbon. It was found that the reduction of NO₂ to NO was very fast, consistent with literature data. The data were best explained by a reaction scheme in which the hydrocarbon was activated primarily by reaction with adsorbed NO₂ to form an adsorbed oxidized N-containing hydrocarbon intermediate, the reaction of which with NO was the principal route to produce N₂ under lean NO _x conditions.On leave from State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China.     

Catalytic reduction of NO by propene in the presence of oxygen over mechanically mixed metal oxides and Ce-ZSM-5

The mechanical mixing of Mn₂O₃ or CeO₂ to Ce-ZSM-5 considerably enhanced the rate of the reduction of NO by propene in the low to medium temperature region, although Mn₂O₃ or CeO₂ itself was much less active for this reaction. In contrast, Mn₂O₃ was highly active and CeO₂ was moderately active for the oxidation of NO to NO₂. On the basis of the comparison of the rates of the C₃H₆ + O₂, NO + C₃H₆ + O₂ and NO₂ + C₃H₆ + O₂ reactions over these catalysts, a bifunctional mechanism is proposed, in which Mn₂O₃ and CeO₂ accelerate the oxidation of NO and the subsequent reaction steps between NO₂ and propene proceed on Ce-ZSM-5.     

Selective catalytic reduction of NO with propane over CoZSM-5 containing alkaline earth cations

Selective catalytic reduction (SCR) of nitric oxide (NO) with propane is studied over CoZSM-5 catalysts with a series of exchanged cobalt concentrations (0.9-7.5 wt.-%). The overall activity for SCR of NO is found to increase linearly with the cobalt content in the range below the maximum exchange capacity (CoAl= 0.5). However, when the cobalt loading exceeds the exchange capacity of the zeolite, viz.CoAl 0.5, the combustion of propane is favored significantly, resulting in a decrease of the NO conversion. The presence of excess Co²⁺ in zeolite appears to bring about the marked falls in adsorption of NO. In this case cobalt oxide particles are presumed to form, which promote the oxidation of propane. Nevertheless, the addition of alkaline-earth metal cations (Ba, Ca) resulted in the suppression of propane oxidation over CoZSM-5, and improved the NO conversion dramatically.     

Selectivity-determining role of C3H8/NO ratio in the reduction of nitric oxide by propane in presence of oxygen over ZSM5 zeolites

The reaction of (NO + C₃H₈ + O₂) can result in selective formation of NO₂ over H-ZSM5, Cu,H-ZSM5, Ag,H-ZSM5, and Li,H-ZSM5 catalysts when the concentrations of NO and O₂ are 0.1 and 9%, SV > 60,000 h⁻¹ (typical for automotive exhausts), and C₃H₈/NO > 1. Despite stoichiometric excess of reductant hydrocarbon below this limit, the in situ formed NO₂ does not react with C₃H₈, thus conversion of NO to N₂ is negligible. NO can be reduced by C₃H₈ selectively to N₂ only when C₃H₈/NO ≧ 1. Contrary to many suggestions the reaction temperature, concentration of oxygen, space velocity, and type of exchange ions have minor influence on the selectivity for N₂. These parameters affect the rates of reactions (NO + ₂), (C₃H₈ + NO_x) and (C₃H₈ + O₂), therefore they also affect the production of N₂ in the HC-SCR process, but only when the ratio of C₃H₈/NO permits. The metal-exchanged zeolites were prepared in situ by solid-state ion exchange from H-ZSM5. Despite the low degree of copper exchange (63%), Cu,H-ZSM5 produces substantially more N₂ than H-ZSM5, Ag,H-ZSM5, or Li,H-ZSM5. However, the selectivity for N₂ is lowest over Cu,H-ZSM5, which also produces considerable NO₂ in the reaction of (NO + C₃H₈ + O₂) even at C₃H₈/NO ≧ 1. Contrary to prior findings, the catalytic activity of Cu,H-ZSM5 for the oxidation of NO by O₂ to NO₂ in absence of hydrocarbon was comparable to that of H-ZSM5 at high space velocities (2.3 l g⁻¹ min⁻¹). By replacing 30 and 40% of the protons of H-ZSM5 by Ag⁺ and Li⁺ ions in Ag,H-ZSM5 and Li,H-ZSM5, respectively, the catalytic activity for this reaction becomes negligible at temperatures ≧100°C. Some mechanistic consequences of these experimental observations are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Unique properties of Ir/ZSM-5 catalyst for NO reduction with CO in the presence of excess oxygen

The reduction of NO with CO in the presence of excess oxygen was investigated over different noble metal catalysts for probing the relationship between catalytic properties and adsorption behaviors. Among the four precious metal catalysts investigated, Ir/ZSM-5 was found to be the only active one for NO reduction with CO under lean conditions. With the decreasing of the Ir content, higher NO conversion and CO selectivity was obtained. Temperature-programmed reaction (TPR) studies of NO/H₂/O₂ and NO/CO/O₂ showed that the Pt/ZSM-5 was active when H₂ was used as the reductant, whereas, the Ir/ZSM-5 was active when CO was the reducing agent. This difference is due to the different mechanisms of the two reactions. Temperature-programmed desorption (TPD) of NO, CO and O₂ showed that NO could dissociate more easily over the Ir/ZSM-5 than on the Pt/ZSM-5, while the oxidation of CO by O₂ proceeded more rapidly on the Pt/ZSM-5 than on the Ir/ZSM-5. The presence of excess O₂ inhibited drastically the dissociation of NO, which is considered as the key step for the NO–CO reaction. The high dissociation rate of NO over the Ir/ZSM-5 is visualized as the key factor for its superior high activity in NO reduction with CO under lean conditions.     

The effect of Si/Al ratio and copper exchange level on isothermal kinetic rate oscillations for N2O decomposition over Cu-ZSM-5: a transient FTIR study

Kinetic rate oscillations in the decomposition of N₂O over Cu-ZSM-5 were studied over a series of catalysts with varying Si/Al ratios and copper exchange levels. Oscillations were observed to occur over all catalysts with Si/Al≥29 and exchange level >100%, including excessively-exchanged catalysts with Cu/Al>1.0. FTIR spectroscopy showed that the same monodentate nitrate species was present under reaction conditions for all catalysts displaying oscillatory behavior, and that the coverage of this species was correlated to the gas phase oscillations. Catalysts with low Si/Al ratios did not show oscillation due to a combination of factors: (1) additional actives sites exist on these catalysts (possibly Cu ion pairs) that stabilize additional nitrate species, (2) the nitrate species desorb at a lower temperature compared to the other zeolite catalysts, and (3) the formation of nitrate on these catalysts was shown to be an order of magnitude slower than on the catalysts which show oscillations. FTIR-based kinetic studies of nitrate formation verified that the most critical reaction occurs between N₂O and extra lattice oxygen in order to form NO, which is converted rapidly to surface nitrate. FTIR also identified a possible intermediate in the formation of nitrate at 1537 cm⁻¹ that has been assigned to monodentate nitrite on Cu²⁺ ions.     

The catalytic activity of Cu-ZSM-5 and Cu-Y zeolites in NO decomposition: dependence on copper concentration

NO decomposition was studied on Cu-ZSM-5 (Cu exchange extent from 23 to 210%) and Cu-Y (Cu exchange extent from 5 to 105%) catalysts at 773 K. The results show that the activity (NO molecules decomposed per gram of catalyst per second) increases by roughly 100-fold when the extent of exchange with copper in the ZSM-5 framework increases from 80 to 100%. This behaviour shows that not all Cu sites are equivalent in their decomposition activity. Cu-ZSM-5 samples prepared with either H-ZSM-5 or Na-ZSM-5 show the same activity pattern.     

The existence of dual Cu site involved in the selective catalytic reduction of NO with propene on Cu/ZSM-5

In order to establish the role of surface species in the selective catalytic reduction (SCR), in situ IR studies were carried out using a DRIFT (diffuse reflectance infrared Fourier transform) cell in gas mixtures of various C₃H₆/NO ratios containing excess oxygen. The location and mobility of Cu ions were investigated by recording the relevant bands of CO adsorbed on Cu/ZSM-5. The nitro species coordinated on Cu²⁺ and the -NCO surface complex as possible intermediates were observed in the reduction of NO with propene on Cu/ZSM-5 between 350 and 400°C. The reactivities of these species toward NO, O₂ and propene were examined. The nitro species can react with propene very rapidly to form N₂ without the formation of NCO species. NCO also reacts with NO₂ and/ or NO at 350°C. IR spectra of CO adsorbed on cuprous ions show that two kinds of Cu ions, which are responsible for the activation of NO and propene respectively, exist on Cu/ZSM-5. From these results, a dual site mechanism involving nitro species and -NCO species as intermediates is suggested.     

Quantification and redox property of the oxygen-bridged Cu<Superscript>2+</Superscript> dimers as the active sites for the NO decomposition over Cu-ZSM-5 catalysts

For a range of Cu-ZSM-5 catalysts with different Cu-exchange levels on the two kinds of ZSM-5 with different Si/A1 ratios, temperature programmed reduction using CO (CO-TPR) followed by H₂ (H₂-TPR), and temperature programmed desorption of oxygen (O₂-TPD) were conducted using an online mass spectrometer to characterize and quantify the copper species on the catalysts in the calcined state. Copper species on the ZSM-5 were quantitatively characterized as Cu²⁺, (Cu-O-Cu)²⁺ and CuO after calcination in oxygen environment. The N₂ formation activities of the catalysts in the decomposition of NO were well correlated with the quantified catalytic amounts of the Cu²⁺ ions involved in the Cu-dimers, (Cu-O-Cu)²⁺. The mol fraction of the Cu ions present as the Cu-dimers increased at the sacrifice of the isolated Cu²⁺ with increasing Cu ion exchange level, suggesting that the species could be formed between the two Cu²⁺ in close proximity. Oxygen that could be thermally desorbed from the oxidized catalysts in the O₂-TPD was responsible for the reduction of the Cu-dimers. It was concluded that the decomposition of NO over Cu-ZSM-5 catalyst proceeded by the redox of (Cu-O-Cu)²⁺, as active centers. With the temperature programmed surface reaction using N₂O or NO over an oxidized catalyst sample as well as the O₂-TPD, it was possible to estimate the change of the oxidation state of the Cu ions engaged in the Cu-dimers.     

Catalytic properties and electronic structure of copper ions in Cu-ZSM-5

The effect of ion exchange conditions, such as Si/Al ratio, precursor copper salt, pH and concentration of the solution, on the catalytic activity in SCR of NO by propane and on the electronic state of copper ions in Cu-ZSM-5 has been studied. The NO conversion in NO SCR by C₃H₈ has been found to reach a maximum value at Cu/Al ratio about 0.37–0.4 and remain constant at higher Cu/Al.

ESR and UV–vis DR spectroscopy have been used to elucidate stabilization conditions of copper ions in Cu-ZSM-5 zeolites as isolated Cu²⁺ ions, chain copper oxide structures and square-plain oxide clusters. The ability of copper ions for reduction and reoxidation in the chain structures may be responsible for the catalytic activity of Cu-ZSM-5. These transformations of copper ions are accompanied by the observation of intervalence transitions Cu²⁺–Cu⁺ and CTLM of the chain structures in the UV–vis spectra.     

Copper-exchanged mordenites as active catalysts for NO selective catalytic reduction by propene under oxidising conditions: Effect of Si/Al ratio, copper content and Brönsted acidity

CuMOR catalysts with different Si/Al ratios and copper contents, prepared from the acid and sodium forms, were studied in NO reduction with propene in the presence of excess oxygen. It was observed that the influence of zeolite Si/Al ratio on CuMOR catalytic activity for NO SCR by propene depends on the catalyst copper content, the reverse being also true. For mordenites prepared from the acid form, it was shown that the most active catalyst must have 60% of copper exchange, whereas for those prepared from the sodium form, the maximum catalytic activity is obtained for catalysts with 20% of copper exchange. Moreover, it was observed that at low copper-exchange levels, the catalyst prepared from the sodium form exhibits much higher activity than those prepared from the acid form. Although, when the copper-exchange level increases, the effect of zeolite form is less pronounced. Thus, it was indicated that Brönsted acidity does not promote the NO selective reduction by propene.     

In situ high temperature FTIR studies of NOx reduction with propylene over Cu/ZSM-5 catalysts

High temperature in situ FTIR has been used to investigate the surface species present on Cu/ZSM-5 during the reduction of NO_x with propylene in a lean environment. Parallels have been observed between adsorbed surface species and catalytic activity for this reaction. Species detected at low temperatures are not representative of those detected at high temperatures where the catalyst is active. An oxidized nitrogen-containing species has been observed at 2580 cm^–1 on Cu during reaction conditions (400°C). In contrast, at low temperatures, where the catalyst is less active, coke and Cu⁺-CO predominated. The effects of Cu weight loading, C/NO ratio, reaction temperature, and catalyst deactivation by steaming have been investigated with IR.