Preparation and characterization of inexpensive heterogeneous catalysts for air pollution control: Two case studies

Relatively inexpensive heterogeneous catalysts for two reactions of great importance in air pollution control, NO reduction and VOC combustion, were prepared and characterized. Apart from their common practical goal and the frequent need for simultaneous removal of air pollutants, these reactions share a similar redox mechanism, in which the formulation of more effective catalysts requires an enhancement of oxygen transfer.

For NO reduction, supported catalysts were prepared by adding a metal (Cu, Co, K) using ion exchange (IE) and incipient wetness impregnation (IWI) to chars obtained from pyrolysis of a subbituminous coal. The effects of pyrolysis temperature, between 550 and 1000 °C, on selected catalyst characteristics (e.g., BET surface area, XRD spectrum, support reactivity in O₂) are reported. For IE catalysts, the surface area increased in the presence of the metals while the opposite occurred for IWI catalysts. For the Co-IE catalysts, the highest surface area was obtained at 700 °C. The XRD results showed that, except for Cu (which exhibited sharp Cu⁰ peaks), the catalysts may be highly dispersed (or amorphous) on the carbon surface. For the C–O₂ reaction the order of (re)activity was K  Co > Cu for IE catalysts and K > Cu > Co for IWI catalysts. For NO reduction the orders were K > Co > Cu (IE catalysts) and Cu > Co > K (IWI catalysts). In all cases the catalytic (re)activity for NO reduction was lower than that exhibited for the C–O₂ reaction. The K-IE and Cu-IWI catalysts appeared to be the most promising ones, although further improvements in catalytic activity will be desirable. Some surprising results regarding CO and CO₂ selectivity are also reported, especially for Co catalysts.

In VOC combustion, the effect of the nature of ion B (Fe and Ni) on the partial substitution of ion A (Ca for La) in ABO₃ perovskites (e.g., LaFeO₃ and LaNiO₃) and on their catalytic activity was studied. The perovskite-type oxides were characterized by means of surface area measurements, XRD, temperature-programmed desorption (TPD) and temperature-programmed reduction (TPR). The effect of partial substitution of La³⁺ by Ca²⁺ was more significant for the La_1−xCa_xFeO₃ perovskites. In this case, the electronic perturbation is compensated by an oxidation state increase of part of Fe³⁺ to Fe⁴⁺. The TPD results revealed that, at higher substitution levels, oxygen vacancies are also formed to preserve electroneutrality. For the La_1−xCa_xNiO₃ perovskites, the characterization results showed no evidence of large differences in electronic properties as calcium substitution increases. The La_1−xCa_xNiO₃ perovskites exhibited lower activity than the simple LaNiO₃ perovskite, whereas for the La_1−xCa_xFeO₃ substituted perovskites the most active catalyst (exhibiting the lowest ignition temperature) was obtained at the highest substitution level, La_0.6Ca_0.4FeO₃.

The performance of both groups of catalysts is briefly discussed in terms of redox processes, in which the interplay between oxygen transfer and electron transfer requires further elucidation for the improvement of catalytic activity.     

Co3O4 based catalysts for NO oxidation and NOx reduction in fast SCR process

Reaction activities of several developed catalysts for NO oxidation and NO_x (NO + NO₂) reduction have been determined in a fixed bed differential reactor. Among all the catalysts tested, Co₃O₄ based catalysts are the most active ones for both NO oxidation and NO_x reduction reactions even at high space velocity (SV) and low temperature in the fast selective catalytic reduction (SCR) process. Over Co₃O₄ catalyst, the effects of calcination temperatures, SO₂ concentration, optimum SV for 50% conversion of NO to NO₂ were determined. Also, Co₃O₄ based catalysts (Co₃O₄-WO₃) exhibit significantly higher conversion than all the developed DeNO_x catalysts (supported/unsupported) having maximum conversion of NO_x even at lower temperature and higher SV since the mixed oxide Co-W nanocomposite is formed. In case of the fast SCR, N₂O formation over Co₃O₄-WO₃ catalyst is far less than that over the other catalysts but the standard SCR produces high concentration of N₂O over all the catalysts. The effect of SO₂ concentration on NO_x reduction is found to be almost negligible may be due to the presence of WO₃ that resists SO₂ oxidation.     

Preparation of CexZr1−xO2 (x = 0.75, 0.62) solid solution and its application in Pd-only three-way catalysts

Nanoparticles of Ce_xZr_1−xO₂ (x = 0.75, 0.62) were prepared by the oxidation-coprecipitation method using H₂O₂ as an oxidant, and characterized by N₂ adsorption, XRD and H₂-TPR. Ce_xZr_1−xO₂ prepared had single fluorite cubic structure, good thermal stability and reduction property. With the increasing of Ce/Zr ratio, the surface area of Ce_xZr_1−xO₂ increased, but thermal stability of Ce_xZr_1−xO₂ decreased. The surface area of Ce_0.62Zr_0.38O₂ was 41.2 m²/g after calcination in air at 900 °C for 6 h. TPR results showed the formation of solid solution promoted the reduction of CeO₂, and the reduction properties of Ce_xZr_1−xO₂ were enhanced by the cycle of TPR-reoxidation. The Pd-only three-way catalysts (TWC) were prepared by the impregnation method, in which Ce_0.75Zr_0.25O₂ was used as the active washcoat and Pd loading was 0.7 g/L. In the test of Air/Fuel, the conversion of C₃H₈ was close to 100% and NO was completely converted at λ < 1.025. The high conversion of C₃H₈ was induced by the steam reform and dissociation adsorption reaction of C₃H₈. Pd-only catalyst using Ce_0.75Zr_0.25O₂ as active washcoat showed high light off activity, the reaction temperatures (T₅₀) of 50% conversion of CO, C₃H₈ and NO were 180, 200 and 205 °C, respectively. However, the conversions of C₃H₈ and NO showed oscillation with continuously increasing the reaction temperature. The presence of La₂O₃ in washcoat decreased the light off activity and suppressed the oscillation of C₃H₈ and NO conversion. After being aged at 900 °C for 4 h, the operation windows of catalysts shifted slightly to rich burn. The presence of La₂O₃ in active washcoat can enhance the thermal stability of catalyst significantly.     

Characterization and catalytic properties of perovskites with nominal compositions La1-xSrxAl1-2yCuyRuyO3

Nine different metal oxide catalysts were prepared by impregnating alumina washcoats with water solutions containing La³⁺, Sr²⁺, Cu²⁺ and Ru³⁺ ions and calcining them at 900°C. The produced samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) studies combined with energy-dispersive spectroscopy (EDS) analysis, X-ray powder diffraction and specific surface area measurements. A perovskite phase of the nominal composition La_1-xSr_xAl_1-2yCu_yRu_yO₃ was found in all samples, in increasing amount in the samples with increasing contents of strontium and ruthenium. The catalysts were evaluated with respect to light-off temperatures and redox characteristics using two gas mixtures, one containing NO/CO/C₃H₆/O₂/N₂ and the other NO/CO/N₂. The light-off temperatures for nitric oxide reduction decreased from 534 to 333°C for the catalysts without and with strontium and ruthenium, respectively. In the presence of oxygen the conversion of nitric oxide declined rapidly under oxidative conditions whereas in absence of oxygen this decline was less pronounced and found to be linear over the entire redox interval studied. These studies suggest that the perovskite phase takes an active part in the conversion of nitric oxide and carbon monoxide to nitrogen and carbon dioxide.     

Palladium-substituted lanthanum cuprates: application to automotive exhaust purification

A series of palladium-substituted La₂CuO₄, corresponding to the formula La₂Cu_{1 −x}Pd_xO₄ (x = 0−0.2) were prepared by metal nitrate decomposition in a polyacrylamide gel. This method allows an easy incorporation of palladium in the mixed-oxides, which are formed at moderate temperature with rather high specific areas (13–17 m²/g). The partial substitution of copper for palladium allows a strong improvement of the three-way catalytic activity, in particular for NO reduction. The light-off temperatures for the conversions of CO, NO and C₃H₆ decreased markedly when increasing the palladium content, the activity of catalysts La₂Cu_0.9Pd_0.1O₄ and La₂Cu_0.8Pd_0.2O₄ being comparable to that of a Pt-Rh/CeO₂–Al₂O₃ catalyst for NO reduction, and higher for CO and C₃H₆ oxidation.

All the La₂Cu_{1 − x} Pd_xO₄ catalysts are activated under reacting conditions. This activation corresponds to the destruction of the mixed-oxide structure, with formation of reduced Pd⁰ ions atomically dispersed, surrounded by Cu⁺ and Cu²⁺ species on a lanthanum oxycarbonate matrix. This high dispersion state of the two transition metals in various oxidation states is supposed to originate from the initial La₂Cu_{1 −x}Pd_xO₄ structure.     

A comparative study of the selective catalytic reduction of NO by propylene over supported Pt and Rh catalysts

The catalytic performance of Pt and Rh catalysts for the selective catalytic reduction (SCR) of NO by propylene in the presence of excess oxygen has been investigated over catalysts supported on six different metal oxide carriers (CeO₂, Al₂O₃, TiO₂, YSZ, ZrO₂ and W⁶⁺-doped TiO₂). It has been found that the nature of the dispersed metal affects strongly the light-off temperature of propylene, the maximum NO conversion to reduction products and the selectivity towards nitrogen. For a given support, Pt catalysts are always more active for both NO reduction and propylene oxidation, but are much less selective towards N₂, compared to Rh catalysts. Rhodium catalysts are able to selectively reduce NO even in the absence of oxygen in the feed. However, their activity is suppressed with increasing oxygen feed concentration possibly due to the formation of less reactive rhodium oxides. In contrast, oxygen promotes the de-NO_x activity of platinum catalysts but decreases selectivity towards nitrogen. Results are explained by considering the effects of the nature of the metallic phase and the support on the elementary steps of the propylene-SCR reaction. It is concluded that the catalytic performance of both metals may be improved by proper selection of the support.     

Catalytic behavior of La–Sr–Ce–Fe–O mixed oxidic/perovskitic systems for the NO+CO and NO+CH4+O2 (lean-NOx) reactions

Mixed oxides of the general formula La_0.5Sr_xCe_yFeO_z were prepared by using the nitrate method and characterized by XRD and Mössbauer techniques. The crystal phases detected were perovskites LaFeO₃ and SrFeO_3−x and oxides -Fe₂O₃ and CeO₂ depending on x and y values. The low surface area ceramic materials have been tested for the NO+CO and NO+CH₄+O₂ (“lean-NO_x”) reactions in the temperature range 250–550°C. A noticeable enhancement in NO conversion was achieved by the substitution of La³⁺ cation at A-site with divalent Sr⁺² and tetravalent Ce⁺⁴ cations. Comparison of the activity of the present and other perovskite-type materials has pointed out that the ability of the La_0.5Sr_xCe_yFeO_z materials to reduce NO by CO or by CH₄ under “lean-NO_x” conditions is very satisfying. In particular, for the NO+CO reaction estimation of turnover frequencies (TOFs, s⁻¹) at 300°C (based on NO chemisorption) revealed values comparable to Rh/-Al₂O₃ catalyst. This is an important result considering the current tendency for replacing the very active but expensive Rh and Pt metals. It was found that there is a direct correlation between the percentage of crystal phases containing iron in La_0.5Sr_xCe_yFeO_z solids and their catalytic activity. O₂ TPD (temperature-programmed desorption) and NO TPD studies confirmed that the catalytic activity for both tested reactions is related to the defect positions in the lattice of the catalysts (e.g., oxygen vacancies, cationic defects). Additionally, a remarkable oscillatory behavior during O₂ TPD studies was observed for the La_0.5Sr_0.2Ce_0.3FeO_z and La_0.5Sr_0.5FeO_z solids.     

Oxidation of CO over Ru containing perovskite type oxides

Perovskite type catalysts La_0.7Sr_0.3Cr_1−xRu_xO₃ (0.025 ≤ x ≤ 0.100) were synthesized by annealing a mixture of metal oxides and carbonates gradually up to 1000 °C in air, and characterized by XRPD, XPS, TPD, SEM-EDS and the van der Pauw method. The CO oxidation activity was investigated in a differential recycle reactor. According to the XRPD results, all samples achieved a perovskite structure, with a small presence of SrCrO₄ phase. The XPS results revealed that the surface composition of all samples differed considerably from the stoichiometric value with an important segregation of strontium and mainly ruthenium with regard to chromium at the surface of the catalysts. The sharp decrease of resistivity with increasing surface concentration of ruthenium and the independence of the resistivity on temperature for the sample with x = 0.100 imply the possible presence of SrRuO₃, La–Ru–O and highly dispersed RuO₂ (invisible by XRPD), known as good electric conductors, at the surface. The CO oxidation activity increases with increasing the degree of substitution (x). The surface concentrations of ruthenium are almost the same in the samples with x = 0.075 and 0.100. Those samples showed the similar values of resistivity in whole investigated temperature range and very close CO oxidation activity, which indicates that the concentration of Ru⁴⁺ in the surface region and its stability are determining factors for the CO oxidation activity. The main results of this study are that ruthenium perovskites have a high thermal stability and CO oxidation activity.     

Regeneration of thermally aged Pt-Rh/CexZr1−xO2-Al2O3 model three-way catalysts by oxychlorination treatments

Pt-Rh/Ce_xZr_1−xO₂-Al₂O₃ with 0.6 and 1.0 wt.% noble metal loadings were prepared and characterized for their metal dispersion with respect to Ce_xZr_1−xO₂-free Pt-Rh/Al₂O₃ in fresh, thermally aged and oxychlorinated states. Thermal ageing at 973 K led to loss of metal dispersion in all cases but to negligible effect on the dispersion of the Ce_xZr_1−xO₂ component where present. Oxychlorination was able to fully recover metal dispersion in all cases but led to different effects on the redox properties of Ce_xZr_1−xO₂ which appeared to be related to the metal loadings. Despite showing improved dispersion following regeneration, higher loaded catalyst showed no improvement in light-off performance for either NO reduction or CO oxidation and showed poorer oxygen storage (OSC) ability, particularly at higher temperatures. Lower loaded catalyst showed improved dispersion, improved OSC and reduced light-off temperatures for NO reduction and CO oxidation after oxychlorination compared to that in the thermally aged state.     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe⁴⁺ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m² g⁻¹ range. XRD analysis showed that LaFeO₃, NdFeO₃, SmFeO₃ and LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO₃ of a very small fraction of Fe⁴⁺ which reduces to Fe³⁺. The fraction of Fe⁴⁺ in the LaFe_1−xMg_xO₃ samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO₂ below 973 and 773 K, respectively. For the AFeO₃ materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe_1−xMg_xO₃ catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO₃ materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

Electrical resistivity and thermopower of (La1−xSrx)MnO3 and (La1−xSrx)CoO3 at elevated temperatures

Electrical resistivity and Seebeck (S) measurements were performed on (La_1−xSr_x)MnO₃ (0.02x0.50) and (La_1−xSr_x)CoO₃ (0x0.15) in air up to 1073 K. (La_1−xSr_x)MnO₃ (x0.35) showed a metal-to-semiconductor transition; the transition temperature almost linearly increased from 250 to 390 K with increasing Sr content. The semiconductor phase above the transition temperature showed negative values of S. (La_1−xSr_x)CoO₃ (0x0.10) showed a semiconductor-to-metal transition at 500 K. Dominant carriers were holes for the samples of x0.02 above room temperature. LaCoO₃ showed large negative values of S below ca. 400 K, indicative of the electron conduction in the semiconductor phase.     

Catalytic performance of Ag–Al2O3 catalyst for the selective catalytic reduction of NO by higher hydrocarbons

Silver–aluminum mixed oxide catalyst (Ag–Al₂O₃) prepared by the sol–gel method was studied for the selective reduction of NO by various alkanes in the presence of water vapor. As the carbon number of alkanes increases, the de-NO_x activity and water tolerance were markedly increased. In the case of n-octane as a reductant, the presence of water vapor markedly promoted NO reduction. The results of reaction studies and in situ IR experiment showed that the possible reasons for the promoting effect by water vapor are the inhibition of the n-octane oxidation by O₂ and the suppression of the poisoning effect caused by carboxylate and carbonate species. Among various alumina-supported transition metal catalysts, Ag–Al₂O₃ showed the highest activity for SCR by n-octane. Ag–Al₂O₃ showed higher NO conversion to N₂ and selectivity than alumina-supported Pt and Cu-ZSM-5 catalysts for the selective reduction of NO by n-octane and i-octane.     

AMnO3 (A=La, Nd, Sm) and Sm1−xSrxMnO3 perovskites as combustion catalysts: structural, redox and catalytic properties

Catalytic combustion of methane has been investigated over AMnO₃ (A = La, Nd, Sm) and Sm_1−xSr_xMnO₃ (x = 0.1, 0.3, 0.5) perovskites prepared by citrate method. The catalysts were characterized by chemical analysis, XRD and TPR techniques. Catalytic activity measurements were carried out with a fixed bed reactor at T = 623–1023 K, space velocity = 40 000 N cm³ g⁻¹ h⁻¹, CH₄ concentration = 0.4% v/v, O₂ concentration = 10% v/v.

Specific surface areas of perovskites were in the range 13–20 m² g⁻¹. XRD analysis showed that LaMnO₃, NdMnO₃, SmMnO₃ and Sm_1−xSr_xMnO₃ (x = 0.1) are single phase perovskite type oxides. Traces of Sm₂O₃ besides the perovskite phase were detected in the Sm_1−xSr_xMnO₃ catalysts for x = 0.3, 0.5. Chemical analysis gave evidence of the presence of a significant fraction of Mn(IV) in AMnO₃. The fraction of Mn(IV) in the Sm_1−xSr_xMnO₃ samples increased with x. TPR measurements on AMnO₃ showed that the perovskites were reduced in two steps at low and high temperature, related to Mn(IV) → Mn(III) and Mn(III) → Mn(II) reductions, respectively. The onset temperatures were in the order LaMnO₃ > NdMnO₃ > SmMnO₃. In Sm_1−xSr_xMnO₃ the Sr substitution for Sm caused the formation of Mn(IV) easily reducible to Mn(II) even at low temperature. Catalytic activity tests showed that all samples gave methane complete conversion with 100% selectivity to CO₂ below 1023 K. The activation energies of the AMnO₃ perovskites varied in the same order as the onset temperatures in TPR experiments suggesting that the catalytic activity is affected by the reducibility of manganese. Sr substitution for Sm in SmMnO₃ perovskites resulted in a reduction of activity with respect to the unsubstituted perovskite. This behaviour was related to the reduction of Mn(IV) to Mn(II), occurring under reaction conditions, hindering the redox mechanism.     

Catalytic oxidation of VOCs on Au/Ce-Ti-O

Ce_xTi_1−xO₂ oxides have been synthesised by sol–gel method with x varying from 0 to 0.3 and characterised by XRD and TPR. The structure of oxides changes with the Ce/Ti molar ratio. The presence of ceria in Ce-Ti oxides inhibits the phase transition from anatase to rutile. When x = 0.3 (Ce_0.3Ti_0.7O₂ sample), the solid presents an amorphous state. The TPR results indicate that the presence of Ti enhances the reducibility of cerium oxide species. Catalytic oxidation of propene is investigated on Ce-Ti oxides and the better conversion is obtained with Ce_0.3Ti_0.7O₂ but the CO₂ selectivity reaches 63% at 400 °C. Gold is then deposited on theses oxides to improve the catalytic activity. On the basis of characterisation data (H₂ TPR), it has been suggested that gold influences the reduction of the Ce-Ti oxide support and the catalytic activity to the propene oxidation. Thus, Au/Ce-Ti-O system catalysts are promising catalysts for propene oxidation.     

Catalytic oxidation of nitrogen monoxide over La1−xCexCoO3 perovskites

This paper presents an investigation on the NO oxidation properties of perovskite oxides. La_1−xCe_xCoO₃ (x = 0, 0.05, 0.1, 0.2, 0.3, 0.4) perovskite-type oxides were synthesized through a citrate method and characterized by XRD, BET and XPS. The catalytic activities were enhanced significantly with Ce substitution, and achieved the best when x was 0.2, but decreased at higher x values. The performed characterizations reveal that the adsorbed oxygen on the surface plays an important role in the oxidation of NO into NO₂. The surface compounds after the co-adsorption of NO and O₂ at room temperature, were investigated by DRIFTS and TPD experiments. Three species: the bridging nitrate, the hyponitrites and the monodentate nitrate, were formed on the surface. The order of thermal stabilities was as follows: monodentate > hyponitrite > bridging. Among them, only the monodentate nitrate which decomposed at above 300 °C, would desorb NO₂ into the gas phase. When Ce was added, the temperature of monodentate nitrate desorption became low and the adsorption of the other two species decreased. This might be related to the oxidation state of Co on the surface. Analysis by synthesizing the characterization results and catalytic activity data shows that large amounts of adsorbed oxygen, small amount of inactive compounds on the surface and low NO₂ desorption temperature are favorable for the oxidation of NO.     

Catalytic combustion of CH4 and CO on La1−xMxMnO3 perovskites

The activities of perovskites depend on compositions and preparation methods. Various perovskites, La_1−xM_xMnO₃ (M=Ag, Sr, Ce, La), have been prepared by two different methods (co-precipitation and spray decomposition). The new preparation method, spray decomposition, produced perovskites of a high surface area of over 10 m²/g. The catalytic activities for CH₄ and CO oxidation have been studied on a series of catalysts, La_1−xM_xMnO₃. The perovskite-type oxide, La_0.7Ag_0.3MnO₃, shows the highest catalytic activity: the complete conversion of CO and CH₄ at 370 and 825 K, respectively.     

Group VI transition metal carbides as alternatives in the hydrodechlorination of chlorofluorocarbons

The synthesis of transition metal carbides of tungsten and molybdenum has been carried out via temperature programmed reactions (TPRs) of metal oxides or passivated nitrides. Their specific chloropentafluoroethane conversion rates were at best one order of magnitude less than that of a reference Pd based catalyst. The intrinsic rates range from 4.7 to 14.7 nmol m⁻² s⁻¹ and decrease as follows: Mo₂C>WC>W₂C≈WC_1−x>MoC_1−x. The group VI carbide samples catalyse hydrodehalogenation and dehydrofluorination. WC appears to be as selective towards pentafluoroethane (HFC-125) as the Pd based catalyst. Then the selectivity decreases in the following sequence: W₂C>Mo₂C>WC_1−x>MoC_1−x. All the carbide catalysts deactivate at the early stages of the reaction. Based on the XPS results and the product distribution of the reaction, the deactivation has been mainly attributed to a site blocking phenomenon due to a strong deposit of polymeric carbon and of hydrofluorocarbon polymers. Polymerisation of detected unsaturated compounds take place on acidic sites probably generated by fluoride and/or chloride in the course of the reaction.     

Catalytic NOx reduction by carbon supporting metals

Catalytic NO_x reduction by carbon supporting transition metals (Fe, Co, Ni, Cu) and potassium has been studied. The effect of oxygen on the catalytic properties of the metals has been analyzed. Temperature-programmed reactions and isothermal reactions have been conducted in a fixed bed flow reactor. Temperature-programmed reduction in hydrogen, XRD and XPS have been used to characterize the catalysts. All the metals studied catalyze the NO_x reduction by carbon in the presence of oxygen, but also the O₂–carbon reaction. Metal catalytic activity is the result of two factors, the tendency of the metal to be oxidized by NO and the easiness of the resulting oxide to be reduced by carbon. Among the metals studied, nickel exhibits the highest selectivity for NO_x reduction.

The results of this study strengthen the possible benefit of the lack of a gaseous reducing agent (such as ammonia or hydrocarbons) since the reduction of NO_x is performed by the carbon support itself.     

Effect of rhodium on the properties of bifunctional MxOy/ZrO2 catalysts in the reduction of nitrogen oxides by hydrocarbons

The catalytic properties of transition metal oxides (Cr, Ce, and Co) supported on ZrO₂ synthesized by various methods, as well as the effect of rhodium on the performance of the M_xO_y/ZrO₂ oxide systems in NO reduction with hydrocarbons (methane, propane–butane mixture, and propene) were studied. Scanning electron microscopy, ammonia thermoprogrammed desorption (NH₃-TPD), XPS, and IR spectroscopy were used to study the physicochemical indices of rhodium-promoted M_xO_y/ZrO₂ oxide catalysts. The enhancement of the redox properties of the oxide catalysts upon the introduction of rhodium does not alter their bifunctional nature in SCR activity: these catalysts have both redox and strong acid Brønsted-sites.     

The bifunctional reaction pathway and dual kinetic regimes in NOx SCR by methane over cobalt mordenite catalysts

The pathway for selective reduction of NO_x by methane over Co mordenite cataysts has been studied by comparing the rates of the individual reactions (NO oxidation, CH₄ oxidation, NO₂ reduction) with that of the combined reaction (NO + O₂ + CH₄). Co⁽⁺²⁾ was exchanged into H-MOR and Na-MOR to give catalysts with different metal loading and number of support protons. Additionally, exchanged Co⁽⁺²⁾ ions were precipitated with NaOH to produce dispersed cobalt oxide on Na-MOR. The NO oxidation rate is the same for ion exchanged Co⁽⁺²⁾ ions in H-MOR and Na-MOR, but the rate of Co⁽⁺²⁾ ions is much lower than that of cobalt oxide. NO oxidation equilibrium is obtained only for those catalysts with high metal loading, cobalt oxide or run at low GHSV. Under the conditions of selective catalytic reduction, methane oxidation by O₂ is low for all catalysts. The turnover frequency of Co on Na-MOR, however, is higher than that on H-MOR. The rate of NO₂ reduction to N₂ is directly proportional to the number of support acid sites and independent of the amount of Co. Comparison of the rates and selectivities for the individual reactions with the combined reaction of NO + O₂ + CH₄ indicates that there are two types of catalysts. For the first, the NO oxidation is in equilibrium and the rate determining step is reduction of NO₂. For these catalysts, the rate (and selectivity) for formation of N₂ is identical from NO + O₂ + CH₄ and NO₂ + CH₄. These catalysts have high metal loading and few acid sites. Nevertheless, the rate of N₂ formation increases with increasing number of protons. For the second type of catalyst, NO oxidation is not in equilibrium and is the rate limiting step. For these catalysts the rate of N₂ formation increases with increasing metal loading. Neither catalyst type, however, is optimized for the maximum formation of N₂. By using a mixture of catalysts, one with high NO oxidation activity and one with a large number of Brønsted acid sites, the rate of N₂ is greater than the weighted sum of the individual catalysts. The current results support the proposal that the pathway for selective catalytic reduction is bifunctional where metal sites affect NO oxidation, while support protons catalyze the formation of N₂.