Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Catalytic decomposition of N2O and catalytic reduction of N2O and N2O + NO by NH3 in the presence of O2 over Fe-zeolite

The decomposition of N₂O, and the catalytic reduction by NH₃ of N₂O and N₂O + NO, have been studied on Fe-BEA, -ZSM-5 and -FER catalysts. These catalysts were prepared by classical ion exchange and characterized by TPR after various activation treatments. Fe-FER is the most active material in the catalytic decomposition because “oxo-species” reducible at low temperature, appearing upon interaction of Fe^II-zeolite with N₂O (-oxygen), are formed in largest amounts with this material. The decomposition of N₂O is promoted by addition of NH₃, and even more with NH₃ + NO in the case of Fe-FER and -BEA. It is proposed that the NO-promoted reduction of N₂O originated from the fast surface reaction between -oxygen O^* and NO^* to yield NO₂^*, which in turn reacts immediately with NH₃.     

Promoting effects of CO2 on dehydrogenation of propane over a SiO2-supported Cr2O3 catalyst

The effects of carbon dioxide on the dehydrogenation of C₃H₈ to produce C₃H₆ were investigated over several Cr₂O₃ catalysts supported on Al₂O₃, active carbon and SiO₂. Carbon dioxide exerted promoting effects only on SiO₂-supported Cr₂O₃ catalysts. The promoting effects of carbon dioxide over a Cr₂O₃/SiO₂ catalyst were to enhance the yield of C₃H₆ and to suppress the catalyst deactivation.     

Selective catalytic reduction of nitric oxide with ammonia using MoO3/TiO2: Catalyst structure and activity

A series of titania supported MoO₃ catalysts (0–20 wt.-% MoO₃) were prepared by dry impregnation. The influence of the MoO₃ content on their catalytic performance for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of oxygen, as well as on their textural and structural properties has been studied. The samples were characterized by XRD, XPS, IR, and BET and porosimetry measurements. The coverage of the TiO₂ support by surface polymeric molybdenum species (where molybdenum is octahedrally coordinated) increases with the molybdenum loading. The formation of a layer of these interacting species on top of the titania surface is complete in the range 15–20 wt.-% MoO₃. The formation of crystallites of bulk MoO₃ starts before the completion of this surface layer (at around 10 wt.-% MoO₃) and increases progressively as the molybdenum loading increases from 10 to 20 wt.-% MoO₃. The SCR activity of the MoO₃/TiO₂ catalysts increases as the MoO₃ content increases to 15 wt.-% and then, for a further increase of the molybdenum loading, it slightly decreases. No specific influence of the molybdenum content on the resistance of catalysts towards SO₂ was observed; the same slight deactivation took place, when the SCR activity was measured in the presence of SO₂ in the feed, for all samples. Our results indicate that the octahedrally coordinated polymeric molybdenum surface species are mainly responsible for the exhibited SCR activity of the MoO₃/TiO₂ catalysts.     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst

The kinetics of the selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂ has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<T_R<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O₂, and essentially 0 with respect to NH₃. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH₃ was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) Cu^I is oxidized by O₂ to “Cu^II-oxo”, (ii) “Cu^II-oxo” reacts with NO to yield “Cu^II-N_xO_y”, and (iii) finally “Cu^II-N_xO_y” is reduced by NH₃ to give N₂, H₂O, and the regeneration of Cu^I (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that Cu^I or “Cu^II-oxo” species constitute the rate-determining active center.     

A comparative study of water gas shift reaction over gold and platinum supported on ZrO2 and CeO2–ZrO2

In this study platinum- and gold-based catalysts supported on ZrO₂ and ceria–zirconia solid solution have been characterized by several techniques (TPR, XRD, BET, HRTEM) and tested in the water gas shift (WGS) reaction under feed conditions typical of an autothermal reformer outlet. Platinum and gold catalysts behave differently especially in the range of 423–513 K, with gold being superior than platinum. The possibility of modifying the redox and structural characteristics of zirconia with the insertion of ceria allowed us to conclude that the bulk redox properties of the support play a secondary role, while the key parameter for an active WGS catalyst is the nature of metal support interface. This, in turn, depends on the metal particle distribution and on the structural and morphological properties of support. It has been found that the synergism between precious metals and support can be designed with an appropriate choice of the parameters of synthesis and the characteristics of support.     

Catalytic activity and solid acidity of vanadium oxide thin layer loaded on TiO2, ZrO2, and SnO2

Vanadium oxide spread highly on TiO₂ (anatase, A) and SnO₂, and rather densely on TiO₂ (rutile, R) and ZrO₂ to make the monolayer in less than 4–5 V nm⁻². Profile of acid site of the monolayer was measured by temperature programmed desorption of ammonia, and its relation with the surface oxidation state was studied. The acid site density was high on the V₂O₅/TiO₂ (A) independent of the degree of oxidation. On the other hand, that of V₂O₅/TiO₂ (R) and V₂O₅/ZrO₂ depended on the oxidation state, and the high value of the concentration was observed on the oxidized one. The strength of acid site generated on the V₂O₅ monolayer on TiO₂ was as high as on the HZSM-5 zeolite. Turnover frequency (TOF) of propane conversion, and product selectivity were measured in propane oxidation. Among tested oxides, the V₂O₅/TiO₂ (A) showed the high TOF and selectivity to form propylene, while those loaded on TiO₂ (R) and ZrO₂ the small TOF and poor selectivity. Therefore, the reaction profile of activity and selectivity could be related with the extent of spreading and solid acidity. An idea of limit of the acid site density ca. 1.5 nm⁻² on the monolayer was elucidated.     

Electrocatalyst materials for fuel cells based on the polyoxometalates—K7 or H7[(P2W17O61)Fe(H2O)] and Na12 or H12[(P2W15O56)2Fe4(H2O)2]

Free acids of the iron substituted heteropoly acids (HPA), H₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (HFe1) and H₁₈[(P₂W₁₅O₅₆)₂Fe^III₂(H₂O)₂] (HFe2) were prepared from the salts K₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (KFe1) and Na₁₂[(P₂W₁₅O₅₆)₂Fe^III₄(H₂O)₂] (NaFe4), respectively. The iron-substituted HPA were adsorbed on to XC-72 carbon based GDLs to form HPA doped GDEs after water washing with HPA loadings of ca. 1 μmol. The HPA was detected throughout the GDL by EDX. Solution electrochemistry of the free acids are reported for the first time in sulfate buffer, pH 1-3. The hydrogen oxidation reaction was catalyzed by KFe1 at 0.33 V, with an exchange current density of 38 mA/cm². Moderate activity for the oxygen reduction reaction was observed for the iron substituted HPA, which was dramatically improved by selectively removing oxygen atoms from the HPA by cycling the fuel cell cathode under N₂ followed by reoxidation to give a restructured oxide catalyst. The nanostructured oxide achieved an OCV of 0.7 V with a Tafel slope of 115 mV/decade. Cycling the same catalysts in oxygen resulted in an improved catalyst/ionomer/carbon configuration with a slightly higher Tafel slope, 128 mV/decade but a respectable current density of 100 mA/cm² at 0.2 V.     

Enhanced activity of an In–Fe2O3/H-ZSM-5 catalyst for NO reduction with methane

Selective reduction of NO by CH₄ on an In–Fe₂O₃/H-ZSM-5 catalyst was investigated in the presence of excess oxygen. Compared with In/H-ZSM-5, the In–Fe₂O₃/H-ZSM-5 catalyst with high Fe₂O₃ contents showed higher activity in a wide range of reaction temperatures. It was found that the addition of Fe₂O₃ yielded a promotion effect on CH₄ activation. The influence of water vapor on NO conversion was also investigated. The activity of the In/H-ZSM-5 catalyst has been found to be strongly inhibited by water vapor, while the In–Fe₂O₃/H-ZSM-5 catalyst remained fairly active in the presence of 3.3% steam.     

Utilization of carbon dioxide as soft oxidant for oxydehydrogenation of ethylbenzene to styrene over V2O5–CeO2/TiO2–ZrO2 catalyst

Vanadium oxide and cerium oxide doped titania–zirconia mixed oxides were explored for oxidative dehydrogenation of ethylbenzene to styrene utilizing carbon dioxide as a soft oxidant. The investigated TiO₂–ZrO₂ mixed oxide support with high specific surface area (207 m² g⁻¹) was synthesized by a coprecipitation method. Over the calcined support (550 °C), a monolayer equivalent (15 wt.%) of V₂O₅, CeO₂ or a combination of both were deposited by using wet-impregnation or co-impregnation methods to make the V₂O₅/TiO₂–ZrO₂, CeO₂/TiO₂–ZrO₂ and V₂O₅–CeO₂/TiO₂–ZrO₂ combination catalysts, respectively. These catalysts were characterized using X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature preprogrammed reduction (TPR), CO₂ temperature preprogrammed desorption (TPD) and BET surface area methods. All characterization studies revealed that the deposited promoter oxides are in a highly dispersed form over the support, and the combined acid–base and redox properties of the catalysts play a major role in this reaction. The V₂O₅–CeO₂/TiO₂–ZrO₂ catalyst exhibited a better conversion and product selectivity than other combinations. In particular, the addition of CeO₂ to V₂O₅/TiO₂–ZrO₂ prevented catalyst deactivation and helped to maintain a high and stable catalytic activity.     

Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.     

Formation of active sites on Ir/WO3–SiO2 for selective catalytic reduction of NO by CO

Pretreatment conditions for the activation of Ir/WO₃–SiO₂ for the selective catalytic reduction of NO by CO in the presence of excess O₂ were studied. Sequential treatment involving calcination in the presence of O₂ and H₂O followed by reduction and then re-oxidation under mild conditions was found to effectively activate Ir/WO₃–SiO₂. Temperature-programmed desorption during calcination, X-ray diffraction, and temperature-programmed reduction by H₂ revealed that calcination was necessary for oxidative removal of the NH₃ ligands from the iridium precursor, that reduction produced metallic iridium and partially reduced tungsten oxide, and that re-oxidation produced tungsten oxide with low reducibility. Transmission electron microscopy revealed that Ir was supported on finely dispersed tungsten oxide and that the iridium particle size after the sequential activation was 1–1.5 nm.     

Fe2O3/Al2O3 catalysts for the N2O decomposition in the nitric acid industry

Fe₂O₃ catalysts supported on Al₂O₃ were used to remove nitrous oxide from the nitric acid plant simulated process stream (containing O₂, NO and H₂O). Catalysts were prepared by the coprecipitation method and were characterized for their physico-chemical properties by BET, XRD, AFM and TPR analysis. A strong influence of the post-preparation heating conditions on the structural and catalytic properties of the catalysts has been evidenced. Laboratory tests revealed 95% conversion of N₂O at temperature 750 °C and a slight decrease in activity in the presence of H₂O and NO. The catalysts were inert towards decomposition of NO. The pilot-plant reactor and real plant studies (up to 3300 h time-on-stream) confirmed high activity and very good mechanical stability of the catalysts as well as no decomposition of nitric oxide.     

NO decomposition and reduction by CH4 over Sr/La2O3

Both NO decomposition and NO reduction by CH₄ over 4%Sr/La₂O₃ in the absence and presence of O₂ were examined between 773 and 973 K, and N₂O decomposition was also studied. The presence of CH₄ greatly increased the conversion of NO to N₂ and this activity was further enhanced by co-fed O₂. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH₄ in the absence of O₂, and reduction with 1% O₂ in the feed were 8.3·10⁻⁴, 4.6·10⁻³, and 1.3·10⁻² μmol N₂/s m², respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N₂ formation by decomposition was inhibited by O₂ in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH₄ continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O₂ with equal activation energies of 26 kcal/mol. The addition of O₂ increased the reaction order in CH₄ at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O₂ was 0.26 up to 0.5% O₂ during which time the CH₄ concentration was not decreased significantly. N₂O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10⁻⁴ μmol N₂/s m² at 623 K and 1220 ppm N₂O and an activation energy of 24 kcal/mol. The addition of CH₄ inhibits this decomposition reaction. Finally, the use of either CO or H₂ as the reductant (no O₂) produced specific activities at 773 K that were almost 5 times greater than that with CH₄ and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H₂ to reduce NO to N₂ over these REO catalysts.     

Transient reaction analysis and steady-state kinetic study of selective catalytic reduction of NO and NO + NO2 by NH3 over Fe/ZSM-5

The reaction kinetics of selective catalytic reduction (SCR) by NH₃ on NO (standard SCR) and on NO + NO₂ (fast SCR) over Fe/ZSM-5 were investigated using transient and steady-state analyses. In the standard SCR, the N₂ production rate was transiently promoted in the absence of gaseous NH₃; this enhancement can be attributed to the negative reaction order of NH₃ (between −0.21 and −0.11). The steady-state data for the standard SCR could be fit to a Langmuir–Hinshelwood-type reaction between NO_ad and O_ad to form NO₂. In the fast SCR, however, the promotion behavior in the absence of gaseous NH₃ was not observed and the apparent NH₃ order changed from positive to negative with NH₃ concentration. The steady-state rate analysis combined with elementary reaction modeling suggested that competitive adsorption between NO₂ and NH₃ was occurring due to strong NO₂ adsorption; this must be the main reason for the absence of the promotion effect.     

Interactions NO—CO and O2—NO—CO on CuCo2O4/γ-Al2O3 and on γ-Al2O3- and CuCo2O4/γ-Al2O3-supported Pt, Rh and Pt—Rh catalysts, a transient response study

The interactions NO—CO and O₂—NO—CO have been studied onCuCo₂O₄γ-Al₂O₃ and on γ-Al₂O₃- and CuCo₂O₄γ-Al₂O₃-supported Pt, Rh and Pt—Rh catalysts. The deposition of noble metals (Pt, Rh and Pt—Rh) on CuCo₂O₄γ-Al₂O₃ instead of γ-Al₂O₃ is beneficial in: lowering the temperature at which maximum N₂O is formed and decreasing the maximum N₂O concentration attained; lowering the onset temperature of NO to N₂ reduction, and increasing the N₂ selectivity; preserving the activity towards NO to N₂ reduction on a higher level following the concentration step NO + COO₂+ NO + CO and changing the conditions from stoichiometric to oxidizing (50% excess of oxidants). The reason for this behaviour of the CuCo₂O₄γ-Al₂O₃-based noble metal catalysts is the formation (reversible) of a reduced surface layer on the CuCo₂O₄ supported spinel under the conditions of a stoichiometric NO + CO mixture.     

Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2

Among various Cu/ZnO/ZrO₂ catalysts with the Cu/Zn ratio of 3/7, the one with 15 wt.% of ZrO₂ obtains the best activity for methanol synthesis by hydrogenation of CO. The TPR, TPO and XPS analyses reveal that a new copper oxide phase is formed in the calcined Cu/ZnO/ZrO₂ catalysts by the dissolution of zirconium ions in copper oxide. In addition, the Cu/ZnO/ZrO₂ catalyst with 15 wt.% of ZrO₂ turns out to contain the largest amount of the new copper oxide phase. When the Cu/ZnO/ZrO₂ catalysts is reduced, the Cu²⁺ species present in the ZrO₂ lattice is transformed to Cu⁺ species. This leads to the speculation that the addition of ZrO₂ to Cu/ZnO catalysts gives rise to the formation of Cu⁺ species, which is related to the methanol synthesis activity of Cu/ZnO/ZrO₂ catalyst in addition to Cu metal particles. Consequently, the ratio of Cu⁺/Cu⁰ is an important factor for the specific activity of Cu/ZnO/ZrO₂ catalyst for methanol synthesis.     

A novel carbon-supported vanadium oxide catalyst for NO reduction with NH3 at low temperatures

A novel activated carbon-supported vanadium oxide catalyst was studied for SCR of NO with NH₃ at low temperatures (100 – 250°C). The effects of reaction temperature, preparation conditions and SO₂ on SCR activity were evaluated. The results show that this catalyst has a high catalytic activity for NO–NH₃–O₂ reaction at low temperatures. Preoxidation of the calcined catalyst helps improve catalytic activity. V₂O₅ loading, other than calcination temperature, gives a significant influence on the activity. SO₂ in the flue gas does not de-activate the catalyst but improves it. A stability test of more than 260 h shows that the catalyst is highly active and stable in the presence of SO₂.     

Modification of the surface reactivity of Cu-MFI during chemisorption and transformation of the reagents in the selective reduction of NO with propane and O2

The steady-and unsteady-state catalytic behaviour of Cu-MFI in the conversion of propane and NO in the presence of O₂ is reported, showing how the chemisorption and transformation of reactants may influence the surface reactivity. Various effects were observed: (i) a change in the surface reactivity and kinetics in going from low to high concentrations of NO or propane, (ii) the transformation of NO to N₂ and N₂O promoted at low temperature (250°C) by oxygen in the absence of hydrocarbon, (iii) the influence of NO over the surface reactivity of the catalyst in the conversion of propane and (iv) the influence of surface precoverage with oxidized nitrogen oxides (N_xO_y) or carboxylate species on the catalyst transient reactivity in the reduction of NO to N₂. In particular, Cu-MFI is initially more active when oxidized nitrogen oxides are present, suggesting that the active intermediate in the reduction of NO with propane is a complex formed by the reaction of nitrate with activated hydrocarbon. It is shown, however, that strongly bound oxidized nitrogen oxides may have also additional effects on the surface reactivity: (i) can promote the conversion of NO to N₂ and N₂O in transient conditions and (ii) can give a partial inhibition of the surface reactivity blocking copper ions due to their strong chemisorption. Furthermore, it is shown that NO reacts faster with oxygen than hydrocarbon forming N_xO_y species which are then the oxidizing agent for the hydrocarbon. It is thus suggested that the surface reactivity of Cu-MFI in the reduction of NO with propane/oxygen depends on the surface population of nitrogen oxide adspecies which influence not only the surface reactivity, but also the pathway of hydrocarbon oxidation.