Novel low temperature NOx storage-reduction catalysts for diesel light-duty engine emissions based on hydrotalcite compounds

A series of Pt and Pt,Cu supported catalysts were prepared by wet impregnation of Mg–Al supports obtained from hydrotalcite-type (HT) precursor compounds. These novel NO_x storage-reduction (NO_xSR) catalysts show improved performances in NO_x storage than Pt,Ba/alumina NO_xSR catalysts at reaction temperatures lower than 200 °C. These catalysts show also improved resistance to deactivation by SO₂. The effect is attributed to the formation of well dispersed Mg(Al)O particles which show good NO_x storage properties. The promoted low temperature activity is explained by the lower basicity of the Mg(Al)O mixed oxide in comparison to BaO, which induces on one hand a lower inhibition on Pt activity (NO to NO₂ oxidation and/or hydrocarbon oxidation) due to electronic effect, and on the other hand a lower thermal stability of the stored NO_x. The presence of Cu slightly inhibits activity at low temperature, although improves activity and resistance to deactivation at 300 °C. On these catalysts FT-IR characterization evidences the formation of a Pt–Cu alloy after reduction.     

Impact of redox conditions on thermal deactivation of NOx traps for diesel

Performance of NO_x traps after high-temperature treatments in different redox environments was studied. Two types of treatments were considered: aging and pretreatment. Lean and rich agings were examined for a model NO_x trap, Pt–Ba/Al₂O₃. These were done at 950 °C for 3 h, in air and in 1% H₂/N₂, respectively. Lean aging had a severe impact on NO_x trap performance, including HC and CO oxidation, and NH₃ and N₂O formation. Rich aging had minimal impact on performance, compared to fresh/degreened performance. Deactivation from lean aging was essentially irreversible due to Pt sintering, but Pt remained dispersed with the rich aging. Pretreatments were examined for a commercially feasible fully formulated NO_x trap and two model NO_x traps, Pt–Ba/Al₂O₃ and Pt–Ba–Ce/Al₂O₃. Pretreatments were done at 600 °C for 10 min, and used feed gas that simulated diesel exhaust under several conditions. Lean pretreatment severely suppressed NO_x, HC, CO, NH₃ and N₂O activities for the ceria-containing NO_x traps, but had no impact on Pt–Ba/Al₂O₃. Subsequently, a relatively mild rich pretreatment reversed this deactivation, which appears to be due to a form of Pt–ceria interaction, an effect that is well known from early work on three-way catalysts. Practical applications of results of this work are discussed with respect to NO_x traps for light-duty diesel vehicles.     

Impact of support oxide and Ba loading on the NOx storage properties of Pt/Ba/support catalysts: CO2 and H2O effects

A series of 1 wt.%Pt/_xBa/Support (Support = Al₂O₃, SiO₂, Al₂O₃-5.5 wt.%SiO₂ and Ce_0.7Zr_0.3O₂, x = 5–30 wt.% BaO) catalysts was investigated regarding the influence of the support oxide on Ba properties for the rapid NO_x trapping (100 s). Catalysts were treated at 700 °C under wet oxidizing atmosphere. The nature of the support oxide and the Ba loading influenced the Pt–Ba proximity, the Ba dispersion and then the surface basicity of the catalysts estimated by CO₂-TPD. At high temperature (400 °C) in the absence of CO₂ and H₂O, the NO_x storage capacity increased with the catalyst basicity: Pt/20Ba/Si < Pt/20Ba/Al5.5Si < Pt/10Ba/Al < Pt/5Ba/CeZr < Pt/30Ba/Al5.5Si < Pt/20Ba/Al < Pt/10BaCeZr. Addition of CO₂ decreased catalyst performances. The inhibiting effect of CO₂ on the NO_x uptake increased generally with both the catalyst basicity and the storage temperature. Water negatively affected the NO_x storage capacity, this effect being higher on alumina containing catalysts than on ceria–zirconia samples. When both CO₂ and H₂O were present in the inlet gas, a cumulative effect was observed at low temperatures (200 °C and 300 °C) whereas mainly CO₂ was responsible for the loss of NO_x storage capacity at 400 °C. Finally, under realistic conditions (H₂O and CO₂) the Pt/20Ba/Al5.5Si catalyst showed the best performances for the rapid NO_x uptake in the 200–400 °C temperature range. It resulted mainly from: (i) enhanced dispersions of platinum and barium on the alumina–silica support, (ii) a high Pt–Ba proximity and (iii) a low basicity of the catalyst which limits the CO₂ competition for the storage sites.     

Effect of the addition of transition metals to Pt/Ba/Al2O3 catalyst on the NOx storage-reduction catalysis under oxidizing conditions in the presence of SO2

The NO_x storage-reduction catalysis under oxidizing conditions in the presence of SO₂ has been investigated on Pt/Ba/Fe/Al₂O₃, Pt/Ba/Co/Al₂O₃, Pt/Ba/Ni/Al₂O₃, and Pt/Ba/Cu/Al₂O₃ catalysts compared with Pt/Ba/Al₂O₃, Pt/Fe/Al₂O₃, Pt/Co/Al₂O₃, Pt/Ni/Al₂O₃, Pt/Cu/Al₂O₃ and Pt/Al₂O₃ catalysts. The NO_x purification activity of Pt/Ba/Fe/Al₂O₃ catalyst was the highest of all the catalysts investigated in this paper after an aging treatment. That of the aged Pt/Ba/Co/Al₂O₃ and Pt/Ba/Ni/Al₂O₃ catalysts was essentially the same as that of the aged Pt/Ba/Al₂O₃ catalyst, while that of the aged Pt/Ba/Cu/Al₂O₃ and Pt/Cu/Al₂O₃ catalysts was substantially lower than the others.

The Fe-compound on the aged Pt/Ba/Fe/Al₂O₃ catalyst has played a role in decreasing the sulfur content on the catalyst after exposure to simulated reducing gas compared with the Pt/Ba/Al₂O₃ catalyst without the Fe-compound. XRD and EDX show that the Fe-compound inhibits the growth in the size of BaSO₄ particles formed on the Pt/Ba/Fe/Al₂O₃ catalyst under oxidizing conditions in the presence of SO₂ and promotes the decomposition of BaSO₄ and desorption of the sulfur compound under reducing conditions.     

Pt–Ba–Al2O3 for NOx storage and reduction: Characterization of the dispersed species

Pt–Ba–Al₂O₃ active and selective for NO_x storage and selective reduction to N₂ has been prepared and tested. Characterization of the parent Al₂O₃, Pt–Al₂O₃ and Ba–Al₂O₃ materials, as well as of Pt–Ba–Al₂O₃ catalyst in the oxidized, reduced and sulphated state has been performed by FT-IR spectroscopy of low-temperature adsorbed carbon monoxide and of adsorbed acetonitrile. XRD, TEM and XPS analyses have also been performed. Evidence for the predominance of Ba species, which are highly dispersed on the alumina support surface, and may be carbonated or sulphated, has been provided. Competitive interaction of Pt and Ba species with the surface sites of alumina has also been found.     

Reversible sorption–desorption of NOx by mixed oxides under various atmospheres

Characteristics of MnO_y–ZrO₂ and Pt–ZrO₂–Al₂O₃ as reversible sorbents of NO_x were investigated under dynamic changes in atmosphere. These sorbents can be used reversibly with a change of C₃H₈ concentration in the reaction gases. Catalytic reduction of NO occurred in the presence of propane, which was more pronounced on Pt–ZrO₂–Al₂O₃ than on MnO_y-ZrO₂ due to high activity of Pt surface for this reaction on MnO_y in MnO_y–ZrO₂. The sorption was observed as soon as the atmosphere changed from a reducing to an oxidizing one. This implies that a high equilibrium partial pressure of O₂ is necessary for NO uptake since the sorbed NO⁻₃ species becomes stable. The beginning of NO_x desorption atmospheres was somewhat dependent on the amount of stored NO_x. The presence of propane in the gas phase strongly affected the characteristic sorption and desorption properties of MnO_y–ZrO₂ and Pt–ZrO₂–Al₂O₃. The sorption and desorption properties are different for MnO_y–ZrO₂ and Pt–ZrO₂–Al₂O₃, since the noble metal or metal oxide possesses unique activity for the NO reaction with C₃H₈ and the amount of oxygen available for oxidative sorption of NO.     

A study of the behaviour of Pt supported on CeO2–ZrO2/Al2O3–BaO as NOx storage–reduction catalyst for the treatment of lean burn engine emissions

The behaviour of a Pt(1 wt.%) supported on CeO₂–ZrO₂(20 wt.%)/Al₂O₃(64 wt.%)–BaO(16 wt.%) as a novel NO_x storage–reduction catalyst is studied by reactivity tests and DRIFT experiments and compared with that of Pt(1%)–BaO(15 wt.%) on alumina. The former catalyst, designed as a hydrothermally stable sample, is composed of an alumina modified with Ba ions and an overlayer of ceria-zirconia. The results pointed out that during the calcination barium ions migrates over the surface of the catalyst which thus show a good NO_x storage–reduction behaviour comparable with that of Pt–BaO on alumina, although Ba ions result much better dispersed.     

On the dynamic behavior of “NOx-storage/reduction” Pt–Ba/Al2O3 catalyst

The NO_x storage and reduction functions of a Pt–Ba/Al₂O₃ “NO_x storage–reduction” catalyst has been investigated in the present work by applying the transient response and the temperature programmed reaction methods, by using propylene as the reducing agent. It is found that: (i) the storage of NO_x occurs first at BaO and then at BaCO₃, which are the most abundant sites following regeneration of catalyst with propylene; (ii) the overall storage process at BaCO₃ is slower than at BaO; (iii) CO₂ inhibits the NO_x storage at low temperatures; (iv) the amount of NO_x stored up to catalyst saturation at 350 °C corresponds to 17.6% of Ba; (v) the reduction of stored NO_x groups is fast and is limited by the concentration of propylene in the investigated T range (250–400 °C); (vi) selectivity to N₂ is almost complete at 400 °C but is significantly lower at 300 °C due to the formation of NO which can be tentatively ascribed to the presence of unselective Pt–O species.     

Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled NO over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (¹⁵NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NO_x storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al₂O₃ catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H₂ and/or CO and NO on reduced Rh and/or Pt sites. The second N₂ peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NO_x, gas phase NO_x or O₂. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H₂.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al₂O₃ catalyst at 250 and 350 °C was found to be dependent on the rate of NO_x storage, since the rate of regeneration was sufficient to remove the NO_x stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al₂O₃ catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NO_x stored on the catalyst deteriorated from cycle to cycle until the amount of NO_x stored in the lean phase matched the NO_x reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al₂O₃ catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.     

Comparative study of structural properties and NOx storage-reduction behavior of Pt/Ba/CeO2 and Pt/Ba/Al2O3

Differences in the NO_x storage-reduction (NSR) behavior of Pt/Ba/CeO₂ and Pt/Ba/Al₂O₃ have been identified and traced to their different chemical and structural properties. The results show that Pt/Ba/CeO₂ exhibits inferior NO_x storage and, particularly, reduction (regeneration) activity compared to the Al₂O₃ supported catalyst. The incomplete reduction of the stored NO_x-species in Pt/Ba/CeO₂ seems to be caused by a faster and more profound reoxidation of Pt particles during the lean period as evidenced by in situ X-ray absorption spectroscopy. Interestingly, the reduction activity could be significantly improved by a pre-reduction step at mild conditions. Exposure of the Pt/Ba/CeO₂ catalyst to reducing H₂ atmosphere in the temperature range 300–500 °C lead to a moderate increase of Pt particle size which beneficially influenced the regeneration activity. In contrast, pre-reduction at temperatures above 500 °C was unfavorable and resulted in a severe decrease of the regeneration activity, probably due to migration of the partially reduced CeO₂ onto the surface of Pt particles.     

Pt-Ba/alumina NOx storage-reduction catalysts: Influence of Ba loading on NOx storage behavior

The NO_x storage behavior of a series of Pt-Ba/Al₂O₃ catalysts, prepared by wet impregnation of Pt/Al₂O₃ with Ba(Ac)₂, has been investigated. The catalysts with Ba loadings in the range 4.5–28 wt.% were calcined at 500 °C in air and subsequently exposed to NO pulses in 5 vol.% O₂/He atmosphere. Catalysts were characterized by means of thermogravimetry (TG) combined with mass spectroscopy (MS) and XRD before and after exposure to NO pulses. Characterization of the calcined catalysts corroborated the existence of three Ba-containing phases which are discernible based on their different thermal stability: BaO, LT-BaCO₃ and HT-BaCO₃. Characterization after NO_x exposure showed that the different Ba-containing phases present in the catalysts possess different reactivity for barium nitrate formation, depending on their interfacial contact. The different Ba(NO₃)₂ species produced upon NO_x exposure could be distinguished based on their thermal stability. The study revealed that during the NO_x storage process a new thermally instable BaCO₃ phase formed by reaction of evolved CO₂ with active BaO. The fraction of Ba-containing species that were active in NO_x storage depended on the Ba loading, showing a maximum at a Ba loading of about 17 wt.%. Lower and higher Ba loading resulted in a significant loss of the overall efficiency of the Ba-containing species in the storage process. The loss in efficiency observed at higher loading is attributed to the lower reactivity of the HT-BaCO₃, which becomes dominant at higher loading, and the increased mass transfer resistance.     

Mean field modelling of NOx storage on Pt/BaO/Al2O3

A mean field model, for storage and desorption of NO_x in a Pt/BaO/Al₂O₃ catalyst is developed using data from flow reactor experiments. This relatively complex system is divided into five smaller sub-systems and the model is divided into the following steps: (i) NO oxidation on Pt/Al₂O₃; (ii) NO oxidation on Pt/BaO/Al₂O₃; (iii) NO_x storage on BaO/Al₂O₃; (iv) NO_x storage on Pt/BaO/Al₂O₃ with thermal regeneration and (v) NO_x storage on Pt/BaO/Al₂O₃ with regeneration using C₃H₆. In this paper, we focus on the last sub-system. The kinetic model for NO_x storage on Pt/BaO/Al₂O₃ was constructed with kinetic parameters obtained from the NO oxidation model together with a NO_x storage model on BaO/Al₂O₃. This model was not sufficient to describe the NO_x storage experiments for the Pt/BaO/Al₂O₃, because the NO_x desorption in TPD experiments was larger for Pt/BaO/Al₂O₃, compared to BaO/Al₂O₃. The model was therefore modified by adding a reversible spill-over step. Further, the model was validated with additional experiments, which showed that NO significantly promoted desorption of NO_x from Pt/BaO/Al₂O₃. To this NO_x storage model, additional steps were added to describe the reduction by hydrocarbon in experiments with NO₂ and C₃H₆. The main reactions for continuous reduction of NO_x occurs on Pt by reactions between hydrocarbon species and NO in the model. The model is also able to describe the reduction phase, the storage and NO breakthrough peaks, observed in experiments.     

Potassium–copper and potassium–cobalt catalysts supported on alumina for simultaneous NOx and soot removal from simulated diesel engine exhaust

This paper deals with the activity of bimetallic potassium–copper and potassium–cobalt catalysts supported on alumina for the reduction of NO_x with soot from simulated diesel engine exhaust. The effect of the reaction temperature, the soot/catalyst mass ratio and the presence of C₃H₆ has been studied. In addition, the behavior of two monometallic catalysts supported on zeolite beta (Co/beta and Cu/beta), previously used for NO_x reduction with C₃H₆, as well as a highly active HC-SCR catalyst (Pt/beta) has been tested for comparison. The preliminary results obtained in the absence of C₃H₆ indicate that, at temperatures between 250 and 400 °C, the use of bimetallic potassium catalysts notably increases the rate of NO_x reduction with soot evolving N₂ and CO₂ as main reaction products. At higher temperatures, the catalysts mainly favor the direct soot combustion with oxygen. In the presence of C₃H₆, an increase in the activity for NO_x reduction has been observed for the catalyst with the highest metal content. At 450 °C, the copper-based catalysts (Cu/beta and KCu2/Al₂O₃) show the highest activity for both NO_x reduction (to N₂ and CO₂) and soot consumption. The Pt/beta catalyst does not combine, at any temperature, a high NO_x reduction with a high soot consumption rate.     

Lean NOx reduction with CO + H2 mixtures over Pt/Al2O3 and Pd/Al2O3 catalysts

The reduction of NO_x by hydrogen under lean burn conditions over Pt/Al₂O₃ is strongly poisoned by carbon monoxide. This is due to the strong adsorption and subsequent high coverage of CO, which significantly increases the temperature required to initiate the reaction. Even relatively small concentrations of CO dramatically reduce the maximum NO_x conversions achievable. In contrast, the presence of CO has a pronounced promoting influence in the case of Pd/Al₂O₃. In this case, although pure H₂ and pure CO are ineffective for NO_x reduction under lean burn conditions, H₂/CO mixtures are very effective. With a realistic (1:3) H₂:CO ratio, typical of actual exhaust gas, Pd/Al₂O₃ is significantly more active than Pt/Al₂O₃, delivering 45% NO_x conversion at 160 °C, compared to >15% for Pt/Al₂O₃ under identical conditions. The nature of the support is also critically important, with Pd/Al₂O₃ being much more active than Pd/SiO₂. Possible mechanisms for the improved performance of Pd/Al₂O₃ in the presence of H₂+CO are discussed.     

Comparative study of Pt-based catalysts on different supports in the low-temperature de-NOx-SCR with propene

Pt-based catalysts have been prepared using supports of different nature (γ-Al₂O₃, ZSM-5, USY, and activated carbon (ROXN)) for the C₃H₆-SCR of NO_x in the presence of excess oxygen. Nitrogen adsorption at 77 K, pH measurements, temperature-programmed desorption of propene, and H₂ chemisorption were used for the characterization of the different supports and catalysts. The performance of these catalysts has been compared in terms of de-NO_x activity, hydrocarbon adsorption and combustion at low temperature, and selectivity to N₂. Maximum NO_x conversions for all the catalysts were achieved in the temperature range of 200–250°C. The order of activity was, Pt-USY>Pt/ROXNPt-ZSM-5Pt/Al₂O₃. At temperatures above 300°C only Pt/ROXN maintains a high activity caused by the consumption of the support, while the other catalysts present a strong deactivation. Propene combustion starts at the same temperature for all the catalytic systems (160°C). Complete hydrocarbon combustion is directly related to the acidity of the support, thus determining the temperature of the maximum NO_x reduction. The support play an important role in the reaction mechanism through the hydrocarbon activation. N₂O formation was observed for all the catalysts. N₂ selectivity ranges from 15 to 30% with the order, Pt/ROXN>Pt-USYPt/Al₂O₃>Pt-ZSM-5. The catalytic systems exhibit a stable operation under isothermal conditions during time-on-stream experiments.     

Impact of copper on the performance and sulfur tolerance of barium-based NOx storage-reduction catalysts

The presence of sulfur in automotive exhaust is known to be detrimental to lean-NO_x traps as SO₂ is oxidized to SO₃ that competes with NO₂ for sites on the trap and is difficult to remove. In this study the effect of adding Cu to the prototypical Pt–BaO/γ-Al₂O₃ formulation on the system's tolerance for sulfur was investigated. It was found that in the absence of sulfur, Cu decreases the performance in terms of both NO_x storage capacity and reduction of NO_x to N₂ during regeneration. In the presence of SO₂, Cu provides a significant improvement in sulfur tolerance so that, after sulfur exposure, the storage capacity of the Cu-modified material can exceed that of the baseline material. The sulfur tolerance afforded by Cu is attributed to a moderation in the activity for SO₂ oxidation resulting from the formation of a Pt–Cu bimetallic phase. The propensity for NO oxidation is also modified, but to a lesser effect. Evidence for the bimetallic phase is provided by temperature-programmed reduction (TPR) and electron microscopy. The impact of SO₂ on the Cu-modified material is greater during the regenerative reduction cycle. In this case, the results suggest that sulfur blocks Pt and possibly Cu sites and that the sulfur is not removed by oxidation during the subsequent storage cycle. Hence, activity lost during the reduction cycle is not restored. In contrast, sulfur that blocks Pt sites on the baseline material during the reduction cycle is subsequently oxidized and desorbs from the Pt, restoring the activity. However, some of the resulting SO₃ reacts with the BaO to form BaSO₄, and there is a partial loss of storage capacity.     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O

A multi-component NO_x-trap catalyst consisting of Pt and K supported on γ-Al₂O₃ was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H₂O and CO₂ on NO_x storage. The Al₂O₃ support was shown to have NO_x trapping capability with and without Pt present (at 250 °C Pt/Al₂O₃ adsorbs 2.3 μmols NO_x/m²). NO_x is primarily trapped on Al₂O₃ in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO_x/m², and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al₂O₃ catalyst are coordinated on the Al₂O₃ support at saturation.

When 5% CO₂ was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H₂O was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al₂O₃-based nitrates decreased by 92%. Interestingly, with both 5% CO₂ and 5% H₂O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al₂O₃ destabilized the K–CO₂ bond; specifically, H₂O mitigates the NO_x storage capacity losses associated with carboxylate competition.     

Pt-Ba/alumina NOx storage-reduction catalysts: Effect of Ba-loading on build-up, stability and reactivity of Ba-containing phases

A series of Pt-Ba/Al₂O₃ catalysts with Ba-loadings in the range 4.5–28 wt.% has been prepared by wet impregnation of Pt/Al₂O₃ with barium acetate (Ba(Ac)₂) as Ba precursor. The build-up and thermal stability of the deposited Ba-containing species was followed by means of XRD and thermogravimetry (TG) combined with mass spectroscopy (MS). Samples were characterized before and after thermal treatment (calcination). The study showed that the thermal stability of the Ba-containing phases depends on their interaction with the alumina support and the presence of dispersed platinum. In calcined catalysts, three different Ba-containing species could be distinguished based on their crystallinity and thermal stability. The relative concentration of these species varied with the Ba-loading. The first layer of Ba-containing species, corresponding to saturation of the alumina surface with Ba(Ac)₂, contained up to 12.5 wt.% of Ba in the form of amorphous BaO. Increasing the Ba-loading further resulted in 5–6 wt.% of Ba in the form of amorphous carbonates with relatively low thermal stability (LT-BaCO₃). At Ba-loadings higher than about 16 wt.%, crystalline barium carbonate became discernible which exhibited remarkably higher thermal stability (HT-BaCO₃). NO_x storage tests accomplished by exposing the catalysts to pulses of NO in oxygen containing carrier gas at 300 °C indicated that from all characterized Ba-containing phases, LT-BaCO₃ possesses the highest reactivity for NO_x storage, i.e. LT-BaCO₃ is transformed most rapidly to Ba(NO₃)₂.     

Influence of CO2 and H2O on NOx storage and reduction on a Pt–Ba/γ-Al2O3 catalyst

In this paper, the effect of CO₂ and H₂O on NO_x storage and reduction over a Pt–Ba/γ-Al₂O₃ (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO₂ and H₂O, NO_x is stored on BaCO₃ sites only. Moreover, H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N₂ as well as complete regeneration of stored NO. In the presence of CO₂, NO is oxidized into NO₂ and more NO_x is stored as in the presence of H₂O, resulting in 30% barium utilization. Bulk barium sites are inactive in NO_x trapping in the presence of CO₂·NH₃ formation is seen in the rich phase and the selectivity towards N₂ is 83%. Ba(NO₃)₂ is always completely regenerated during the subsequent rich phase. In the absence of CO₂ and H₂O, both surface and bulk barium sites are active in NO_x storage. As lean/rich cycling proceeds, the selectivity towards N₂ in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NO_x storage.