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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

A study of the deactivation by sulfur and regeneration of a model NSR Pt/Ba/Al2O3 catalyst

The deactivation by sulfur and regeneration of a model Pt/Ba/Al₂O₃ NO_x trap catalyst is studied by hydrogen temperature programmed reduction (TPR), X-ray diffraction (XRD), and NO_x storage capacity measurements. The TPR profile of the sulfated catalyst in lean conditions at 400 °C reveals three main peaks corresponding to aluminum sulfates (550 °C), “surface” barium sulfates (650 °C) and “bulk” barium sulfates (750 °C). Platinum plays a role in the reduction of the two former types of sulfates while the reduction of “bulk” barium sulfates is not influenced by the metallic phase. The thermal treatment of the sulfated catalyst in oxidizing conditions until 800 °C leads to a stabilization of sulfates which become less reducible. Stable barium sulfides are formed during the regeneration under hydrogen at 800 °C. However, the presence of carbon dioxide and water in the rich mixture allows eliminating more or less sulfides and sulfates, depending on the temperature and time. The regeneration in the former mixture at 650 °C leads to the total recovery of the NO_x storage capacity even if “bulk” barium sulfates are still present on the catalyst.     

Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts

A method to quantify DRIFT spectral features associated with the in situ adsorption of gases on a NO_x adsorber catalyst, Pt/K/Al₂O₃, is described. To implement this method, the multicomponent catalyst is analysed with DRIFT and chemisorption to determine that under operating conditions the surface comprised a Pt phase, a pure γ-Al₂O₃ phase with associated hydroxyl groups at the surface, and an alkalized-Al₂O₃ phase where the surface –OH groups are replaced by –OK groups. Both DRIFTS and chemisorption experiments show that 93–97% of the potassium exists in this form. The phases have a fractional surface area of 1.1% for the 1.7 nm-sized Pt, 34% for pure Al₂O₃ and 65% for the alkalized-Al₂O₃. NO₂ and CO₂ chemisorption at 250 °C is implemented to determine the saturation uptake value, which is observed with DRIFTS at 250 °C. Pt/Al₂O₃ adsorbs 0.087 μmol CO₂/m²and 2.0 μmol NO₂/m², and Pt/K/Al₂O₃ adsorbs 2.0 μmol CO₂/m²and 6.4 μmol NO₂/m². This method can be implemented to quantitatively monitor the formation of carboxylates and nitrates on Pt/K/Al₂O₃ during both lean and rich periods of the NO_x adsorber catalyst cycle.     

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.     

A new NOx storage-reduction electrochemical catalyst

A new NO_x storage-reduction electrochemical catalyst has been prepared from a polycrystalline Pt film deposited on 8 mol% Y₂O₃-stabilized ZrO₂ (YSZ) solid electrolyte. BaO has been added onto the Pt film by impregnation method. The NO_x storage capacity of Pt-BaO/YSZ system was investigated at 350 °C and 400 °C under lean conditions. Results have shown that the electrochemical catalyst was effective for NO_x storage. When nitric oxides are fully stored, the catalyst potential is high and reaches its maximum. On the other hand, when a part of NO and also NO₂ desorb to the gas phase, the catalyst potential remarkably drops and finally stabilizes when no more NO_x storage occurs but only the reaction of NO oxidation into NO₂. Furthermore, the investigation has clearly demonstrated that the catalyst potential variation versus temperature or chemical composition is an effective indicator for in situ following the NO_x storage-reduction process, i.e. the storage as well as the regeneration phase. The catalyst potential variations during NO_x storage process was explained in terms of oxygen coverage modifications on the Pt.     

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.     

NOx storage-reduction catalysts based on hydrotalcite: Effect of Cu in promoting resistance to deactivation

Novel NO_x storage-reduction (NO_xSR) catalysts prepared by Pt and/or Cu impregnation of Mg–Al (60:40) hydrotalcite (HT)-type compounds show better performances in NO_x storage than Pt–Ba/Al₂O₃ Toyota-type NO_xSR catalysts at reaction temperatures lower than 250 °C. The presence of Pt or Cu considerably enhances the activity, with the former more active. The nature of the HT source, however, also influences performance. The co-presence of Pt and Cu slightly worsens the low temperature activity, but considerably promotes the resistance to deactivation after severe hydrothermal treatment and in the presence of SO₂. This effect is attributed to both the possibility of formation of a Pt–Cu alloy after reduction, and the modification of the HT induced during the deposition of Cu. The overall Pt–Cu/HT performances are thus superior to those of the Pt–Ba/Al₂O₃ Toyota-type NO_xSR catalysts.     

The reduction phase in NOx storage catalysis: Effect of type of precious metal and reducing agent

The effect of different reducing agents (H₂, CO, C₃H₆ and C₃H₈) on the reduction of stored NO_x over PM/BaO/Al₂O₃ catalysts (PM = Pt, Pd or Rh) at 350, 250 and 150 °C was studied by the use of both NO₂-TPD and transient reactor experiments. With the aim of comparing the different reducing agents and precious metals, constant molar reduction capacity was used during the reduction period for samples with the same molar amount of precious metal. The results reveal that H₂ and CO have a relatively high NO_x reduction efficiency compared to C₃H₆ and especially C₃H₈ that does not show any NO_x reduction ability except at 350 °C over Pd/BaO/Al₂O₃. The type of precious metals affects the NO_x storage-reduction properties, where the Pd/BaO/Al₂O₃ catalyst shows both a high storage and a high reduction ability. The Rh/BaO/Al₂O₃ catalyst shows a high reduction ability but a relatively low NO_x storage capacity.     

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.     

The activity and characterization of sol–gel Sn/Al2O3 catalyst for selective catalytic reduction of NOx in the presence of oxygen

Catalytic performance of Sn/Al₂O₃ catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NO_x by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO₂ had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al₂O₃ (SG) catalyst, and the maximum NO₂ conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NO_x desorption accompanied with O₂ around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H₂O and SO₂ at low temperature, and the temperature window was also broadened in the presence of H₂O and SO₂, however the NO_x desorption and NO conversion decreased sharply on the 300 ppm SO₂ treated catalyst, the catalytic activity was inhibited by the presence of SO₂ due to formation of sulfate species (SO₄²⁻) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al₂O₃ (SG) was not decreased in the presence of large oxygen.     

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.     

Reactor and in situ FTIR studies of Pt/BaO/Al2O3 and Pd/BaO/Al2O3 NOx storage and reduction (NSR) catalysts

The reduction of NO under cyclic “lean”/“rich” conditions was examined over two model 1 wt.% Pt/20 wt.% BaO/Al₂O₃ and 1 wt.% Pd/20 wt.% BaO/Al₂O₃ NO_x storage reduction (NSR) catalysts. At temperatures between 250 and 350 °C, the Pd/BaO/Al₂O₃ catalyst exhibits higher overall NO_x reduction activity. Limited amounts of N₂O were formed over both catalysts. Identical cyclic studies conducted with non-BaO-containing 1 wt.% Pt/Al₂O₃ and Pd/Al₂O₃ catalysts demonstrate that under these conditions Pd exhibits a higher activity for the oxidation of both propylene and NO. Furthermore, in situ FTIR studies conducted under identical conditions suggest the formation of higher amounts of surface nitrite species on Pd/BaO/Al₂O₃. The IR results indicate that this species is substantially more active towards reaction with propylene. Moreover, its formation and reduction appear to represent the main pathway for the storage and reduction of NO under the conditions examined. Consequently, the higher activity of Pd can be attributed to its higher oxidation activity, leading both to a higher storage capacity (i.e., higher concentration of surface nitrites under “lean” conditions) and a higher reduction activity (i.e., higher concentration of partially oxidized active propylene species under “rich” conditions). The performance of Pt and Pd is nearly identical at temperatures above 375 °C.     

NOx storage/reduction over lean-burn automotive catalysts

This paper shows the behavior of a Pt/Ba/γ–Al₂O₃ automotive catalyst in a fixed bed reactor during cyclic operation at lean and rich gas phase conditions at short (seconds) and long (hours) cycling times at different temperatures. Reactor exit gas phase concentrations have been measured and catalyst properties have been determined before and after selective cycling experiments. The experimental results indicate that: (i) Upon 9 h lean and 15 h rich cycling, the NO oxidation efficiency of the catalyst decreases with time while incomplete regeneration is seen, even after 15 h rich exposure with H₂. The cyclic steady state is reached after 3 lean/rich cycles, at which only 60% of the available barium is involved in the NO_x storage/reduction. (ii) The BET surface area, pore volume, and Pt dispersion decrease by approximately 40%, which may be a result of masking of Pt sites or blocking of pores of the barium clusters as BaCO₃ becomes Ba(NO₃)₂. Experiments with catalyst pellet sizes of 180 and 280 μm along with XPS measurements show that blocking of catalyst pellet pores is not taking place. (iii) When applying lean/rich cycling in the order of seconds, it appears that catalyst history and lean/rich timing affect the number of cycles required to arrive at a closed N balance. XRD results after lean exposure confirm the formation of barium nitrate in the bulk of the barium cluster.