Influence of the Type of Reducing Agent (H2, CO, C3H6 and C3H8) on the Reduction of Stored NOX in a Pt/BaO/Al2O3 Model Catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.     

Steam effect on NO x reduction over lean NO x trap Pt–BaO/Al2O3 model catalyst

The effect of steam on NO _x reduction over lean NO _x trap (LNT) Pt–Ba/Al₂O₃ and Pt/Al₂O₃ model catalysts was investigated with reaction protocols of rich steady-state followed by lean–rich cyclic operations using CO and C₃H₈ as reductants, respectively. Compared to dry atmosphere, steam promoted NO _x reduction; however, under rich conditions the primary reduction product was NH₃. The results of NO _x reduction and NH₃ selectivity versus temperature, combined with temperature programmed reduction of stored NO _x over Pt–BaO/Al₂O₃ suggest that steam causes NH₃ formation over Pt sites via reduction of NO _x by hydrogen that is generated via water gas shift for CO/steam, or via steam reforming for C₃H₈/steam. During the rich mode of lean–rich cyclic operation with lean–rich duration ratio of 60 /20 s, not only the feed NO, but also the stored NO _x contributed to NH₃ formation. The NH₃ formed under these conditions could be effectively trapped by a downstream bed of Co²⁺ exchanged Beta zeolite. When the cyclic operation was switched into lean mode at T < 450 °C, the trapped ammonia in turn participated in additional NO _x reduction, leading to improved NO _x storage efficiency.     

NOx Storage and Reduction Catalysts for Automotive Lean-Burn Engines: Effect of Parameters and Storage Materials on NOx Conversion

The effect of various parameters on the NO _x conversion over NO _x storage and reduction catalysts supported on alumina was investigated. The Pt/BaO/Al₂O₃ catalyst exhibited a higher NO _x reduction activity than the Pt/Al₂O₃ catalyst under the static and cycling conditions. The activity of Pt/BaO/Al₂O₃ catalyst was improved in the cycled feedstream. The Pt/SrO/Al₂O₃ was found to have as high activity as Pt/BaO/Al₂O₃ for NO _x reduction. In order to achieve effective reduction of NO _x , NO _x storage in the form of Me(NO₃)₂ (Me = Ba or Sr) is more favorable than other nitrates and the rich condition should be chosen in such a way that the sorption capacity can be fully regenerated at a fast rate and the inhibition effect by strongly adsorbed molecules derived from C₃H₆ and CO can be minimized.     

Changes in Ba Phases in BaO/Al2O3 upon Thermal Aging and H2O Treatment

The effects of thermal aging and H₂O treatment on the physicochemical properties of BaO/Al₂O₃ (the NO_x storage component in the lean NO_x trap systems) were investigated by means of X-ray diffraction (XRD), BET, TEM/EDX and NO₂ TPD. Thermal aging at 1000 °C for 10 h converted dispersed BaO/BaCO₃ on Al₂O₃ into low surface area crystalline BaAl₂O₄. TEM/EDX and XRD analysis showed that H₂O treatment at room temperature facilitated a dissolution/reprecipitation process, resulting in the formation of a highly crystalline BaCO₃ phase segregated from the Al₂O₃ support. Crystalline BaCO₃ was formed from conversion of both BaAl₂O₄ and a dispersed BaO/BaCO₃ phase, initially present on the Al₂O₃ support material after calcinations at 1000 and 500 °C, respectively. Such a phase change proceeded rapidly for dispersed BaO/BaCO₃/Al₂O₃ samples calcined at relatively low temperatures with large BaCO₃ crystallites observed in XRD within 10 min after contacting the sample with water. Significantly, we also find that the change in barium phase occurs even at room temperature in an ambient atmosphere by contact of the sample with moisture in the air, although the rate is relatively slow. These phenomena imply that special care to prevent the water contact must be taken during catalyst synthesis/storage, and during realistic operation of Pt/BaO/Al₂O₃ NO_x trap catalysts since both processes involve potential exposure of the material to CO₂ and liquid and/or vapor H₂O. Based on the results, a model that describes the behavior of Ba-containing species upon thermal aging and H₂O treatment is proposed.     

Sulfur deactivation and regeneration of Pt/BaO/Al2O3 and Pt/SrO/Al2O3 NO x storage catalysts

Transient experiments were performed to study sulfur deactivation and regeneration of Pt/BaO/Al₂O₃ and Pt/SrO/Al₂O₃ NO _x storage catalysts. It was found that the strontium-based catalysts are more easily regenerated than the barium-based catalysts and that a higher fraction of the NO _x storage sites are regenerated when H₂ is used in combination with CO₂ compared to H₂ only.     

Kinetic modeling of storage and reduction with different reducing agents (CO, H2, and C2 H4) on a Pt–Ba/-Al2O3 catalyst in the presence of CO2 and H2O

In this paper a global reaction kinetic model is used to understand and describe the NO_x storage/reduction process in the presence of CO₂ and H₂O. Experiments have been performed in a packed bed reactor with a Pt–Ba/γ-Al₂O₃ powder catalyst (1 wt% Pt and 30 wt% Ba) with different lean/rich cycle timings at different temperatures (200, 250, and ) and using different reductants (H₂, CO, and C₂H₄). Model simulations and experimental results are compared. H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. The rate of NO storage increases with temperature. The reduction of stored NO with H₂ is complete for all investigated temperatures. At temperatures above , the water gas shift (WGS) reaction takes place and H₂ acts as reductant instead of CO. At , CO and C₂H₄ are not able to completely regenerate the catalyst. At the higher temperatures, C₂H₄ is capable of reducing all the stored NO, although C₂H₄ poisons the Pt sites by carbon decomposition at . The model adequately describes the NO breakthrough profile during 100 min lean exposure as well as the subsequent release and reduction of the stored NO. Further, the model is capable of simulating transient reactor experiments with 240 s lean and 60 s rich cycle timings.     

Dynamics and Selectivity of N<Subscript>2</Subscript>O Formation/Reduction During Regeneration Phase of Pt-Based Catalysts

The formation of N₂O has been studied by means of isothermal lean-rich experiments at 150, 180 and 250 °C over Pt–Ba/Al₂O₃ and Pt/Al₂O₃ catalysts with H₂ and/or C₃H₆ as reductants. This allows to provide further insights on the mechanistic aspects of N₂O formation and on the influence of the storage component. Both gas phase analysis and surface species studies by operando FT-IR spectroscopy were performed. N₂O evolution is observed at both lean-to-rich (primary N₂O) and rich-to-lean (secondary N₂O) transitions. The production of both primary and secondary N₂O decreases by increasing the temperature. The presence of Ba markedly decreases secondary N₂O formation. FT-IR analysis shows the presence of adsorbed ammonia at the end of the rich phase only for Pt/Al₂O₃ catalyst. These results suggest that: (i) primary N₂O is formed when undissociated NO in the gas phase and partially reduced metal sites are present; (ii) secondary N₂O originates from reaction between adsorbed NH₃ and residual NO_x at the beginning of the lean phase. Moreover, N₂O reduction was studied performing temperature programming temperature experiments with H₂, NH₃ and C₃H₆ as reducing agents. The reduction is completely selective to nitrogen and occurs at temperature higher than 250 °C in the case of Pt–Ba/Al₂O₃ catalyst, while lower temperatures are detected for Pt/Al₂O₃ catalyst. The reactivity order of the reductants is the same for the two catalysts, being hydrogen the more efficient and propylene the less one. Having H₂ a high reactivity in the reduction of N₂O, it could react with N₂O when the regeneration front is developing. Moreover, also ammonia present downstream to the H₂ front could react with N₂O, even if the reaction with stored NO_x seems more efficient.     

Influence of the storage material on the storage of NO x at low temperatures

The NO _x storage performance at low temperature (100–200 °C) has been studied for model NO _x storage catalysts. The catalysts were prepared by sequentially depositing support, metal oxide and platinum on ceramic monoliths. The support material consisted of acidic aluminium silicate, alumina or basic aluminium magnesium oxide, and the added metal oxide was either ceria or barium oxide. The NO _x conversion was evaluated under net-oxidising conditions with transients between lean and rich gas composition and the NO _x storage performance was studied by isothermal adsorption of NO₂ followed by temperature programmed desorption of adsorbed species. The maximum in NO _x storage capacity was observed at 100 °C for all samples studied. The Pt/BaO/Al₂O₃ catalyst stored about twice the amount of NO _x compared with the Pt/Al₂O₃ and Pt/CeO₂/Al₂O₃ samples. The storage capacity increased with increasing basicity of the support material, i.e. Pt/Al₂O₃ · SiO₂ < Pt/Al₂O₃ < Pt/Al₂O₃ · MgO. Water did not significantly affect the NO _x storage performance for Pt/Al₂O₃ or Pt/BaO/Al₂O₃.

     

Cyclic Lean Reduction of NO by CO in Excess H2O on Pt–Rh/Ba/Al2O3: Elucidating Mechanistic Features and Catalyst Performance

This study provides insight into the mechanistic and performance features of the cyclic reduction of NO_x by CO in the presence and absence of excess water on a Pt–Rh/Ba/Al₂O₃ NO_x storage and reduction catalyst. At low temperatures (150–200 °C), CO is ineffective in reducing NO_x due to self-inhibition while at temperatures exceeding 200 °C, CO effectively reduces NO_x to main product N₂ (selectivity >70 %) and byproduct N₂O. The addition of H₂O at these temperatures has a significant promoting effect on NO_x conversion while leading to a slight drop in the CO conversion, indicating a more efficient and selective lean reduction process. The appearance of NH₃ as a product is attributed either to isocyanate (NCO) hydrolysis and/or reduction of NO_x by H₂ formed by the water gas shift chemistry. After the switch from the rich to lean phase, second maxima are observed in the N₂O and CO₂ concentrations versus time, in addition to the maxima observed during the rich phase. These and other product evolution trends provide evidence for the involvement of NCOs as important intermediates, formed during the CO reduction of NO on the precious metal components, followed by their spillover to the storage component. The reversible storage of the NCOs on the Al₂O₃ and BaO and their reactivity appears to be an important pathway during cyclic operation on Pt–Rh/Ba/Al₂O₃ catalyst. In the absence of water the NCOs are not completely reacted away during the rich phase, which leads to their reaction with NO and O₂ upon switching to the subsequent lean phase, as evidenced by the evolution of N₂, N₂O and CO₂. In contrast, negligible product evolution is observed during the lean phase in the presence of water. This is consistent with a rapid hydrolysis of NCOs to NH₃, which results in a deeper regeneration of the catalyst due in part to the reaction of the NH₃ with stored NO_x. The data reveal more efficient utilization of CO for reducing NO_x in the presence of water which further underscores the NCO mechanism. Phenomenological pathways based on the data are proposed that describes the cyclic reduction of NO_x by CO under dry and wet conditions.     

Reduction of Surface Nitrates via C3H6 Oxidation Over a Pt/Al2O3 Catalyst

Reduction of surface nitrates with C₃H₆ on a Pt/Al₂O₃ catalyst was investigated using diffuse reflectance infrared spectroscopy (DRIFTS) and a reactor system designed for monolith-supported catalysts. C₃H₆ oxidation was inhibited by the presence of NO, and vice versa, and data indicate that adsorbed NO_X reacted with gas phase C₃H₆. DRIFTS results confirm reaction between C₃H₆ and surface nitrates with linear nitrites as the reaction products. Data show that Pt is required for this reaction, which suggests the nitrates in proximity to the Pt particles are affected/relevant.     

Influence of Activation and the HDS Reaction on the Structure of Magnesium Fluoride-Supported Ru Catalysts Derived from Ruthenium Chloride Hydrate

The effect of water and reductants (CO and H₂) on the decomposition of NO _x stored on BaO/Al₂O₃ at 300 °C has been investigated. Water eliminates the initial rapid total uptake of NO₂ but has little effect on the subsequent formation of nitrates that is accompanied by evolution of NO. Water hinders liberation of NO₂ and NO during temperature-programmed decomposition of stored NO _x . Both CO and H₂ lower the temperatures required for decomposition through reduction of NO₂ to NO and N₂ thus restricting NO₂ readsorption. The rate of reduction is lower with H₂ than with CO.     

NO x uptake mechanism on Pt/BaO/Al2O3 catalysts

The NO _x adsorption mechanism on Pt/BaO/Al₂O₃ catalysts was investigated by performing NO _x storage/reduction cycles, NO₂ adsorption and NO + O₂ adsorption on 2%Pt/(x)BaO/Al₂O₃ (x = 2, 8, and 20 wt%) catalysts. NO _x uptake profiles on 2%\Pt/20%BaO/Al₂O₃ at 523 K show complete uptake behavior for almost 5 min, and then the NO _x level starts gradually increasing with time and it reaches 75% of the inlet NO _x concentration after 30 min time-on-stream. Although this catalyst shows fairly high NO _x conversion at 523 K, only ~2.4 wt% out of 20 wt% BaO is converted to Ba(NO₃)₂. Adsorption studies by using NO₂ and NO + O₂ suggest two different NO _x adsorption mechanisms. The NO₂ uptake profile on 2%Pt/20%BaO/Al₂O₃ shows the absence of a complete NO _x uptake period at the beginning of adsorption and the overall NO _x uptake is controlled by the gas–solid equilibrium between NO₂ and BaO/Ba(NO₃)₂ phase. When we use NO + O₂, complete initial NO _x uptake occurs and the time it takes to convert ~4% of BaO to Ba(NO₃)₂ is independent of the NO concentration. These NO _x uptake characteristics suggest that the NO + O₂ reaction on the surface of Pt particles produces NO₂ that is subsequently transferred to the neighboring BaO phase by spill over. At the beginning of the NO _x uptake, this spill-over process is very fast and so it is able to provide complete NO _x storage. However, the NO _x uptake by this mechanism slows down as BaO in the vicinity of Pt particles are converted to Ba(NO₃)₂. The formation of Ba(NO₃)₂ around the Pt particles results in the development of a diffusion barrier for NO₂, and increases the probability of NO₂ desorption and consequently, the beginning of NO _x slip. As NO _x uptake by NO₂ spill-over mechanism slows down due to the diffusion barrier formation, the rate and extent of NO₂ uptake are determined by the diffusion rate of nitrate ions into the BaO bulk, which, in turn, is determined by the gas phase NO₂ concentration.     

Influence of the Storage Material on the Storage of NOx at Low Temperatures

The NO _x storage performance at low temperature (100–200 °C) has been studied for model NO _x storage catalysts. The catalysts were prepared by sequentially depositing support, metal oxide and platinum on ceramic monoliths. The support material consisted of acidic aluminium silicate, alumina or basic aluminium magnesium oxide, and the added metal oxide was either ceria or barium oxide. The NO _x conversion was evaluated under net-oxidising conditions with transients between lean and rich gas composition and the NO _x storage performance was studied by isothermal adsorption of NO₂ followed by temperature programmed desorption of adsorbed species. The maximum in NO _x storage capacity was observed at 100 °C for all samples studied. The Pt/BaO/Al₂O₃ catalyst stored about twice the amount of NO _x compared with the Pt/Al₂O₃ and Pt/CeO₂/Al₂O₃ samples. The storage capacity increased with increasing basicity of the support material, i.e. Pt/Al₂O₃·SiO₂ < Pt/Al₂O₃ < Pt/Al₂O₃ · MgO. Water did not significantly affect the NO _x storage performance for Pt/Al₂O₃ or Pt/BaO/Al₂O₃.     

Enhanced Sulfur Tolerance of Ceria-Promoted NO x Storage Reduction (NSR) Catalysts: Sulfur Uptake, Thermal Regeneration and Reduction with H2(g)

SO _x uptake, thermal regeneration and the reduction of SO _x via H₂(g) over ceria-promoted NSR catalysts were investigated. Sulfur poisoning and desulfation pathways of the complex BaO/Pt/CeO₂/Al₂O₃ NSR system was investigated using a systematic approach where the functional sub-components such as Al₂O₃, CeO₂/Al₂O₃, BaO/Al₂O₃, BaO/CeO₂/Al₂O₃, and BaO/Pt/Al₂O₃ were studied in a comparative fashion. Incorporation of ceria significantly increases the S-uptake of Al₂O₃ and BaO/Al₂O₃ under both moderate and extreme S-poisoning conditions. Under moderate S-poisoning conditions, Pt sites seem to be the critical species for SO _x oxidation and SO _x storage, where BaO/Pt/Al₂O₃ and BaO/Pt/CeO₂/Al₂O₃ catalysts reveal a comparable extent of sulfation. After extreme S-poisoning due to the deactivation of most of the Pt sites, ceria domains are the main SO _x storage sites on the BaO/Pt/CeO₂/Al₂O₃ surface. Thus, under these conditions, BaO/Pt/CeO₂/Al₂O₃ surface stores more sulfur than that of BaO/Pt/Al₂O₃. BaO/Pt/CeO₂/Al₂O₃ reveals a significantly improved thermal regeneration behavior in vacuum with respect to the conventional BaO/Pt/Al₂O₃ catalyst. Ceria promotion remarkably enhances the SO _x reduction with H₂(g).     

Effect of Co and Rh promoter on NOx storage and reduction over Pt/BaO/Al2O3 catalyst

Effect of cobalt and rhodium promoter on NO_x storage and reduction (NSR) kinetics was investigated over Pt/BaO/Al₂O₃. Kinetics of 2% cobalt loading over Pt/BaO/Al₂O₃ demonstrated highest NO_x uptake during lean cycle, while reduction efficiency during rich cycle appeared most poor. In contrast to this, rhodium showed suppressing effect of NO_x uptake during lean cycle and demonstrated an enhanced effect for the higher efficiency of NO_x reduction during rich cycle. DRIFT study for NO_x uptake and regeneration confirmed formation of surface BaNO_x from the band at 1300 cm⁻¹ and formation of bulk BaNO_x from the band at 1330 cm⁻¹.     

Influence of Pt location on BaCO3 or Al2O3 during NOx storage reduction

Catalysts for NO_x storage–reduction (NSR) were made selectively with Pt on either the Al- or the Ba-components without altering significantly the Al₂O₃ or BaCO₃ crystal sizes, Al/Ba weight ratio, specific surface area, porosity, and Pt dispersion using a two-nozzle flame spray pyrolysis (FSP) unit. The NO_x storage performance at 300 °C was best for Pt located near Al₂O₃ as it facilitates the oxidation of NO to NO₂ during the fuel lean period but the reduction rate during the subsequent short fuel rich period was much slower resulting in incomplete regeneration. This contributed to a gradual decrease of the NO_x conversion at increasing cycling. In contrast, Pt on BaCO₃ resulted in an initially lower NO_x storage rate but during ten storage–reduction cycles a stable NO_x conversion of about 50% was reached. When using NO₂ instead of NO or higher NO_x oxidation-reduction temperatures (e.g. 350 °C) the Pt location did not affect the NSR performance of the Pt/Ba/Al₂O₃ catalysts.     

Performance Improvement of NO x -Storage BaO/Al2O3 by Using Barium Peroxide as the Precursor of BaO

Comparison of barium peroxide, Ba(OH)₂ and Ba(NO₃)₂ as the precursor of BaO for the preparation of NO _x -storage BaO/Al₂O₃ material was carried out. The as prepared materials were calcined at 550 and 800 °C and characterized by N₂ physisorption, XRD, Raman and FT-IR spectroscopy. Measurements of the NO _x storage performances of these BaO/Al₂O₃ materials by NO₂ adsorption and NO _x -TPD experiments showed that the use of barium peroxide as the precursor of BaO inhibited the formation of BaAl₂O₄ and led to remarkable improvements in the thermal stability as well as NO _x storage capacity of the final BaO/Al₂O₃ material calcined at 800 °C.     

Reaction Kinetics of C3H6 Oxidation for Various Reaction Pathways Over Diesel Oxidation Catalysts

Reaction kinetics studies of C₃H₆ oxidation over Pt/Al₂O₃ and Pt/SiO₂ catalysts were characterized using temperature-programmed oxidation with different oxidants: O₂, NO₂ and surface nitrates. Activation energies and conversion performance were compared in order to determine which hydrocarbon oxidation reaction pathway(s) is relevant in diesel exhaust gas aftertreatment applications. NO _x adsorption did not occur on the SiO₂ surface so the reaction between C₃H₆ and NO₂ could be isolated, i.e. no nitrate effect would complicate the analysis and their significance could be decoupled. These results were then compared with Pt/Al₂O₃ where surface nitrates did form upon exposure to NO _x . The onset of C₃H₆ oxidation was observed at a lower temperature with O₂ than with NO₂, but the activation energy was lower with NO₂. This apparent discrepancy is related to the different oxidant concentrations used and the different adsorption pathways. The results indicate that hydrocarbons must be activated first for oxidation to begin, for either NO₂ or O₂. In analyzing the reaction between C₃H₆ and nitrates, the reaction did not occur until NO _x started to desorb from the catalyst at higher temperatures, i.e. when nitrates became unstable and decomposed, thus providing a readily available oxidant source. However, when O₂ was added to the nitrate/C₃H₆ system, the reaction began at even lower temperature than with just C₃H₆ and O₂. Nitrate consumption was also observed once oxidation began. The presence of the combination of nitrates and O₂ resulted in a lower C₃H₆ oxidation activation energy.     

Reduction of NOx by H2 on WOx-Promoted Pt/Al2O3/SiO2 Catalysts Under O2-Rich Conditions

This work addresses the reduction of NO_x by H₂ under O₂-rich conditions using Al₂O₃/SiO₂-supported Pt catalysts with different loads of WO_x promotor. The samples were thoroughly characterised by N₂ physisorption, temperature-programmed desorption of CO, scanning electron microscopy, X-ray diffraction, laser raman spectroscopy, X-ray photoelectron spectroscopy and diffuse reflectance infrared fourier transform spectroscopy with probe molecule CO. The catalytic studies of the samples without WO_x showed pronounced NO_x conversion below 200 °C, whereas highest efficiency was related to small Pt particles. The introduction of WO_x provided increasing deNO_x activity as well as N₂ selectivity. This promoting effect was referred to an additional reaction path at the Pt-WO_x/Al₂O₃/SiO₂ interface, whereas an electronic activation of Pt by strong metal support interaction was excluded.

Graphic Abstract