Loss of NOx storage capacity of Pt–Ba/Al2O3 catalysts due to incorporation of phosphorous

This work aims at determining the effect of the incorporation of P on NO_x storage capacity by NO_x storage-reduction (NSR) catalysts. Different amounts of phosphorous were deposited on a Pt–Ba/Al₂O₃ catalyst (1 wt% Pt and 17 wt% Ba) by impregnation of a phosphate salt. Samples were calcined at 723 K and characterized using X-ray diffraction (XRD), N₂ adsorption isotherms and X-ray photoelectron spectroscopy (XPS). Their NO_x storage capacity was also measured. It was observed that storage capacity decreased almost linearly with the P/Ba ratio and besides at a phosphorous concentration P/Ba ratio of <0.1 deterioration was low. At higher P concentrations (P/Ba ratio = 0.7) the NO_x storage was significantly reduced. It is proposed that the cause of the decline in NO_x retention capacity would be the formation of Ba–P phases (very likely Ba phosphates) at the expense of Ba carbonate or Ba oxide. These new phases would be unable to exchange NO_x.     

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.     

Multifunctional catalyst for de-NOx processes: The selective reduction of NOx by methane

A multifunctional catalyst has been applied for the reduction of NO_x by methane in excess of oxygen. The catalyst includes a heteropolyacid (HPW) and a noble metal (Pt) deposited on a ceria–zirconia mixed oxide. The presence of hydrogen is necessary for reducing NO_x into N₂ with methane. During several alternate cycles of NO_x storage (2 min) and reduction (1 min), the average NO_x reduction percentage into nitrogen was of ca. 60% with a constant storage efficiency of ca.70%. A coherent picture of the catalytic process emerged from two separated experimental tests: water gas shift and steam methane reforming reactions.     

Electrochemical decomposition of NO over composite electrodes on YSZ electrolyte

NO decomposition over electrochemical cells that involve a bilayered composite electrode has been investigated. NO was decomposed only after a minimum current density was applied and its conversion increased abruptly with increasing applied current. The compositions of phases and their spatial distribution on the cathode strongly influenced the decomposition activity as a function of the current density since they are directly correlated with the site and number densities of the triple-phase boundary and the electrochemically induced active site, i.e., F-center. The [(La₂Sn₂O₇ + YSZ)/Pt] electrode could convert more than 85% of NO into N₂ at 200 mA/cm² whereas only 27% was decomposed over the platinum electrode although the latter was more electrochemically active at lower current ∼70 mA/cm². The addition of Pt into the [(La₂Sn₂O₇ + YSZ)/Pt] composite electrode not only expands the densities of the tpb and F-centers but also enhances competitive NO adsorption as indirectly confirmed by impedance spectroscopy, both of which promote NO conversion at the lower current density.     

Redox features in the catalytic mechanism of the “standard” and “fast” NH3-SCR of NOx over a V-based catalyst investigated by dynamic methods

The redox mechanism governing the selective catalytic reduction (SCR) of NO/NO₂ by ammonia at low temperature was investigated by transient reactive experiments over a commercial V₂O₅/WO₃/TiO₂ catalyst for diesel exhaust aftertreatment. NO + NH₃ temperature-programmed reaction runs over reduced catalyst samples pretreated with various oxidizing species showed that both NO₂ and HNO₃ were able to reoxidize the V catalyst at much lower temperature than gaseous O₂: furthermore, they significantly enhanced the NO + NH₃ reactivity below 250 °C via the buildup of adsorbed nitrates, which act as a surface pool of oxidizing agents but are decomposed above that temperature. Both such features, which were not observed in comparative experiments over a V-free WO₃/TiO₂ catalyst, point out a key catalytic role of the vanadium redox properties and can explain the greater deNO_x efficiency of the “fast” SCR (NO + NH₃ + NO₂) compared with the “standard” SCR (NO + NH₃ + O₂) reaction. A unifying redox approach is proposed to interpret the overall NO/NO₂–NH₃ SCR chemistry over V-based catalysts, in which vanadium sites are reduced by the reaction between NO and NH₃ and are reoxidized either by oxygen (standard SCR) or by nitrates (fast SCR), with the latter formed via NO₂ disproportion over other nonreducible oxide catalyst components.     

Regeneration mechanism of a Lean NOx Trap (LNT) catalyst in the presence of NO investigated using isotope labelling techniques

The presence of NO during the regeneration period of a Pt–Ba/Al₂O₃ Lean NO_x Trap (LNT) catalyst modifies significantly the evolution of products formed from the reduction of stored nitrates, particularly nitrogen and ammonia. The use of isotope labelling techniques, feeding ¹⁴NO during the storage period and ¹⁵NO during regeneration allows us to propose three different routes for nitrogen formation based on the different masses detected during regeneration, i.e. ¹⁴N₂ (m/e = 28), ¹⁴N¹⁵N (m/e = 29) and ¹⁵N₂ (m/e = 30). It is proposed that the formation of nitrogen via Route 1 involves the reaction between hydrogen and ¹⁴NO_x released from the storage component to form ¹⁴NH₃ mainly. Then, ammonia further reacts with ¹⁴NO_x located downstream to form ¹⁴N₂. In Route 2, it is postulated that the incoming ¹⁵NO reacts with hydrogen to form ¹⁵NH₃ in the reactor zone where the trap has been already regenerated. This isotopically labelled ammonia travels through the catalyst bed until it reaches the regeneration front where it participates in the reduction of stored nitrates (¹⁴NO_x) to form ¹⁴N¹⁵N. The formation of ¹⁵N₂ via Route 3 is believed to occur by the reaction between incoming ¹⁵NO and H₂. The modification of the hydrogen concentration fed during regeneration affects the relative importance of H₂ or ¹⁵NH₃ as reductants and thus the production of ¹⁴N₂ via Route 1 and ¹⁴N¹⁵N via Route 2.     

Resistance to sulfidation of the catalytic reduction of NOx over Ag/Al2O3 by controlling the loadings of Ag and Ag+

SO₂ strongly decreased the catalytic activities of low loading Ag/Al₂O₃ below 500 °C in selective catalytic reduction (SCR) of NO_x by propene with or without the assistance of non-thermal plasma (NTP), which was mainly attributed to the competition between SO₂ and NO. By controlling the loadings of Ag and Ag⁺ over alumina, the resistance of SO₂ was remarkably enhanced between 400 °C and 500 °C in thermal SCR. In the NTP-assisted SCR, most of the NO_x conversions were also apparently recovered from 250 °C to 500 °C.     

Regeneration of sulfur-poisoned CeO2 catalyst for NH3-SCR of NOx

The effects of regeneration on the activities and structure of CeO₂ catalysts for NH₃-SCR of NO_x have been studied in this article. CeO₂ catalyst is deactivated by SO₂ for NH₃-SCR of NO_x in a 200 h long-term operation at 350 °C due to the formation of sulfates, and its NO_x conversion decreases from 100% to 83% gradually. However, sulfates can be removed from sulfur-poisoned CeO₂ catalysts under high temperature thermal treatment in air. After regeneration, NO_x conversion of sulfur-poisoned CeO₂ catalyst is recovered to about 100% at 350 °C. Moreover, the regeneration temperature is related to the nature of the sulfates formed on the sulfur-poisoned CeO₂ catalysts.     

A novel catalyst for diesel soot oxidation

In this study, cobalt and lead based mixed oxide catalysts were tested for their soot oxidation ability. In addition to a mixed oxide formerly marketed as ceramic paint, a home made set was also prepared by incipient wetness impregnation of a cobalt oxide powder with a lead acetate solution and subsequent calcination. The materials investigated in this study were shown to decrease the peak combustion temperature of home made soot from 500 to 385 °C in air. Soot oxidation tests under inert (N₂) atmospheres revealed that the oxidation took place by using the lattice oxygen of the catalyst. Reaction temperature could be further decreased when these mixed oxide catalysts were impregnated with platinum. An optimum platinum loading was determined as 0.5 wt% based on the peak combustion temperature of the soot. The role of Pt was to assist the oxygen transfer from the gas phase to the lattice. It was observed that NO₂ is a better oxidizing agent as compared to air whereas NO had hardly any activity against soot oxidation reaction. When the mixed oxide catalyst was impregnated with platinum, the peak combustion temperature was measured as 310 °C in the presence of NO_x and air. The catalyst's unique performance was in terms of the rate of soot oxidation. Under the experimental conditions studied here, the soot oxidation was so facile that the oxygen in the gas phase was completely depleted. This stream of oxygen depleted and CO enriched gas phase can be used to reduce NO_x in the presence of a downstream or a co-catalyst.     

NOx removal efficiency and N2 selectivity during selective catalytic reduction processes over Al2O3 supported highly cross-linked polyethylene catalysts

The performance of a highly cross-linked polyethylene catalyst supported on alumina for low temperature selective catalytic reduction of NO_x by unburned hydrocarbons (HCs) existing in an exhaust gas was examined at different engine conditions with the addition of exhaust-gas recirculation. The HXPE catalyst was shown to exhibit good NO_x reduction activity at low temperatures (100–250 °C) where the only reductant was the unburned HC, which was already present in the exhaust flow. The maximum NO_x reduction of approximately 52% was achieved at a temperature of 150 °C. HXPE demonstrated very good selectivity toward N₂ in the majority of tested conditions (∼80%).     

Mechanism of NO reduction by CO over Pt/SBA-15

The mechanism of the CO + NO reaction catalyzed by Pt/SBA-15 was studied via independent investigations of CO oxidation and NO disproportionation. Below 400 °C, both CO + O₂ and CO + NO reactions approach 100 % conversion, while the catalyst shows negligible activity for NO disproportionation. These results suggest that CO oxidation by atomic oxygen arising from NO dissociation is not a major route for CO₂ formation in the CO + NO reaction. In situ IR spectra reveal the formation of isocyanates (NCO⁻) adsorbed on silica. Their surface concentration changes with the extent of the CO + NO reaction. A mechanism is proposed in which isocyanates are reaction intermediates.     

Study of thin films of yttria-stabilized zirconia (YSZ) for the oxidation of some volatile organic compounds

Thin films of YSZ and 1%Pt/YSZ were deposited onto stainless steel tubes by an electrophoretic deposition technique. O₂-TPD from r.t. to 600 °C using induction heating was used to characterize the two films considering (i) the amount of oxygen desorbed (5.1 and 1.4 × 10^− 2 μmol O₂·g^− 1 for 1%Pt/YSZ and YSZ respectively) and (ii) the apparent activation energy of desorption E_app. Finally, complete oxidation of some VOCs (isopropanol and toluene) in air was studied on both films. From r.t. to 400 °C, oxidation of isopropanol can be achieved with either YSZ or 1%Pt/YSZ but only this last catalyst can achieve the complete oxidation of toluene.     

Soot oxidation on a catalytic NOx trap: Beneficial effect of the Ba–K interaction on the sulfated Ba,K/CeO2 catalyst

The Ba,K/CeO₂ catalyst is active both for NO_x trapping and soot combustion. In this work we report a Ba–K interaction that prevents K sulfation when NO_x is present, thus preserving the activity of K towards soot combustion during the working period of the trap. This effect is originated in the K₂SO₄(s) + Ba(NO₃)₂(s) → 2KNO₃(s) + BaSO₄(s) reaction, which is thermodynamically favored. In the absence of NO_x, the soot combustion reaction is strongly depressed by SO₂ whereas when NO_x is present both the sulfated and the non-sulfated catalysts present similar TPO patterns.     

Role of oxygen pressure on the stability of lanthanum strontium manganite–yttria stabilized zirconia composite

We have investigated the structural and chemical stability of La_0.8Sr_0.2MnO₃ (LSM)–8 mol.% yttria stabilized zirconia (YSZ) composite. LSM and YSZ powders were mixed and sintered at 1400 °C for 10 h in controlled atmosphere (PO₂ = 0.21 to 10^?6 atm). The unit cell volume of LSM increases during exposure to reduced oxygen partial pressure while it remains unchanged for YSZ. During reduction in the oxygen partial pressure from 0.21 atm to 10^?6 atm, the solubility of manganese in YSZ increases from ～10 at.% to ～15 at.%. Lower oxygen partial pressure also results in the grain growth and formation of La₂Zr₂O₇ and MnO_x (Mn₃O₄) compounds lowering the stability of the LSM–YSZ composite. On subsequent sintering in 0.21 atm PO₂, the La₂Zr₂O₇ and MnO_x compounds tend to disappear indicating the reversibility of the interaction. The reversibility of LSM–YSZ reaction has been independently confirmed using La₂Zr₂O₇ and MnO_x.     

Electrochemical performance of intermediate temperature micro-tubular solid oxide fuel cells using porous ceria barrier layers

We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce_0.9Gd_0.1O_2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr_0.92Y_0.16O_2.08; LSCF: La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H₂ as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm⁻² at 650 °C and about 700 mW cm⁻² at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.     

A Ce–Sn–Ox catalyst for the selective catalytic reduction of NOx with NH3

A series of Ce–Sn–O_x catalysts prepared by the facile coprecipitation method exhibited good catalytic activity in a broad temperature range from 100 °C to 400 °C for the selective catalytic reduction of NO_x with NH₃ at the space velocity of 20,000 h^− 1. The Ce₄Sn₄O_x catalyst calcined at 400 °C showed high resistance to H₂O, SO₂, K₂O and PbO under our test conditions. The better catalytic performance was associated with the synergistic effect between CeO₂ and SnO₂, which strengthened the NH₃ and NO_x adsorption capacity on the surface of the catalyst.     

The effects of deposition temperature on structure and dielectric properties of Ba0.6Sr0.4TiO3 thin films produced by pulsed laser deposition

The effects of deposition temperature on orientation, surface morphology and dielectric properties of the thin films for Ba_0.6Sr_0.4TiO₃ thin films deposited on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition were investigated. X-ray diffraction patterns revealed a (2 1 0) preferred orientation for all the films. With rising substrate temperature from 650 °C to 700 °C, the crystallinity and crystal grain size of the films increase, the relative dielectric constant increases, but the dielectric losses have not obvious difference. The film deposited at 350 °C and annealed at 700 °C has strongly improved roughness and dielectric permittivity compared with the film only deposited directly at 700 °C. Three distinct relaxation processes within tan(δ) were found for the Ba_xSr_1?xTiO₃ film: a broadened process of the film relaxation, an intermediate peak which originates from Maxwell–Wagner–Sillars polarization, and an extremely slow process ascribed to leak current. The complex dielectric permittivity and loss can be fitted by an improved Cole–Cole model corresponding to a stretched relaxation function.     

Adsorption and temperature programmed desorption of NO,NO + O2, NO2 and NO + NO2 over CoH-ZSM-5

The NO₂, NO (O₂) adsorption and temperature programmed desorption (TPD) were studied systematically to probe into the selective catalytic reduction of NO by methane (CH₄–SCR) over CoH-ZSM-5 (SiO₂/Al₂O₃ = 25, Co/Al = 0.132–0.312). Adsorption conditions significantly affect the adsorption of NO, NO₂ and NO + O₂. Adsorbed NO species are unstable and desorbed below the reactive temperature 523 K. Increasing adsorption temperature results in the decrease of the adsorbed NO species amount. The amount of –NO_y species formed from NO₂ adsorption increases with the increase of NO₂ concentration in the adsorption process, while decreases significantly with the increase of adsorption temperature. Though NO species are adsorbed weakly on CoH-ZSM-5, competitive adsorption between NO and –NO_y species decreases the amount of adsorbed –NO_y species. Similar desorption profiles of NO₂ were obtained over CoH-ZSM-5 while they were contacted with NO₂ or NO + O₂ followed by TPD. If NO₂ was essential to form adsorbed –NO_y species, the amount of adsorbed –NO_y species for NO + O₂ adsorption should be the least among the adsorptions of NO₂, NO + O₂ and NO + NO₂ because of the lowest NO₂ concentration and highest NO concentration. In fact, the amount of adsorbed –NO_y species is between the other two adsorption processes. These indicate that the formation of adsorbed –NO_y species may not originate from NO₂.     

Effect of calcination temperature on morphology of mesoporous YSZ

A nano-structured mesoporous yttria-stabilized zirconia (YSZ) powders were prepared for the first time using cetyltrimethylammonium bromide (CTAB) as the surfactant and urea as the hydrolyzing agent and using ZrO(NO₃)·6H₂O and Y(NO₃)₃·6H₂O as inorganic precursors. The Brunauer–Emmett–Teller (BET) surface area, Barrett–Joyner–Halender (BJH) pore size distribution and crystallite/particle size of mesoporous YSZ varied with calcine temperatures were studied. Characterizations revealed that the mesoporous YSZ powder calcined at 600 °C was weakly agglomerated and had a high surface area of 137 m²/g with an average grain size of ∼5.8 nm. It was demonstrated that the mesoporous structure remained up to 900 °C. The low-densified YSZ sample with porosity as high as 33% was prepared from mesoporous YSZ powder sintered at 1500 °C for 6 h.     

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.