Dynamics and selectivity of NOx reduction in NOx storage catalytic monolith

Several nitrogen compounds can be produced during the regeneration phase in periodically operated NO_x storage and reduction catalyst (NSRC) for conversion of automobile exhaust gases. Besides the main product N₂, also NO, N₂O, and NH₃ can be formed, depending on the regeneration phase length, temperature, and gas composition. This contribution focuses on experimental evaluation of the NO_x reduction dynamics and selectivity towards the main products (NO, N₂ and NH₃) within the short rich phase, and consequent development of the corresponding global reaction-kinetic model. An industrial NSRC monolith sample of PtRh/Ba/CeO₂/ -Al₂O₃ type is employed in nearly isothermal laboratory micro-reactor. The oxygen and NO_x storage/reduction experiments are performed in the temperature range 100–500 °C in the presence of CO₂ and H₂O, using H₂, CO and C₃H₆ as the reducing agents.The spatially distributed NSRC model developed earlier is extended by the following reactions: NH₃ is formed by the reaction of H₂ with NO_x and it can further react with oxygen and NO_x deposited on the catalyst surface, producing N₂. Considering this scheme with ammonia as an active intermediate of the NO_x reduction, a good agreement with experiments is obtained in terms of the NO_x reduction dynamics and selectivity. A reduction front travelling in the flow direction along the reactor is predicted, with the NH₃ maximum on the moving boundary. When the front reaches the reactor outlet, the NH₃ peak is observed in the exhaust gas. It is assumed that the ammonia formation during the NO_x reduction by CO and HCs at higher temperatures proceed via the water gas shift and steam reforming reactions producing hydrogen. It is further demonstrated that oxygen storage effects influence the dynamics of the stored NO_x reduction. The temperature dependences of the outlet ammonia peak delay and the selectivity towards NH₃ are correlated with the effective oxygen and NO_x storage capacity.     

Microcalorimetric and infrared spectroscopic studies ofγ-Al2O3 modified by tin oxides

Microcalorimetric and infrared spectroscopic studies of ammonia and carbon dioxide adsorption have been used to study the effects on the acid/base properties of adding tin oxide to-Al₂O₃. The addition of SnO₂ to-Al₂O₃ decreases the number of strong acid sites (heats of ammonia adsorption higher than 140 kJ/mol), increases the number of weaker acid sites (heats from 110 to 130 kJ/mol), and decreases slightly the number of basic sites (heats of carbon dioxide adsorption from 70 to 150 kJ/mol). In contrast, the presence of SnO on-Al₂O₃ decreases the total number of acid sites (heats of ammonia adsorption higher than 70 kJ/mol) and eliminates most of the basic sites. Infrared spectroscopy of adsorbed ammonia reveals interactions between aluminum cations and stannous ions, leading to a decrease in the strength of the Lewis acid sites associated with aluminum cations.     

The dissociative adsorption of N2 on a multiply promoted iron catalyst used for ammonia synthesis: a temperature-programmed desorption study

The temperature-programmed desorption (TPD) of N₂ from a multiply promoted iron catalyst used for ammonia synthesis has been studied in a microreactor system at atmospheric pressure. From TPD experiments with various heating rates a preexponential factorA = 2 × 10⁹ molecules/site s and an activation energyE = 146 kJ/mol was derived assuming second-order desorption. The observed dependence of the TPD peak shapes on the heating rates indicated the influence of readsorption of N₂ in agreement with the results obtained for various initial coverages. Simulating the N₂ TPD curves using the model by Stoltze and Nørskov revealed that the calculated TPD curves were not influenced by the molecular precursor to desorption. However, the calculated rate of readsorption was found to be overestimated at high coverage compared with the experimental results. A coverage-dependent net activation energy for dissociative chemisorption (E*) was introduced as the simplest assumption rendering the dissociative chemisorption of N₂ activated at high coverage. The best fit of the experimental data yieldedE* = (–15+30) kJ/mol using only a single type of atomic nitrogen species. These findings are in satisfactory agreement with the parameters underlying the Stoltze-Nørskov model for the kinetics of ammonia synthesis as well as with the data reported for Fe(111) single crystal surfaces.     

Microcalorimetric studies of ammonia adsorption on γ-Al2O3, HNa-Y zeolite,and H-mordenite

The acidities of-Al₂O₃, HNa-Y zeolite, and H-mordenite have been examined by microcalorimetric measurements of ammonia adsorption at 423 K. The differential heat of adsorption on -Al₂O₃ decreases continuously with ammonia coverage from an initial value of 165 kJ/ mol at low coverages to a value of 70 kJ/mol at higher coverages. The differential heat of adsorption on HNa-Y zeolite shows similar behavior, with a plateau of nearly constant heat at 115 kJ/mol. H-mordenite exhibits a nearly constant heat of adsorption equal to 155 kJ/mol. The results from these microcalorimetric measurements are in agreement with thermogravimetric and temperature-programmed desorption results collected at higher temperatures. Adsorbed ammonia has sufficient mobility at 423 K to equilibrate with the catalyst surface on the time scale of microcalorimetric measurements, and these measurements provide an effective method for quantifying acid site distributions of solid-acid catalysts.     

Composition dependence of the oxygen-evolution reaction rate on Ir x Ti1−x O2 mixed-oxide electrodes

Mudcrack-free oxide films of Ir _x Ti_1–x O₂ (0 < x 1) on titanium substrates were obtained, and the effects of the oxide composition on the rate of oxygen-evolution reaction were investigated. At x 0.6, Ir-rich grains appear on the mudcrack-free surface. In the purely single-phase region (0 < x 0.5), the pseudo-capacitive charge is proportional to the surface composition, x _s, and the exchange-current density for the oxygen-evolution reaction increases linearly with x _s at 0.2 x _s 0.5, with an extrapolated intercept at x _s 0.15, below which the oxides are inactive.     

Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications

Catalytic decomposition of ammonia has been investigated as a method to produce hydrogen for fuel cell applications. The absence of any undesirable by-products (unlike, e.g., CO_x, formed during reforming of hydrocarbons and alcohols) makes this process an ideal source of hydrogen for fuel cells. In this study a variety of supported metal catalysts have been studied. Supported Ru catalysts were found to be the most active, whereas supported Ni catalysts were the least active. The supports were found to play a profound role in the ammonia decomposition process. The activation energies for the ammonia decomposition process varied from 17 to 22 kcal/mol depending upon the catalyst employed. The activation energies of the supported Ir catalysts were found to be in excellent agreement with our recent studies addressing ammonia decomposition on single crystal Ir.     

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.     

The temperature-programmed desorption of N2 from a Ru/MgO catalyst used for ammonia synthesis

The temperature-programmed desorption (TPD) of N₂ from a Ru/MgO catalyst used for ammonia synthesis was studied in a microreactor flow system operating at atmospheric pressure. Saturation with chemisorbed atomic nitrogen (N-*) was achieved by exposure to N₂ at 573 K for 14 h and subsequent cooling in N₂ to room temperature. With a heating rate of 5 K/min in He, a narrow and fairly symmetric N₂ TPD peak at about 640 K results. From experiments with varying heating rates a preexponential factor A_des = 1.5×10¹⁰ molecules/(site s) and an activation energy E_des = 158 kJ/mol was derived assuming secondorder desorption. This rate constant of desorption is in good agreement with results obtained with a Ru(0001) single crystal surface in ultra-high vacuum (UHV). The rate of dissociative chemisorption was determined by varying the N₂ exposure conditions. Determination of the coverage of N-^* was based on the integration of the subsequently recorded N₂ TPD traces yielding A_ads = 2×10^–6 (Pa s)^–1 and E_ads = 27 kJ/mol. The corresponding sticking coefficient of about 10^–14 at 300 K is in agreement with the inertness of Ru(0001) in UHV towards dissociative chemisorption of N₂. However, if the whole catalytic surface were in this state, then the resulting rate of N₂ dissociation would be several orders of magnitude lower than the observed rate of NH₃ formation. Hence only a small fraction of the total Rumetal surface area of Ru/MgO seems to be highly active dominating the rate of ammonia formation.     

Nitrous Oxide Reduction with Ammonia and Methane Over Mesoporous Silica Materials Modified with Transition Metal Oxides

Transition metal oxides (Cu, Cr and Fe) were deposited on various mesoporous silicas (MCM-48, SBA-15, MCF and x-MSU) by an impregnation method. Electron microprobe analysis, BET, UV-VIS-DRS and temperature programmed desorption of NH₃ were used for the characterization of the samples. The modified mesoporous silicas were tested as catalysts of the N₂O decomposition and the N₂O reduction using ammonia and methane. The Cu-containing samples presented the highest catalytic activity in the N₂O decomposition, while the Cr- and Fe-modified materials were more active in the reduction of nitrous oxide with NH₃ and CH₄. The type of the silica support strongly influenced the catalytic performance of the studied materials.     

An acid catalyzed step in the catalytic reduction of NO x to N2

Contact of adsorbed ammonium nitrite, NH₄NO₂, with HCl vapor or a solid acid such as the zeolite HY, significantly lowers the temperature of its decomposition to N₂ + H₂O. Protonated NH₄NO₂ decomposes at room temperature. The decomposition of ammonium nitrite is one of the steps in the catalytic reduction of NO _x with ammonia or other reductants.     

Highly Active CNT-Promoted Cu–ZnO–Al2O3 Catalyst for Methanol Synthesis from H2/CO/CO2

With types of in-house-synthesized multi-walled carbon nanotubes (CNTs) and the nitrates of the corresponding metallic components, highly active CNT-promoted Cu–ZnO–Al₂O₃ catalysts, symbolized as Cu _i Zn _j Al _k -x%CNTs, were prepared by the co-precipitation method. Their catalytic performance for methanol synthesis from H₂/CO/CO₂ was studied and compared with the corresponding CNT-free co-precipitated catalyst, Cu _i Zn _j Al _k . It was shown experimentally that appropriate incorporation of a minor amount of the CNTs into the Cu _i Zn _j Al _k could significantly increase the catalyst activity for methanol synthesis. Under the reaction conditions of 493 K, 5.0 MPa, H_2/CO/CO₂/N₂ = 62/30/5/3 (v/v), GHSV = 8000 h^-1, the observed CO conversion and methanol formation rate over a co-precipitated catalyst of Cu₆Zn₃Al₁-12.5%CNTs reached 36.8% and 0.291 mol CH₃OH s^-1 (m²-surf. Cu)^-1, which was about 44 and 25% higher than those (25.5% and 0.233 mol CH₃OH s^-1 (m²-surf. Cu)^-1) over the corresponding CNT-free co-precipitated catalyst, Cu₆Zn₃Al₁. Addition of a minor amount (10–15 wt%) of the CNTs to the Cu₆Zn₃Al₁ catalyst was found to considerably increase specific surface area, especially Cu surface area of the catalyst. H₂-TPD measurements revealed that the CNTs and the pre-reduced CNT-promoted catalyst systems could reversibly adsorb and store a considerably greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to 573 K. This unique feature would be beneficial for generating microenvironments with higher stationary-state concentration of active hydrogen adspecies on the surface of the functioning catalyst, especially at the interphasial active sites since the highly conductive CNTs might promote hydrogen spillover from the Cu sites to the Cu/Zn interphasial active sites, and thus be favorable for increasing the rate of the CO hydrogenation reactions. Alternatively, the operation temperature for methanol synthesis over the CNT-promoted catalysts can be 15–20 degrees lower than that over the corresponding CNT-free contrast system. This would contribute considerably to an increase in equilibrium CO conversion and CH₃OH yield. The results of the present work indicated that the CNTs could serve as an excellent promoter.     

Low Activation Energy Pathway for the Catalyzed Reduction of Nitrogen Oxides to N<Subscript>2</Subscript> by Ammonia

A low activation energy pathway for the catalytic reduction of nitrogen oxides to N₂, with reductants other than ammonia, consists of two sets of reaction steps. In the first set, part of the NO _x is reduced to NH₃; in the second set ammonium nitrite, NH₄NO₂ is formed from this NH₃ and NO + NO₂. The NH₄NO₂ thus formed decomposes at ~100 °C to N₂ + H₂O, even on an inert support, whereas ammonium nitrate, NH₄NO₃, which is also formed from NH₃ and NO₂ + O₂, (or HNO₃), decomposes only at 312 °C yielding mainly N₂O. Upon applying Redhead's equations for a first order desorption to the decomposition of ammonium nitrite, an activation energiy of 22.4 is calculated which is consistent with literature data. For the reaction path via ammonium nitrite a consumption ratio of 1/1 for NO and NO₂ is predicted and confirmed experimentally by injecting NO into a mixture of NH₃ + NO₂ flowing over a BaNa/Y catalyst. This leads to a yield increase of one N₂ molecule per added molecule of NO. Little N₂ is produced from NH₃ + NO in the absence of NO₂.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

Electrochemical oxidation of ammonia (NH4/NH3) on thermally and electrochemically prepared IrO2 electrodes

The electrochemical oxidation of ammonia (NH₄⁺/NH₃) in sodium perchlorate was investigated on IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor and the anodic oxidation of metallic iridium. The electrochemical behaviour of Ir(IV)/Ir(III) surface redox couple differs between the electrodes indicating that on the anodic iridium oxide film (AIROF) both, the surface and the interior of the electrode are electrochemically active whereas on the thermally decomposed iridium oxide films (TDIROF), mainly the electrode surface participates in the electrochemical processes.On both electrodes, ammonia is oxidized in the potential region of Ir(V)/Ir(IV) surface redox couple activity, thus, may involve Ir(V). During ammonia oxidation, TDIROF is deactivated, probably by adsorbed products of ammonia oxidation. To regenerate TDIROF, it is necessary to polarize the electrode in the hydrogen evolution region. On the contrary, AIROF seems not to be blocked during ammonia oxidation indicating its fast regeneration during the potential scan. The difference between both electrodes results from the difference in the activity of the iridium oxide surface redox couples.     

Effects of thermal treatments on the textural properties of chromium oxides CrO x obtained by oxalate decomposition

The porosity of oxides has an influence on their catalytic activity. An accurate knowledge of the effects of thermal treatments on the textural characteristics of oxides obtained by precursors decomposition is therefore an essential step. The porosity of the studied chromium oxides was analyzed by nitrogen adsorption-desorption measurements. Decomposition under air at 310–340°C of chromium oxalate allowed us to obtain more or less microporous X-ray amorphous chromium oxides, CrO _x (x 2), according to the heating and cooling rates and the treatment temperatures used. The oxides obtained from chromium hydroxides were mesoporous and had lower specific surface areas. Using high heating and cooling rates for the oxalate decomposition, the prepared chromium oxides were more microporous. By this way, the control of the textural properties of the resulting oxides is possible.     

Characterization of the Li1−x H x AlO2 system; 0.00 ⩽x ⩽ 0.90

The mechanism of cation replacement in the Li_1–x H _x AlO₂; 0.00 x 0.90 system was investigated with XRD. Examination of the peak position and intensity associated with the 018 and 110 Bragg reflections in a series of partially replaced samples showed that the cation replacement process proceeded by a two phase mechanism. Catalytic characterization of LiAlO₂ with the 2-propanol probe reaction revealed the formation of the condensation products methyl-cyclopentene, 4-methyl-2-pentanone, and 4-methyl-2-pentanol. These products were seen in addition to propylene and acetone. Catalytic characterization of Li_1–x H _x AlO₂;x = 0.90 with 2-propanol showed a significant decrease in condensation activity and no change in the propylene/acetone ratio relative to LiAlO₂. This suggests that the decrease in the amount of lithium eliminated the basic sites necessary for the condensation reactions.     

Selective Decomposition of NO in the Presence of Excess O2 in Electrochemical Cells

NO decomposition in solid electrolyte cells was investigated in the presence of excess O₂. The results show that NO is decomposed via an electrocatalytic mechanism rather than electrolysis in the range of 1–4 V of applied voltage. The NO is catalytically decomposed to N₂ on the cathode surface and O^2– produced in situ is transferred through the yttria-stabilized zirconia (YSZ) to the anode by direct current (d.c.) and then is evolved in the form of O₂, which helps to maintain the active state of the cathode. In a Pd/YSZ/Pd cell, the palladium metal surface is the active site for NO decomposition, while in the RuO₂/Pd/YSZ/Pd cell, the partially reduced RuO _x (0 < x < 2) is the main active site for NO decomposition. At 600 °C, the rate-determining step for the overall transportation of O^2– from cathode to anode in the RuO₂/Pd/YSZ/Pd cell is the transportation of O^2– at the cathode Pd/YSZ interface. The transportation rate of O^2– at the cathode M/YSZ interface decreases in the order of Ag > Au > Pd > Pt. Substitution of the Pd cathode by Ag leads to an increase in current density by a factor of 3.5. A higher NO decomposition parameter (=13.4) is also achieved at a lower temperature of 500 °C.     

Structure and magnetic properties of Fe1−xCox nanowires in self-assembled arrays

Fe_1−xCo_x nanowires in self-assembled arrays with varying compositions were produced by the template-assisted pulsed electrochemical deposition method. The structural and magnetic properties of the arrays were investigated using several experimental techniques. TEM analyses indicated that the nanowires were regular, uniform, 8 μm in length and 50 nm in diameter. The results of X-ray diffraction indicated that the body-centered-cubic (bcc) (α), face-centered-cubic (fcc) (γ), and hexagonal-close-packed (hcp) () Fe–Co phases appeared in different compositions. Magnetic measurements showed that the coercivity and squareness of the hysteresis loops of the Fe_1−xCo_x changed with their compositions, which may be attributable to shape anisotropy. The room temperature ⁵⁷Fe Mössbauer spectra of the arrays of the Fe_1−xCo_x nanowires revealed strong shape anisotropy.