Effects of Tb and Ba introduction on the reaction mechanism of direct NO decomposition over C-type cubic rare earth oxides based on Y2O3

Direct decomposition of NO into N 2 and O 2 over La(Ba)Mn(In)O 3 perovskite oxide

Catalytic activities for direct NO decomposition were investigated on C-type cubic Y2O3–ZrO2 and Y2O3–ZrO2–BaO prepared by coprecipitation. Introduction of excess oxide anions in the Y2O3 lattice was achieved by partial substitution of the Y3+ sites with Zr4+, and high NO decomposition activity was obtained for the (Y0.97Zr0.03)2O3.03 catalyst. In addition, the catalytic activity was further enhanced by partial substitution of the Y3+ sites in the Y2O3–ZrO2 solid solution with Ba2+, and the (Y0.89Zr0.07Ba0.04)2O3.03 catalyst exhibited the highest NO decomposition activity among the samples prepared; NO conversion to N2 reached 90% at 1173 K in the absence of O2 (NO/He atmosphere), and a relatively high conversion ratio was observed even in the presence of O2, H2O, or CO2, compared with the activities of conventional direct NO decomposition catalysts. These results indicate that the C-type cubic Y2O3–ZrO2–BaO catalyst is a new potential candidate for direct NO decomposition.

Catalytic activities for direct NO decomposition were investigated over C-type cubic Y2O3–Tb4O7–ZrO2 prepared by a coprecipitation method. The NO decomposition activity was enhanced by partial substitution of the yttrium sites with terbium in a (Y0.97Zr0.03)2O3.03 catalyst, which shows high NO decomposition activity. Among the catalysts synthesized in this study, the (Y0.67Tb0.30Zr0.03)2O3.33 catalyst exhibited the highest NO decomposition activity; NO conversion to N2 was as high as 67% at 900℃ in the absence of O2 (NO/He atmosphere), and a relatively high conversion ratio was observed even in the presence of O2 or CO2, compared with those obtained over conventional direct NO decomposition catalysts. These results indicate that the C-type cubic Y2O3–Tb4O7–ZrO2 catalyst is a new potential candidate for direct NO decomposition.

The basic aspects of rare earth oxides (REOs) that affect their capacity for direct NO decomposition catalysis were investigated. A correlation between crystal structure and catalytic activity was found, which is related to the NO adsorption ability of the REOs. The crystal structure was the most important factor affecting direct NO decomposition over REOs, since the adsorption of NO was significantly dependent on the coordination environments of the rare earth cations within each crystal lattice. Among the REOs, cubic C‐type oxides showed higher NO decomposition activities than those of the others. Within a series of C‐type cubic REOs, the activity was typically dominated by the density of the surface basic sites, and the effects of particle morphology and lattice parameters were small.

NO decomposition over supported alkaline earth metal oxide catalysts was strongly dependent on the type of metal oxide support. Y 2 O 3 was the most effective support. Ba/Y 2 O 3 showed the highest NO decomposition activity, which decreased in the order of Ba/Y 2 O 3 > Sr/Y 2 O 3 > Ca/Y 2 O 3 > Mg/Y 2 O 3 ∼Y 2 O 3 . The catalytic activity of Ba/Y 2 O 3 for NO decomposition at 900°C gradually increased with reaction time. The activity enhancement was due to the decomposition of barium carbonate into barium oxide during the reaction. Barium carbonate was completely decomposed by reduction with H 2 at 900°C, resulting in significant enhancement of NO decomposition activity. The activity of Ba/Y 2 O 3 increased with higher barium loading up to 5 wt%, and then became constant. There was a strong relationship between NO conversion and the amount of NO adsorption on Ba/Y 2 O 3 , suggesting that NO adsorption sites are the reaction sites for NO decomposition. The relationship between the activity for 1-butene isomerization, which is an indicator for the basicity of Ba/Y 2 O 3 catalysts, and the activity for NO decomposition suggests direct participation of basic sites in the NO decomposition reaction over supported alkaline earth metal oxide catalysts.

Support and particle size effects on direct NO decomposition over platinum

Direct NO decomposition over conventional and mesoporous Cu-ZSM-5 and Cu-ZSM-11 catalysts: Improved performance with hierarchical zeolites

Catalytic activity of perovskite-type oxide catalysts for direct decomposition of NO: Correlation between cluster model calculations and temperature-programmed desorption experiments

Direct decomposition of NO into N2 and O2 (2NO→N2 + O2) is recognized as the “ideal” reaction for NOx removal because it needs no reductant. It was reported that the spinel Co3O4 is one of the most active single-element oxide catalysts for NO decomposition at higher reaction temperatures, however, activity remains low below 650 °C. The present study aims to investigate new promoters for Co3O4, specifically PdO vs. PtO. Interestingly, the PdO promoter effect on Co3O4 was much greater than the PtO effect, yielding a 4 times higher activity for direct NO decomposition at 650 °C. Also, Co3O4 catalysts with the PdO promoter exhibit higher selectivity to N2 compared to PtO/Co3O4 catalysts. Several characterization measurements, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2-temperature programmed reduction (H2-TPR), and in situ FT-IR, were performed to understand the effect of PdO vs. PtO on the properties of Co3O4. Structural and surface analysis measurements show that impregnation of PdO on Co3O4 leads to a greater ease of reduction of the catalysts and an increased thermal stability of surface adsorbed NOx species, which contribute to promotion of direct NO decomposition activity. In contrast, rather than remaining solely as a surface species, PtO enters the Co3O4 structure, and it promotes neither redox properties nor NO adsorption properties of Co3O4, resulting in a diminished promotional effect compared to PdO.

Adsorption and decomposition of NO on K-deposited Pd(1 1 1)

NO direct decomposition on doped SrFeO3 perovskite oxide was investigated. The ability of SrFeO3 for direct decomposition of NO is strongly affected by the dopant in Fe sites. Among the examined dopants and compositions, the highest yield of N2 was achieved on SrFe0.7Mg0.3O3. When SrFe0.7Mg0.3O3 was loaded with Pt, the N2 yield further improved, and the light-off temperature fell by 100 K. On this catalyst, the yields of N2 and O2 were 56 and 35%, respectively, at 1123 K. On the Pt-loaded SrFe0.7Mg0.3O3 catalyst, the NO decomposition rate increased with increase in the NO partial pressure with PNO1.31. The presence of oxygen slightly decreased the N2 yield with PO2−0.12. Therefore, the effect of oxygen poisoning on NO decomposition upon Pt-loaded SrFe0.7Mg0.3O3 is small. From the result of O2-TPD, Pt loading possibly weakens the adsorption strength of surface oxygen and enhances NO adsorption. In summary, this study shows that the substitution of Fe with lower valence cation in SrFeO3 and also loading a small amount of Pt are highly effective for increasing the NO decomposition activity.

An ab initio-based kinetic Monte Carlo algorithm was developed to simulate the direct decomposition of NO over Pt and different PtAu alloy surfaces. The algorithm was used to test the influence of the composition and the specific atomic surface structure of the alloy on the simulated activity and selectivity to form N2. The apparent activation barrier found for the simulation of lean NO decomposition over Pt(100) was 7.4 kcal/mol, which is lower than the experimental value of 11 kcal/mol that was determined over supported Pt nanoparticles. Differences are likely due to differences in the surface structure between the ideal (100) surface and supported Pt particles. The apparent reaction orders for lean NO decomposition over the Pt(100) substrate were calculated to be 0.9 and -0.5 for NO and O2, respectively. Oxygen acts to poison Pt. Simulations on the different Pt-Au(100) surface alloys indicate that the turnover frequency goes through a maximum as the Au composition in the surface is increased, and the maximum occurs near 44% Au. Turnover frequencies, however, are dictated by the actual arrangements of Pt and Au atoms in the surface rather than by their overall composition. Surfaces with similar compositions but different alloy arrangements can lead to very different activities. Surfaces composed of 50% Pt and 50% Au (Pt4 and Au4 surface ensembles) showed very little enhancement in the activity over that which was found over pure Pt. The Pt-Pt bridge sites required for NO adsorption and decomposition were still effectively poisoned by atomic oxygen. The well-dispersed Pt(50%)Au(50%) alloy, on the other hand, increased the TOF over that found for pure Pt by a factor of 2. The most active surface alloy was one in which the Pt was arranged into "+" ensembles surrounded by Au atoms. The overall composition of this surface is Pt(56.2%)Au(43.8%). The unique "+" ensembles maintain Pt bridge sites for NO to adsorb on but limit O2 as well as NO activation by eliminating next-nearest neighbor Pt-bridge sites. The repulsive interactions between two adatoms prevent them from sharing the same metal atoms. The decrease in the oxygen coverage leads to a greater number of vacant sites available for NO adsorption. This increases the NO coupling reaction and hence N2 formation. The inhibition of the rate of N2 formation by O2 is therefore suppressed. The coverage of atomic oxygen decreases from 53% on the Pt(100) surface down to 19% on the "+" ensemble surface. This increases the rate of N2 formation by a factor of 4.3 over that on pure Pt. The reaction kinetics over the "+" ensemble Pt(56.2%)Au(43.8%) surface indicate apparent reaction orders in NO and oxygen of 0.7 and 0.0, respectively. This suggests that oxygen does not poison the PtAu "+" alloy ensemble. The activity and selectivity of the PtAu ensembles significantly decrease for alloys that go beyond 60% Au. Higher coverages of Au shut down sites for NO adsorption and, in addition, weaken the NO and O bond strengths, which subsequently promotes desorption as well as NO oxidation. The computational approach identified herein can be used to more rapidly test different metal compositions and their explicit atomic arrangements for improved catalytic performance. This can be done "in silico" and thus provides a method that may aid high-throughput experimental efforts in the design of new materials. The synthesis and stability of the metal complexes suggested herein still ultimately need to be tested.

Comparative study of Nickel-based perovskite-like mixed oxide catalysts for direct decomposition of NO

The direct catalytic decomposition of NO into N2 and O2 with high activity and N2 selectivity at low temperature under excess oxygen is a challenge. Herein, we report a new approach for the direct decomposition of NO into N2 and O2 by microwave catalysis over MeOx‐Cu‐ZSM‐5 (Me=Mn, Ni) under excess oxygen. We observed that the microwave direct catalytic decomposition of NO over MeOx‐Cu‐ZSM‐5 under excess oxygen is highly efficient, and the NO conversions are 94.3 % over MnO2‐Cu‐ZSM‐5 at 300 °C and 92.3 % over Ni2O3‐Cu‐ZSM‐5 at 350 °C. Meanwhile, the N2 selectivity remains more than 98 %. Importantly, the apparent activation energies of MnO2‐Cu‐ZSM‐5 and Ni2O3‐Cu‐ZSM‐5 are as low as 15.5 and 25.7 kJ mol−1, which suggests a significant microwave catalytic effect. Furthermore, microwave irradiation exhibits a microwave selective effect. The oxygen concentration has almost no influence on the activity of catalytic decomposition of NO over MeOx‐Cu‐ZSM‐5 under microwave irradiation.

N2 yield on Ba0.8La0.2Mn0.8Mg0.2O3 decreased from 70% to 30% on the addition of 1% CO2, which is a much larger negative effect than that seen with O2. The CO2 negative effects are not permanent and this may result from the inhibition of NO adsorption. Co-feeding of H2 as a reductant is effective for increasing NO conversion. This suggests that the catalyst surface was covered with strongly adsorbed nitrate or nitride species which formed by adsorption of NO on oxygen formed by the decomposition of NO, and the removal of this surface species might be the most important step for the NO decomposition reaction. Co-feeding of H2 is also effective for increasing the NO decomposition activity in the presence of CO2. The reaction mechanism was studied by IR measurements which also revealed that the surface of the catalyst was covered with strongly bound nitrate species (NO3−). The addition of H2 to the reaction mixture is effective for NO3− removal and so accelerates the NO decomposition under coexistence of CO2.