Catalytic activity of Cu/η-Al2O3 catalysts prepared from aluminum scraps in the NH3-SCO and in the NH3-SCR of NO.

Copper-loaded η-alumina catalysts with different copper contents were prepared by impregnation/evaporation method. The catalysts were characterized by XRD, FTIR, BET, UV-Vis, and H2-TPR and evaluated, for the first time, in the selective catalytic reduction of NO by NH3 and in the selective catalytic oxidation of NH3. The characterization techniques showed that the impregnation/evaporation method permits to obtain highly dispersed copper oxide species on the η-alumina surface when a low amount of copper is used (1wt. % and 2 wt.%). The wet impregnation method made it possible to reach a well dispersion of the copper species on the surface of the alumina for the low copper contents Cu(1)-Al2O3 and Cu(2)-Al2O3. The latter justifies the similar behavior of Cu(1)-Al2O3) and Cu(2)-Al2O3 in the selective catalytic oxidation of NH3 where these catalysts exhibit a conversion of NH3 to N2 of the order of 100% at T> 500 °C.

Catalytic decomposition of N2O over Cu-Al-O x mixed metal oxides.

Cu-Al-O x mixed metal oxides with intended molar ratios of Cu/Al = 85/15, 78/22, 75/25, 60/30, were prepared by thermal decomposition of precursors at 600 °C and tested for the decomposition of nitrous oxide (deN2O). Techniques such as XRD, ICP-MS, N2 physisorption, O2-TPD, H2-TPR, in situ FT-IR and XAFS were used to characterize the obtained materials. Physico-chemical characterization revealed the formation of mixed metal oxides characterized by different specific surface area and thus, different surface oxygen default sites. The O2-TPD results gained for Cu-Al-O x mixed metal oxides conform closely to the catalytic reaction data. In situ FT-IR studies allowed detecting the form of Cu+⋯N2 complexes due to the adsorption of nitrogen, i.e. the product in the reaction between N2O and copper lattice oxygen. On the other hand, mostly nitrate species and NO were detected but those species were attributed to the residue from catalyst synthesis.

Selective catalytic reduction of nitrogen oxides over a modified silicoaluminophosphate commercial zeolite.

Nitrogen oxides (NOx: NO, NO2) are a concern due to their adverse health effects. Diesel engine transport sector is the major emitter of NOx. The regulations have been strengthened and to comply with them, one of the two methods commonly used is the selective catalytic reduction of NOx by NH3 (NH3-SCR), NH3 being supplied by the in-situ hydrolysis of urea. Efficiency and durability of the catalyst for this process are highly required. Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800°C. In this study, very active catalysts for the NH3-SCR of NOx were prepared by using a silicoaluminophosphate commercial zeolite as copper host structure. Characterizations by X-ray diffraction (XRD), scanning electron microscopy (SEM) and temperature programmed desorption of ammonia (NH3-TPD) showed that this commercial zeolite was hydrothermally stable up to 850°C and, was able to retain some structural properties up to 950°C. After hydrothermal treatment at 850°C, the NOx reduction efficiency into NH3-SCR depends on the copper content. The catalyst with a copper content of 1.25wt.% was the most active. The difference in activity was much more important when using NO than the fast NO/NO2 reaction mixture.

Valorization of vitreous China waste to EMT/FAU, FAU and Na-P zeotype materials.

In this study, Na-X, Na-P, SOD and EMT/FAU zeotype materials have been prepared from vitreous China waste by conventional hydrothermal route and alkaline fusion prior to hydrothermal synthesis. The conventional route has shown its limits in the activation of the waste in the chosen experimental conditions, [NaOH] = 3.5 M and T = 60 °C. The amorphous phase of vitreous China waste plays an important role during the zeolitization process because it easily dissolves into the alkaline solution compared to crystalline phases like quartz and mullite. By the conventional route, Na-X and Na-P1 and SOD zeolites were obtained. The alkaline fusion step using NaOH as mineralizer at 550 °C converted the waste to highly active soluble aluminate and silicate salts. The fused material was mixed with distilled water to have liquid to solid ratio L/S = 5, under vigorous stirring at room temperature for 1 day. The obtained gel with molar composition of 7.0 Na2O: 1.0 Al2O3: 4.8 SiO2: 209.4 H2O was converted by hydrothermal crystallization at 60 °C to nanosized EMT/FAU zeotype and geopolymeric amorphous aluminosilicate material. With the increase of fusion time, there is a decrease of the amount of EMT-type zeolite.

Ultrasound-assistant preparation of Cu-SAPO-34 nanocatalyst for selective catalytic reduction of NO by NH3.

The influence of the various preparation methods of Cu-SAPO-34 nanocatalysts on the selective catalytic reduction of NO with NH3 under excess oxygen was studied. Cu-SAPO-34 nanocatalysts were prepared by using four techniques: conventional impregnation (IM), ultrasound-enhanced impregnation (UIM), conventional deposition precipitation (DP) using NaOH and homogeneous deposition precipitation (HDP) using urea. These catalysts were characterized in detail by various techniques such as N2-sorption, XRD, TEM, H2-TPR, NH3-TPD and XPS to understand the catalyst structure, the nature and the dispersed state of the copper species, and the acid sites for NH3 adsorption. All of the nanocatalysts showed high activities for NO removal. However, the activities were different and followed the sequence of Cu-SAPO-34 (UIM)>Cu-SAPO-34 (HDP)>Cu-SAPO-34 (IM)>Cu-SAPO-34 (DP). Based on the obtained results, it was concluded that the NO conversion on Cu-SAPO-34 nanocatalysts was mainly related to the high reducibility of the isolated Cu(2+) ions and CuO species, the number of the acid sites and the dispersion of CuO species on SAPO-34.

A highly efficient silver niobium alumina catalyst for the selective catalytic reduction of NO by n-decane.

AgNb/Al(2)O(3) prepared by a nonhydrolytic sol-gel process is a highly efficient catalyst for NO(x) removal through selective catalytic reduction by hydrocarbons (HC-SCR). This result shows that the HC-SCR process remains a challenging method for lean engine DeNO(x).

Probing Cu(I)-exchanged zeolite with CO: DFT modeling and experiment.

Addition of CO on Cu-exchanged zeolite was investigated by means of quantum chemical calculations based on density functional theory. The aim of this investigation was to get insights about changes of electronic properties of a copper site with zeolite composition by using a CO probe molecule. Calculated nu(CO) frequency values show that various Si/Al ratios of faujasite zeolite reproduce the expected experimental decrease of the nu(CO) values with decreasing Si/Al ratio. These calculations predict that H/Na ratio variations also induce changes in the nu(CO) values. These results illustrate that different compositions of the zeolite change the electronic properties of copper that are reflected in the nu(CO) frequency values. DFT results showed also that different structures and CO adsorption energies are obtained due to various Si/Al and H/Na ratios of the zeolite. Finally, these calculations evidence the possibility for CO to be connected at the same time to Cu(I) and to a close Na cation, Cu being at site II and Na at site II in Cu(I)-exchanged faujasite. A DRIFT experiment on two samples of faujasite, Cu(28)H(51)NaY and Cu(25)H(0)NaY, supports nu(CO) displacements to higher energy values with increasing H/Na ratio.

Theoretical study of N2O reduction by CO in Fe-BEA Zeolite.

Quantum mechanical (QM) and QM/molecular mechanics (MM) studies of the full catalytic cycle of N(2)O reduction by CO in Fe-BEA zeolite, that is, oxidation of BEA-Fe by N(2)O and reduction of BEA-Fe-alphaO by CO, is presented. A large QM cluster, representing half of the channel of the BEA zeolite, is used. The contribution of the MM embedding to the calculated activation energies is found to be negligible. The minimum-energy paths for N(2)O decomposition and reduction with CO are calculated using the nudged elastic band (NEB) method. Calculated and experimental activation energies are in good agreement. The two possible orientations for the gaseous molecules adsorbing on the Fe site that are found lead to different activation energies.

Novel non-hydrolytic synthesis of a V2O5-TiO2 xerogel for the selective catalytic reduction of NOx by ammonia.

A vanadia-titania mesoporous xerogel (10.5 wt% V(2)O(5)) was prepared from chloride precursors using a one-step non-hydrolytic sol-gel route and subsequent drying at ambient pressure; after calcination at 773 K for 5 h no crystalline V(2)O(5) was detected and the resulting mixed oxide exhibited remarkable activity in the selective reduction of NO with NH(3).

Selective catalytic reduction of NO by NH3 on Cu-faujasite catalysts: an experimental and quantum chemical approach.

The selective catalytic reduction (SCR) of NO by NH3 in the presence of O2 on Cu-faujasite (Cu-FAU) has been studied. Substitution of some Cu2+ with H+ and Na+ cations, compensating for the negative charge of the zeolite framework, forms the various CuHNa-FAU studied. The amount of Cu was held constant and the proportion of H+ and Na+ varied in the sample. The substitution of Na+ for H+ increases sharply the SCR rate by lowering the temperature of reaction by about 150 K. It is proposed that the rate increase mainly comes from an unhindered migration of Cu from hidden to active sites and a modification of the redox properties of Cu species. The former was demonstrated by diffuse reflectance IR spectroscopy of adsorbed CO. The change in redox properties was demonstrated by a faster oxidation of Cu+ to Cu2+ (rate-determining step). Quantum chemical calculations on model clusters of CuHNa-FAU indicate that the faster rate of oxidation can be explained by a higher lability of protons in the absence of Na, which can be then removed from the catalyst more easily to yield H2O during the oxidation process.