Oxidation of ethane on high specific surface SmCoO3 and PrCoO3 perovskites

An adapted sol–gel method allowed synthesizing SmCoO₃ and PrCoO₃ oxides with high specific surface (ca. 28 m² g⁻¹) and a relatively clean perovskite phase at 600 °C, a temperature much lower than the one required in ceramic methods. The perovskites were investigated as catalysts for the oxidation of ethane in the temperature range 300–400 °C. Both catalysts were very active: ethane was activated already at 300 °C, i.e., 100 °C below the temperatures previously reported for perovskites. The main product was CO₂ on both catalysts, but on PrCoO₃ oxidehydrogenation (ODH) to ethylene was observed already at 300 °C, with the low selectivity. Even so, this was quite unusual for simple perovskites, and for such a low temperature. TPR data showed that praseodymium decreases the reducibility of Co³⁺ in the perovskite, what could explain the observed ODH, and suggest it proceeds via a Mars–van Krevelen mechanism. Kinetic study showed a similar apparent activation energy for both catalysts (ca. 80 kJ/mol), but a difference in the nature of the participating oxygen species: while on PrCoO₃ both adsorbed and lattice species contribute to the reaction, on SmCoO₃ contribution of adsorbed species is practically negligible, due to its very high oxygen lability. The results show that these simple perovskites may be promising catalysts for ethane oxidation at relatively low temperatures.     

Catalytic oxidation of CO over Ag-Co/alumina catalysts

Low-loading silver cobalt catalysts on alumina for the catalytic oxidation of carbon monoxide were synthesized following different preparation methods: the single-step sol-gel method and the impregnation method. A catalyst synthesized by the single-step sol-gel method gave high surface area values. The activities of alumina-supported silver-cobalt catalysts were studied to obtain the effects of the calcination temperature, metal loading, and preparation methods on CO oxidation at low temperature. The catalysts prepared by impregnation metals on the alumina synthesized by the sol-gel method gave the best activity for the CO oxidation. Catalytic activity conversion of (5 wt% Ag-5 wt% Co)/Al 2 O 3 catalysts prepared by the sol-gel-impregnation method reached 100% at 200°C. Increasing silver loading over the catalysts gave rise to more active catalysts. The sol-gel catalysts had poor activity at low temperature.     

Catalytic combustion of soot over alkali doped SrTiO3

The effect of introduction of alkalies (Me = Li, K, Cs) into SrTiO₃ on the physico-chemical properties of resulted materials and their catalytic activity in soot combustion was studied. Two groups of SrTiO₃ based perovskites were prepared: substituted in A-position of the structure (Sr_1 − xMe_xTiO₃, x = 0.05–0.2) and impregnated with the same amount of alkali metals. Prepared materials exhibit low specific surface area and perovskite structure, only these ones impregnated with the highest amount of Cs (K) show weak XRD signals of Me₂O. TPD-O₂ experiments show bimodal profiles of O₂ desorption curves with maximums corresponding to individual step of alkali nitrates thermal decomposition. It is supposed that second peak of O₂ desorption from impregnated SrTiO₃ can be related to reversible decomposition of MeNO₃. XPS shows that surface of SrTiO₃ substituted with K (Cs) is much richer in these elements than the surface of impregnated one. Prepared materials lower the temperature of soot ignition from 530 (inert) to 470 °C for SrTiO₃ and to 302–303 °C for Sr_0.8K_0.2TiO₃ and Sr_0.8K_0.2TiO₃, respectively. Substituted materials are more active in soot combustion than impregnated ones. A mechanism explaining effect of alkali metals nitrate addition to SrTiO₃ on its catalytic activity in soot combustion is proposed.     

Catalytic oxidation of HCN over a 0.5% Pt/Al2O3 catalyst

The adsorption of HCN on, its catalytic oxidation with 6% O₂ over 0.5% Pt/Al₂O₃, and the subsequent oxidation of strongly bound chemisorbed species upon heating were investigated. The observed N-containing products were N₂O, NO and NO₂, and some residual adsorbed N-containing species were oxidized to NO and NO₂ during subsequent temperature programmed oxidation. Because N-atom balance could not be obtained after accounting for the quantities of each of these product species, we propose that N₂ and was formed. Both the HCN conversion and the selectivity towards different N-containing products depend strongly on the reaction temperature and the composition of the reactant gas mixture. In particular, total HCN conversion reaches 95% above 250 °C. Furthermore, the temperature of maximum HCN conversion to N₂O is located between 200 and 250 °C, while raising the reaction temperature increases the proportion of NO_x in the products. The co-feeding of H₂O and C₃H₆ had little, if any effect on the total HCN conversion, but C₃H₆ addition did increase the conversion to NO and decrease the conversion to NO₂, perhaps due to the competing presence of adsorbed fragments of reductive C₃H₆. Evidence is also presented that introduction of NO and NO₂ into the reactant gas mixture resulted in additional reaction pathways between these NO_x species and HCN that provide for lean-NO_x reduction coincident with HCN oxidation.     

Fe/Al_2O_3催化剂催化氧化兰炭废水

采用浸渍法制备Fe/Al_2O_3催化剂,采用BET、XRD和穆斯堡尔谱等进行结构和性能表征。以自制Fe/Al_2O_3为催化剂,应用催化湿式过氧化氢氧化技术处理COD为6 742 mg·L-1的兰炭废水,通过建立正交实验确定最佳实验条件,结果表明,在p H=4、过氧化氢添加量9.6 m L、反应时间150 min和反应温度80℃条件下,兰炭废水COD去除率达66.30%。对催化氧化后的废水进行GC-MS分析,确定最终氧化产物主要为乙酸。表明自制Fe/Al_2O_3催化剂具有优良的催化效果,并使大分子难降解有机污染物分解为易生化的小分子污染物,甚至被完全分解矿化。     

Catalytic oxidation of nitrogen monoxide over La1−xCexCoO3 perovskites

This paper presents an investigation on the NO oxidation properties of perovskite oxides. La_1−xCe_xCoO₃ (x = 0, 0.05, 0.1, 0.2, 0.3, 0.4) perovskite-type oxides were synthesized through a citrate method and characterized by XRD, BET and XPS. The catalytic activities were enhanced significantly with Ce substitution, and achieved the best when x was 0.2, but decreased at higher x values. The performed characterizations reveal that the adsorbed oxygen on the surface plays an important role in the oxidation of NO into NO₂. The surface compounds after the co-adsorption of NO and O₂ at room temperature, were investigated by DRIFTS and TPD experiments. Three species: the bridging nitrate, the hyponitrites and the monodentate nitrate, were formed on the surface. The order of thermal stabilities was as follows: monodentate > hyponitrite > bridging. Among them, only the monodentate nitrate which decomposed at above 300 °C, would desorb NO₂ into the gas phase. When Ce was added, the temperature of monodentate nitrate desorption became low and the adsorption of the other two species decreased. This might be related to the oxidation state of Co on the surface. Analysis by synthesizing the characterization results and catalytic activity data shows that large amounts of adsorbed oxygen, small amount of inactive compounds on the surface and low NO₂ desorption temperature are favorable for the oxidation of NO.     

Catalytic decomposition of nitric oxide by perovskites

Catalytic decomposition of nitric oxide has been studied for nearly a century, using materials ranging from noble metals to alkaline earth metal oxides, without much success. Only since about last fifteen years some progress in finding promising materials has been made. Of the numerous catalyst systems studied, very few show tangible decomposition rates : copper substituted zeolites, silver-cobalt mixed oxides, some perovskites, and supported noble metals. Although at 773 K the rates of decomposition over zeolites are two to three orders higher than those over remaining systems, these materials have very low thermal stability, above 773 K. In this respect, perovskites have much higher potential, although so far no composition exhibiting practical decomposition rates has been found. Systematic study of the effect of composition on the performance should help to advance the complete understanding of this important reaction. In this paper a current state of art is outlined, and some latest preliminary results for new specially formulated perovskites are presented.     

催化氧化法分解邻二氯苯

通过实验室研究邻二氯苯在TiO₂-V₂O₅-WO₃等催化剂上氧化分解的特性，筛选出一种合适的催化剂，用于分解脱除垃圾焚烧废气中的二恶英。实验表明，在温度为300 ℃和气体空速为7000 h^－1的反应条件下，邻二氯苯在TiO₂-V₂O₅-WO₃催化剂上的分解率大于90%。     

Mullite-Al2O3-SiC oxidation protective coating for carbon/carbon composites

In order to exploit the unique high temperature mechanical properties of carbon/carbon (C/C) composites, a new type of oxidation protective coating has been produced by a two-step pack cementation technique in an argon atmosphere. XRD analysis showed that the internal coating obtained from the first step was a gradient SiC layer that acts as a buffer layer, and the multi-layer coating formed in the second step was an Al₂O₃-mullite layer. It was found that the as-received coating characterized by excellent thermal shock resistance on the surface of C/C composites during exposure to an oxidizing atmosphere at 1873 K, could effectively protect the C/C composites from oxidation for 45 h. The failure of the coating is due to the formation of bubble holes on the coating surface.     

CO3O4/MPS催化氧化NO性能

微乳法制备的介孔二氧化硅（MPS）负载Co3O4构成了Co3O4/MPS催化剂,考察了负载量、焙烧温度等制备条件和反应温度、空速、NO进口浓度、O2体积分数等操作条件对Co3O4/MPS催化氧化NO性能的影响,并对载体及催化剂进行了BET和XRD表征。结果表明：MPS比表面积远大于其它载体,Co3O4呈立方晶型,MPS负载25%的Co3O4在300 ℃下焙烧3 h得到催化剂的晶体颗粒最小,分散性好,具有最佳催化氧化活性和良好的稳定性,在NO进口浓度500 μL/L、O2体积分数10%、空速12 000 h－1的条件下,250 ℃时NO氧化率可达50%～60%（此时可获得最高的NOx吸收效率）,300 ℃氧化率达到80%以上,接近热力学平衡值。     

Mechanical behavior of La0.8Sr0.2Ga0.8Mg0.2O3 perovskites

This paper examines the important mechanical properties of commercially purchased La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ at room temperature and 800 °C. Sr and Mg-doped lanthanum gallates (LSGM) are strong candidates for use as solid electrolytes in lower temperature solid oxide fuel cells operating at or below 800 °C. The material was found to be phase pure with a Young's modulus value of ∼175 GPa. The four point bending strength of the LSGM samples remained almost constant from 121 ± 35 MPa at room temperature to 126 ± 20 MPa at 800 °C. The fracture toughness, as measured by the single edge V notch beam (SEVNB) method, was 1.22 ± 0.06 MPa√m at room temperature, 1.04 ± 0.09 MPa√m at 700 °C followed by a small increase 1.31 ± 0.16 MPa√m at 800 °C. We also report, for the first time, the static subcritical (or slow) crack-growth (SCG) behavior of natural cracks in LSGM performed in four point bending tests at room temperature. The exponent of a power-law representation in the SCG tests was found to be n = 15, a rather low value showing LSGM to be highly susceptible to room temperature SCG.     

Catalytic properties of novel La–Sr–Cu–O–S perovskites for automotive C3H6/CO oxidation in the presence of SOx

A La–Sr–Cu–O–S system with K₂NiF₄ perovskite-type structure has been studied as a novel SO_x-resistant combustion catalyst. The XRD result implied that sulfur is incorporated into the structure as non-sulfate-type cations. An introduction of sulfur with highly positive valence (S⁶⁺ or S⁴⁺) into the lattice requires the charge compensation by decreasing the oxidation number of Cu. This is accompanied by the creation of more reducible Cu species, which would achieve the light-off of catalytic C₃H₆ oxidation at lower temperatures. More important feature of sulfur-containing compounds is that the catalytic C₃H₆ oxidation was significantly accelerated by addition of SO₂ to the gas feed. The catalytic performance for the oxidation of C₃H₆ and CO and the reduction of NO was finally evaluated in a simulated automotive exhaust in the presence of SO₂.     

Catalytic oxidation of sulfide ions over nickel hydroxides

The catalytic sulfide ion oxidation by oxygen to elemental sulfur over β-Ni(OH)₂ and LiNiO₂ has been studied. As a result of experimental investigation performed, a reaction mechanism is suggested which involves heterogeneous and homogeneous processes. Dioxygen activation in the heterogeneous process proceeds via a redox Ni²⁺ ↔ Ni³⁺ transition and participation of OH⁻ groups. The active HO⁻₂ species thus formed carries on the reaction in homogeneous phase. Nickel hydroxides are promising catalysts for practical application.     

Influence of chlorine ions in Pt/A12O3 catalysts for methane total oxidation

Residual chlorine ions on a Pt/Al₂O₃ catalyst surface prepared from chlorine-containing precursors appear to inhibit the total oxidation of methane. At 450°C, as chlorine is eliminated with time on stream, the reaction rate increases despite the sintering of the platinum particles. The steady state reaction rate which is reached after 60 h is identical to that obtained with a catalyst prepared from a precursor containing no chlorine. Whether chlorine is present or not in the initial state of the catalyst does not appear to have an influence on the evolution of the platinum particle size.     

Effect of Y2O3 on the oxidation properties of ZrSi2/SiC coating prepared by SAPS on the carbon-carbon composites

In order to improve the oxidation resistance of carbon-carbon (C/C) composites at high temperature, different content of Y₂O₃ modified ZrSi₂/SiC coating for C/C composites were prepared by pack cementation and supersonic atmosphere plasma spraying (SAPS). Microstructure observation and phase identification of the coatings were analyzed by SEM, XRD, DSC/TG and EDS. Experimental results shown that the coating with 10?wt% Y₂O₃ effectively protected C/C composites from oxidation at 1500?°C in air for 301?h with a mass loss of 0.13% and experienced 18 thermal shock times from room temperature (RT) to 1500?°C. First, Y₂O₃ could restrain the phase transition of ZrO₂ to reduce the formation of thermal stresses of the coating; second, the random distribution of ZrO₂ ceramic particles and the formation of ZrSiO₄ enhanced the stability of the SiO₂; third, the formation of Y₂Si₂O₇ and Y₂SiO₅ could relieve the thermal mismatch between ZrSi₂-Y₂O₃ outer layer and the inner layer.     

Catalytic oxidation of hydrocarbons over Co3O4 catalyst prepared by CVD

The total oxidation of C₂H₂, C₃H₆, C₃H₈, n-C₄H₈, n-C₄H₁₀ and i-C₄H₁₀ was studied in a monolithic flow reactor under temperature-programmed mode and highly diluted conditions. The non-catalytic combustion of the investigated hydrocarbons leads to a substantial formation of CO and traces of methane at intermediate temperatures. This drawback was suppressed upon the deposition of a thin layer of Co₃O₄ on the monolith and all investigated hydrocarbons tend to light off at 250–290 °C. The apparent activation energy was found to exhibit a linear correlation with the C–H bond dissociation energy, indicating that the C–H activation is still the rate-limiting step.     

The role of acidity in the decomposition of 1,2-dichlorobenzene over TiO2-based V2O5/WO3 catalysts

The influence of Lewis and Brønsted acid sites on the performance of V₂O₅/TiO₂ and V₂O₅–WO₃/TiO₂ catalysts in the total oxidation of o-dichlorobenzene was investigated. Catalytic activity of these materials resulted strongly affected by their acidic properties. The presence of Brønsted acid sites significantly increases the o-DCB conversion but also leads to the uncompleted degradation of chlorinated compounds, promoting the formation of partial oxidation products, as dichloromaleic anhydride. On the contrary, Lewis acid sites, acting as absorbing sites, promote the further oxidation of intermediates to CO and CO₂, without any by-products desorption.

Furthermore, the presence of water in the feed-stream was proven to decrease o-DCB conversion but also to play a positive role on process selectivity, increasing COx production. Plausible reasons for this effect are the reduction of Brønsted acid sites and the hydrolysis of anhydride during wet tests.     

Catalytic combustion of methane over perovskites

Perovskite-type oxides of the series La_{1− x}A_xMnO₃ (A Sr, Eu and Ce) were prepared by the amorphous citrate process, leading to high surface area catalysts (up to 45 m² g⁻¹). They were tested in a flow reactor for the total combustion of methane. Complete conversion was obtained over all of the catalysts between 500 and 600°C and catalyst performance did not change significantly after 100 h on-stream. Specific activity was found to decrease monotonically with increasing the temperature of the O₂ TPD desorption peak maximum. The rate of methane combustion was low below 500°C, then grew very fast, showing that two kinds of oxygen are active in these catalysts: an adsorbed oxygen species, that reacts at low temperature, and a lattice oxygen species, that becomes available at high temperature, boosting the catalytic activity.     

Oxidation behaviour and catalytic properties of Pd/Al2O3 catalysts in the total oxidation of methane

A series of Pd/Al₂O₃ catalysts with a wide range of mean Pd particle sizes (ca. 2–30 nm in diameter) was prepared by using various precursors (H₂PdCl₄, Pd(NO₃)₂ and Pd(AcAc)₂) and pre-treatments. The mean particle size of reduced samples was determined by H₂ chemisorption. The catalytic activity in methane oxidation under lean burn conditions was measured. The oxidation of reduced samples was studied at 300 °C. The extent of oxidation was found to decrease with increasing mean particle size. While small particles (<5 nm) oxidised very rapidly, the oxidation of large particles (ca. >15 nm) proceeded via a two-step process, being first fast and then slow. The decomposition of oxide species was studied by temperature-programmed experiments under vacuum. Two distinct oxidised species with different stability were evidenced depending on the particle size. Oxidised species in larger particles were found of lower stability than in smaller ones. A correlation between the existence of distinct types of oxide species and catalytic properties in methane oxidation was discussed.     

Exchange and oxidation of CO on O-predosed Rh---Al2O3 and Rh---CeO2 catalysts

Exchange and oxidation of C¹⁶O were investigated at 450°C on ¹⁸O-predosed Rh and Pt catalysts supported on A1₂O₃, CeO₂ and CeO₂-Al₂O₃. In all cases, a rapid exchange of C¹⁶O with the surface can be observed. CO oxidation leads to C¹⁶O₂, C¹⁶O¹⁸O and C¹⁸O₂. Significant formation of C¹⁶O₂ is due to the relatively high ¹⁶O coverage in reaction resulting from the C¹⁶O exchange and from an exchange between O surface species and ¹⁶O internal atoms. Hydrogen is also formed via a water-gas shift reaction (CO + surface OH) in higher proportion on CeO₂-containing catalysts than on A1₂O₃. Chlorine inhibits all the reactions (exchange, oxidation and WGS) and particularly the internal exchange.