Re-investigating the CO oxidation mechanism over unsupported MnO, Mn2O3 and MnO2 catalysts

Kinetic study of CO oxidation in combination with experiments of temperature-programmed oxidation (TPO) and reduction (TPR) have been performed on various unsupported crystalline manganese oxides (MnO_x); while the reactivity shows an order of MnO ≤ MnO₂ < Mn₂O₃ in a mixture of unit ratio of O₂/CO at/below 523 K. We propose that under the current conditions the interaction of adsorbed CO and O is mainly responsible for CO₂ formation on Mn₂O₃ and MnO₂ catalysts, following either the Langmuir–Hinshelwood mechanism or Eley–Rideal mechanism. Meanwhile, direct evidence from transient CO oxidation suggests that the Mars-van-Krevelen mechanism may occur for all catalysts simultaneously, especially, it is predominant for the MnO catalyst. The evidence of structural modifications during reaction was confirmed by Raman spectra obtained from used MnO.     

CO oxidation catalysts based on copper and manganese or cobalt oxides supported on MgF2 and Al2O3

The catalytic activity of a mixed phase of copper–cobalt and copper–manganese oxides supported on magnesium fluorine or alumina has been studied in low temperature CO oxidation at 30 °C. During calcination, the oxides studied partially react to form different type spinels depending on the calcination temperature. These spinels have different effect on the catalytic activity. In low temperature CO oxidation the copper–manganese catalysts are more active than the copper–cobalt ones.     

Reactivation of sintered Pt/Al2O3 oxidation catalysts

The reactivation of thermally sintered Pt/Al₂O₃ catalysts used in the simultaneous oxidation of CO and propene has been achieved by an oxychlorination treatment. The catalyst can be considered to model the active component of the catalytic converter fitted to diesel driven cars. Platinum crystallites redispersion was verified by XRD, H₂ chemisorption, TEM and FTIR. The extent of regeneration reflects the platinum particle redispersion achieved by such a treatment. Oxychlorination also introduced electronic effects in the Pt particle caused by the presence of chlorine at the Pt-Al₂O₃ interface but no detrimental result of this was observed in the oxidation reactions. The results indicate that the deactivation of the diesel oxidation catalysts (DOCs) can be reverted by this simple treatment resulting in a remarkable recovery of the catalytic activity.     

Preferential oxidation of CO over CuO/CeO2 and Pt-Co/Al2O3 catalysts in micro-channel reactors

Micro-channel plates with dimension of 1 mm × 0.3 mm × 48 mm were prepared by chemical etching of stainless steel plates followed by wash coating of CeO₂ and Al₂O₃ on the channels. After coating the support on the plate, Pt, Co, and Cu were added to the plate by incipient wetness method. Reaction experiments of a single reactor showed that the micro-channel reactor coated with CuO/CeO₂ catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al₂O₃ catalyst was highly active for CO oxidation. The 7-layered reactors coated with two different catalysts were prepared by laser welding and the performances of each reactor were tested in large scale of PROX conditions. The multi-layered reactor coated with Pt-Co/Al₂O₃ catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O₂/CO ratio due to the oxidation of H₂ which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO₂ showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O₂/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al₂O₃, CuO/CeO₂), a serial reactor was prepared by connecting the two multi-layered micro-channel reactors with different catalysts. The prepared serial reactor exhibited excellent performance for PROX.     

Methane oxidation over vanadium-modified Pd/Al2O3 catalysts

Three different vanadium-modified Pd/Al₂O₃ catalysts were prepared and tested as catalysts for the deep oxidation of methane. Vanadium was added to the palladium catalyst by incipient wetness of palladium catalyst in order to modify its properties and improve its thermal stability and thioresistance. The behaviour of vanadium-modified catalysts depends on the concentration of this compound, being 0.5 wt.% the optimum amount. However, when strong catalyst poisons are present in the gas (SO₂), these modified catalysts do not show a better performance than unmodified catalyst. Bimetallic catalysts were tested with and without further reduction, being observed that reduced bimetallic catalysts perform worse than the non-reduced ones.     

MnOx/Pt/Al2O3 catalysts for CO oxidation in H2-rich streams

The catalytic activity of Pt on alumina catalysts, with and without MnO_x incorporated to the catalyst formulation, for CO oxidation in H₂-free as well as in H₂-rich stream (PROX) has been studied in the temperature range of 25–250 °C. The effect of catalyst preparation (by successive impregnation or by co-impregnation of Mn and Pt) and Mn content in the catalyst performance has been studied. A low Mn content (2 wt.%) has been found not to improve the catalyst activity compared to the base catalyst. However, catalysts prepared by successive impregnation with 8 and 15 wt.% Mn have shown a lower operation temperature for maximum CO conversion than the base catalyst with an enhanced catalyst activity at low temperatures with respect to Pt/Al₂O₃. A maximum CO conversion of 89.8%, with selectivity of 44.9% and CO yield of 40.3% could be reached over a catalyst with 15 wt.% Mn operating at 139 °C and λ = 2. The effect of the presence of 5 vol.% CO₂ and 5 vol.% H₂O in the feedstream on catalysts performance has also been studied and discussed. The presence of CO₂ in the feedstream enhances the catalytic performance of all the studied catalysts at high temperature, whereas the presence of steam inhibits catalysts with higher MnO_x content.     

Partial oxidation of ethanol on Ru/Y2O3 and Pd/Y2O3 catalysts for hydrogen production

The partial oxidation of ethanol was investigated over Ru and Pd catalysts supported onto yttria over a wide range of temperatures (473–1073 K). The product distributions obtained over these catalytic systems were correlated with diffuse reflectance infrared spectroscopy analyses (DRIFTS). Results showed that reaction route depended strongly on the type of metal. The decomposition of ethoxy species to CH₄ and CO or oxidation to CO₂ was promoted by Pd, and the acetaldehyde desorption was predominant over Ru in the low temperature region. Furthermore, the acetate and carbonate formation prevailed over Pd, which explained the lower acetaldehyde selectivity. The presence of CH₄ and CO₂ at high temperature is assigned to the decomposition of acetate species via carbonates over Pd-based catalysts. Ru was more suitable system for H₂ production than Pd by achieving a selectivity of about 59%.     

MoO_3-CeO-Co_3O_4催化剂CO催化氧化及耐硫性能

采用共沉淀法和浸渍法联用制备不同Mo质量分数的x MoO_3-6CeO-Co_3O_4催化剂,测试催化剂催化氧化CO效率及其耐硫性能,并对催化剂进行BET、SEM、FT-IR和H2-TPR等表征。结果表明,MoO_3的添加可以提高催化剂低温活性,5.61MoO_3-6CeO-Co_3O_4催化剂低温活性最佳,40℃时CO去除率达98%,耐硫性能达90 min。     

Characterization and catalytic activity of Pd/V2O5/Al2O3 catalysts on benzene total oxidation

The role of vanadium oxide and palladium on the benzene oxidation reaction over Pd/V₂O₅/Al₂O₃ catalysts was investigated. The Pd/V₂O₅/Al₂O₃ catalysts were more active than V₂O₅/Al₂O₃ and Pd/Al₂O₃ catalysts. The increase of vanadium oxide content decreased the Pd dispersion and increased the benzene conversion. A strong Pd particle size effect on benzene oxidation reaction was observed. Although the catalysts containing high amount of V⁴⁺ species were more active, the Pd particle size effect was responsible for the higher activity.     

Effects of ZrO2/Al2O3 properties on the catalytic activity of Pd catalysts for methane combustion and CO oxidation

Zirconia supported on alumina was prepared and characterized by BET surface area, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), temperature programmed desorption (TPD), and pulse reaction. 0.2% Pd/ZrO₂/Al₂O₃ catalyst were prepared by incipient wetness impregnation of supports with aqueous solution of Pd(NO₃)₂. The effects of support properties on catalytic activity for methane combustion and CO oxidation were investigated. The results show that ZrO₂ is highly dispersed on the surface of Al₂O₃ up to 10 wt.% ZrO₂, beyond this value tetragonal ZrO₂ is formed. The presence of a small amount of ZrO₂ can increase the surface area, pore volume and acidity of support. CO–TPD results show that the increase of CO adsorption capacity and the activation of CO bond after the presence of ZrO₂ lead to the increase of catalytic activity of Pd catalyst for CO oxidation. CO pulse reaction results indicate that the lattice oxygen of support can be activated at lower temperature following the presence of ZrO₂, but it does not accelerate the activity of 0.2% Pd/ZrO₂/Al₂O₃ for methane combustion. 0.2% Pd/ZrO₂/Al₂O₃ dried at 120 °C shows highest activity for CH₄ combustion, and the activity can be further enhanced following the repeat run. The increase of treatment temperature and pre-reduction can decrease the activity of catalyst for CH₄ combustion.     

Limonene oxidation over V2O5/TiO2 catalysts

Vanadia-titania catalysts prepared by different sol–gel procedures were studied as heterogeneous catalysts for the liquid phase oxidation of limonene. The catalysts were characterized by XRD, XPS, ICP and nitrogen adsorption. According to the XRD results the catalyst samples can be divided in two different groups: anatase samples and anatase + rutile samples. XRD signals of vanadia are not found in the diffractograms.

The main reaction products are polymers. Limonene oxide, limonene glycol, carveol and carvone are obtained in small amounts. A number of autoxidation products, alcohols, aldehydes and ketones, are also obtained.

The effects of titania composition on the reaction orientation are discussed.     

The promoting effect of Nb2O5 addition to Pd/Al2O3 catalysts on propane oxidation

Pd/Nb₂O₅/Al₂O₃ catalysts were investigated on propane oxidation. Diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) analysis suggested that monolayer coverage was attained between 10 and 20 wt.% of Nb₂O₅. Temperature programmed reduction (TPR) evidenced the partial reduction of niobium oxide. The maximum propane conversion observed on the Pd/10% Nb₂O₅/Al₂O₃ corresponded to the maximum Nb/Al surface ratio. The presence of NbO_x polymeric structures near to the monolayer could favor the ideal Pd⁰/Pd²⁺ surface ratio to the propane oxidation which could explain the promoting effect of niobium oxide.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

Lean NOx reduction with CO + H2 mixtures over Pt/Al2O3 and Pd/Al2O3 catalysts

The reduction of NO_x by hydrogen under lean burn conditions over Pt/Al₂O₃ is strongly poisoned by carbon monoxide. This is due to the strong adsorption and subsequent high coverage of CO, which significantly increases the temperature required to initiate the reaction. Even relatively small concentrations of CO dramatically reduce the maximum NO_x conversions achievable. In contrast, the presence of CO has a pronounced promoting influence in the case of Pd/Al₂O₃. In this case, although pure H₂ and pure CO are ineffective for NO_x reduction under lean burn conditions, H₂/CO mixtures are very effective. With a realistic (1:3) H₂:CO ratio, typical of actual exhaust gas, Pd/Al₂O₃ is significantly more active than Pt/Al₂O₃, delivering 45% NO_x conversion at 160 °C, compared to >15% for Pt/Al₂O₃ under identical conditions. The nature of the support is also critically important, with Pd/Al₂O₃ being much more active than Pd/SiO₂. Possible mechanisms for the improved performance of Pd/Al₂O₃ in the presence of H₂+CO are discussed.     

Reactivation of sulphated Pt/Al2O3 catalysts by reductive treatment in the simultaneous oxidation of CO and C3H6

A Pt/Al₂O₃ catalyst prepared by incipient wetness impregnation was used as a diesel oxidation model catalyst and tested in the simultaneous total oxidation of CO and C₃H₆. Sulphur incorporation by wet impregnation results in deactivation of the Pt/Al₂O₃ catalyst in both oxidation reactions. Characterization of the catalysts by evolved gas analysis by mass spectrometry (EGA-MS), X-ray diffraction (XRD), isotherm of adsorbed nitrogen, X-ray photoelectron spectroscopy (XPS), infrared spectroscopy of probe molecules (pyridine and carbon monoxide) and finally temperature-programmed surface reaction (O₂-TPSR of chemisorbed CO) demonstrated that the formation of aluminium sulphate modifies the acidic properties of the support and the electronic properties of the platinum particles. Thus, new Brønsted acid sites are formed and, moreover, the capacity of the Pt particles to chemisorb CO and O₂, the latter as strongly chemisorbed O species, is seriously deteriorated. The alteration of the electronic properties of the particles (they become electronically deficient) is related to the modification of the acidic properties of the support. Treatment of the deactivated catalysts by a reductive treatment at 873 K resulted in the removal of the sulphur due to decomposition of the aluminium sulphate. Thus, the original acidic properties of the support and the electronic properties of the Pt particles were largely recovered and a high degree of catalytic reactivation was achieved.     

Modeling preferential CO oxidation over promoted Au/Al2O3 catalysts using decision trees and modular neural networks

In this work, the experimental data for CO oxidation over promoted Au/Al₂O₃ catalysts were analyzed using decision trees and modular neural networks. The full dataset was first classified by decision trees to identify and select the conditions for high catalytic activity; then the reduced dataset containing only the promising data were modeled using neural networks, at which the compositional and operating variables were processed in a modular manner to be able to model their effects together but treat them separately. It was found that operating variables were more influential on catalytic activity than catalyst compositional variables. The temperature was found to be the most significant operating variable while Mg and Mn were the best performing promoters. It was also concluded that decision trees and neural networks can complement each other to extract easily comprehensible knowledge, and they can be used for similar catalytic systems for the same purpose.     

Selective catalytic reduction of NO by hydrocarbons on Ga2O3/Al2O3 catalysts

Catalytic properties of supported gallium oxides have been examined for the selective reduction of NO by CH₄ in excess oxygen. The activity was greatly affected by the support; Ga₂O₃/Al₂O₃ (Al₂O₃ supported Ga₂O₃) and Ga₂O₃–Al₂O₃ mixed oxide exhibited high activity and selectivity as comparable to Ga-ZSM-5, while unsupported Ga₂O₃ and the other supported Ga₂O₃ were ineffective. For Ga₂O₃/Al₂O₃, the activity changed with Ga₂O₃ content, and was highest at about 30 wt% Ga₂O₃, which corresponds to a theoretical monolayer coverage. Gallium oxide highly dispersed on Al₂O₃ is considered to be responsible for the high activity and selectivity. The reaction characteristics of Ga₂O₃/Al₂O₃ were studied and compared with Ga-ZSM-5 and Co-ZSM-5. Ga₂O₃/Al₂O₃ exhibited the highest activity and selectivity at high temperature. In addition, Ga₂O₃/Al₂O₃ showed higher tolerance against water than Ga-ZSM-5. C₃H₈ and C₃H₆ were also evaluated as reducing agents, and Ga₂O₃/Al₂O₃ showed higher activity than Ga-ZSM-5 above 723 K achieving almost complete reduction of NO to N₂.     

Cu/Al2O3 catalysts for soot oxidation: Copper loading effect

Cu/Al₂O₃ catalysts with metal loading from 0.64 to 8.8 wt.% have been prepared and characterized by different techniques: N₂ adsorption at −196 °C (BET surface area), ICP (Cu loading), XRD, selective copper surface oxidation with N₂O (Cu dispersion), TPR-H₂ (redox properties), and XPS (copper surface species). The catalytic activity for soot oxidation has been tested both in air and NO_x/O₂. The activity in air depends on the amount of easily-reduced Cu(II) species, which are reduced around 275 °C under TPR-H₂ conditions. The amount of the most active Cu(II) species increases with the copper loading from Cu_1% to Cu_5% and remains almost constant for higher copper loading. In the presence of NO_x, the first step of the mechanism is NO oxidation to NO₂, and the catalytic activity for this reaction depends on the copper loading. For catalysts with copper loading between Cu_1% and Cu_5%, the catalytic activity for soot oxidation in the presence of NO_x depends on NO₂ formation. For catalysts with higher copper loading this trend is not followed because of the low reactivity of model soot at the temperature of maximum NO₂ production. Regardless the copper loading, all the catalysts improve the selectivity towards CO₂ formation as soot oxidation product both under air and NO_x/O₂.     

Reduction of NO by CO on Cu/ZrO2/Al2O3 catalysts: Characterization and catalytic activities

ZrO₂, γ-Al₂O₃ and ZrO₂/γ-Al₂O₃-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H₂, Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO₂/γ-Al₂O₃ matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO₂. Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO₂.