The influence of the active component and support nature, gas mixture composition on physicochemical and catalytic properties of catalysts for soot oxidation

Physicochemical and catalytic properties of compositions Fe(Ce)–Mn–O/support (gamma-, theta-, alpha-Al₂O₃, SiO₂ as the support) and Pt/CeO₂/theta-Al₂O₃ for oxidation of soot were characterized. It was established that the phase composition of the initial catalysts depended mainly on the nature of the active component and preparation conditions. Non-isothermal treatment of the soot–catalyst compositions at the temperature up to 1000 °C resulted in a change in the phase composition depending mainly on the final treatment temperature. The catalyst surface area was determined by the support nature. It was established that catalyst activities for oxidation of soot are determined by both catalyst nature and composition of gas mixture. The process of the soot oxidation is thought to involve oxygen from the catalyst surface. The higher proportion of weakly bound surface oxygen, the higher was the catalyst activity. An increase in the oxygen concentration from 5% O₂/N₂ to 15% O₂/N₂ is shown to lead to a decrease of the temperature of the soot oxidation. The influence of the oxygen concentration on the process of soot oxidation becomes weaker in the presence of water vapor. Results showed that the presence of NO in the gas mixture favors a decrease in the oxidation temperature of the soot, the higher being the nitrogen oxide concentration, the more pronounced effect. Introduction of SO₂ in amount of 50 ppm in the gas mixture has no noticeable effect on the process of the soot oxidation. Among the catalysts under study, Fe–Mn–K–O/gamma-Al₂O₃ is most effective to oxidation of the soot at otherwise identical conditions.     

Comparative Study of the Decomposition of CCl4 in Cold and Thermal Plasma

Decomposition of carbon tetrachloride was studied in an inductively coupled thermal plasma reactor and in a low temperature, non-equilibrium plasma reactor, in neutral and oxidative conditions, respectively. In neutral conditions formation of solid soot, aliphatic- and cyclodienes was observed in equilibrium, and products, such as Cl₂ and C₂Cl₆ were detected in non-equilibrium plasma. Feeding of oxygen into the thermal plasma reactor depressed both soot and dienes formation and induced the formation of oxygen containing intermediates and products. GC-MS analyses of the gaseous products and the extract of the soot referred to as complex decomposition and recombination mechanism at given conditions. Presence of oxygen in the low temperature plasma reactor results in the formation of carbonyl compounds as intermediers. CO₂ and Cl₂ revealed as final products of CCl₄ decomposition in cold plasma.     

Role of nitrogen dioxide in the oxidation of diesel soot on promoted mixed catalysts with fluorite and perovskite structures

The oxidation of soot on catalysts with the perovskite and fluorite structures (including platinum-promoted catalysts) in the presence and in the absence of NO₂ was studied using in situ IR spectroscopy and temperature-programmed techniques (TPR, TPD, and TPO). It was found that, as a rule, the temperature of the onset of soot oxidation considerably decreased upon the addition of NO₂ to a flow of O₂/N₂, whereas the amount of oxygen consumed in soot oxidation considerably increased. To explain these facts, we hypothesized that the initiation of soot combustion in the presence of NO₂ was related to the activation of the NO₂ molecule through the formation (at a low temperature) and decomposition (at a high temperature) of nitrate structures on the catalyst. Superequilibrium amounts of NO₂ resulted from the decomposition of nitrate complexes immediately on the catalyst for soot combustion. Based on a comparison between catalyst activities and data obtained by TPR and the TPD of oxygen, a conclusion was drawn that the presence of labile oxygen in the catalyst is a necessary but insufficient condition for the efficient occurrence of a soot oxidation reaction in the presence of NO₂. The introduction of platinum as a constituent of the catalyst increased the amount of labile oxygen and, as a consequence, increased the amount of highly reactive nitrate complexes. As a result, this caused a decrease in the temperature of the onset of soot combustion.     

三维有序大孔SnO2基固溶体用于有效燃烧碳烟颗粒

柴油车尾气排放的碳烟颗粒对人类的生存环境和身体健康带来了严重危害.催化燃烧是消除碳烟颗粒污染的有效途径.碳烟颗粒催化燃烧是固-固-气相反应,因此催化剂本身具有活泼的氧中心且其能与碳烟颗粒有效接触是提高反应效率的关键因素.为改善碳烟颗粒与催化剂的接触,设计制备三维有序大孔(3DOM)催化剂,使碳烟颗粒可以进入催化剂孔道内部,增加其与催化剂的有效接触,是提高反应活性的有效途径.此外,在催化剂晶格中掺杂其它金属离子形成固溶体结构,可提高其氧化还原性能,也可有效提高其碳烟燃烧活性.SnO2富含活泼的表面缺位氧和可还原的晶格氧,且其熔点高达1630 oC,具有良好的热稳定性,被广泛用于制备气体传感、电化学和催化等材料.在过去的6年中,本课题组在SnO2催化化学领域做了大量系统的工作,将SnO2基催化材料用于多种环保和能源反应.发现通过其它阳离子Fe3+,Cr3+,Ta5+,Ce4+和Nb5+等的掺杂,替换晶格中部分Sn4+形成金红石型SnO2固溶体结构,可显著提高催化剂氧物种的流动性、活性和本身的热稳定性.本文采用胶体晶体模板法制备出了Ce4+,Mn3+和Cu2+离子掺杂的SnO2三维有序大孔固溶体催化剂用于松散接触条件下的碳烟催化燃烧.采用SEM,TEM,XRD,STEM-mapping,O2-TPD和XPS等手段对催化剂进行表征,研究其碳烟催化燃烧性能.SEM和TEM结果表明已成功合成三维有序大孔结构样品.XRD,Raman和STEM-mapping结果表明,Ce4+,Mn3+和Cu2+离子均进入四方金红石型SnO2晶格形成固溶体结构.另外,Raman,H2-TPR,XPS和O2-TPD等结果发现上述离子掺杂三维大孔SnO2后,催化剂表面形成了更活泼、丰富的氧物种,有利于碳烟颗粒燃烧.其中3DOM-Cu1Sn9催化剂具有最丰富的活泼氧中心,因此表现出最高的活性.     

Characterization and reactivity with NO/O2 of the soot formed in the pyrolysis of acetylene–ethanol mixtures

Characterization analyses and soot–O₂ and soot–NO interaction experiments have been performed for soot samples obtained in the pyrolysis of acetylene–ethanol mixtures at different temperatures from 1275 to 1475 K. The objective of these analyses is to address the influence of soot formation conditions on soot properties and structure, as well as on its capability to interact with gaseous compounds.The characterization techniques used are: elemental analysis, transmission electron microscopy (TEM), Brunnauer–Emmett–Teller (BET) surface area analysis, Raman spectroscopy and X ray diffraction (XRD). The characterization of soot samples is useful to increase the database on soot composition and structure and may help to find a dependence of those characteristics with soot formation conditions and the fuel from which soot is formed. From these data it can be observed a certain degree of graphitization for the soot samples formed at higher temperatures and/or from fuel mixtures with a higher content in ethanol.The interaction of soot with NO and O₂ is investigated in order to analyze the capability of soot to interact with gas reactants. Soot samples formed at the highest temperatures are less reactive towards O₂ and NO than those formed at lower temperatures. Soot samples appear to be more reactive when the fuel mixture presents a lower initial volume of ethanol. These observations can be related to the higher C/H ratio, associated to slightly higher degree of ordering, for the soot samples formed in such conditions. Experimental results have also demonstrated that soot samples are more reactive towards O₂ than NO, although the initial concentration of O₂ is lower.     

Diesel Soot Combustion over Mn2O3 Catalysts with Different Morphologies: Elucidating the Role of Active Oxygen Species in Soot Combustion

Catalytic diesel soot combustion was examined using a series of Mn₂O₃ catalysts with different morphologies, including plate, prism, hollow spheres and powders. The plate‐shaped Mn₂O₃ (Mn₂O₃‐plate) exhibited superior carbon soot combustion activity compared to the prism‐shaped, hollow‐structured and powdery Mn₂O₃ under both tight and loose contact modes at soot combustion temperatures (T₅₀) of 327 °C and 457 °C, respectively. Comprehensive characterization studies using scanning electron microscopy, scanning transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, temperature‐programmed reduction and oxygen release measurements, revealed that the improved activity of Mn₂O₃‐plate was mainly attributed to the high oxygen release rate of surface‐adsorbed active oxygen species, which originated from oxygen vacancy sites introduced during the catalyst preparation, rather than specific surface‐exposed planes. The study provides new insights for the design and synthesis of efficient oxidation catalysts for carbon soot combustion as well as for other oxidation reactions of harmful hydrocarbon compounds.     

铈基复合氧化物催化碳烟燃烧的性能及其H2-TPR研究

采用溶胶-凝胶法或浸渍法制备了不同金属离子掺杂的铈基复合氧化物催化剂,并采用热重法考察其催化碳烟燃烧的活性,借助H₂-TPR(程序升温还原)手段探讨了催化剂氧化还原性对碳烟燃烧性能的影响. 结果表明,过渡金属的掺杂促使催化剂在低温下提供更多的表面氧和晶格氧,显著降低了碳烟的氧化温度,催化剂于200~400℃释放的活性氧数量对于碳烟燃烧性能提高至关重要; 而结构性助剂金属、碱金属或碱土金属的掺入可提高中温活性氧数量,虽然对碳烟起燃温度无明显改善,但加快了碳烟的燃烧速率.     

Preparation of Cerium-Bismuth Oxide Catalysts for Diesel Soot Oxidation Including Evaluation of an Automated Soot-Catalyst Contact Mode

Cerium-bismuth oxides have emerged as promising candidates for Diesel soot oxidation. The catalysts are synthesized via automated co-precipitation methods. T₅₀ values, where 50 % of soot is oxidized, and the dynamic oxygen storage capacity (OSC_dyn) are used to compare the catalytic activity. The activity is measured by thermogravimetric methods. The synthesized catalysts are characterized through powder X-ray diffraction (PXRD), Raman spectroscopy, and specific surface area (S_BET) measurements. This work investigates the influence of the contact mode between soot and catalyst. The literature-known manual contact modes “loose”, “tight”, and “wet” are compared with our developed automated contact mode, using a dual asymmetric centrifuge. The rotation speed rs and mixing time t_M have been varied independently. Both factors influence the T₅₀ value. A continuous transition from loose to tight contact mode with increasing rotation speed rs can be shown. Furthermore, the automated contact mode shows better reproducibility behavior compared to manual contact modes.     

Environmental Transmission Electron Microscopy Study of Diesel Carbon Soot Combustion under Simulated Catalytic‐Reaction Conditions

Environmental transmission electron microscopy (ETEM) is used to monitor the catalytic combustion of diesel carbon soot upon exposure to molecular oxygen at elevated temperatures by using a gas‐injection specimen heating holder. The reaction conditions simulated in the ETEM experiments reconstruct real conditions effectively. This study demonstrated for the first time that soot combustion occurs at the soot–catalyst interface for both Ag/CeO₂ and Cu/BaO/La₂O₃ catalysts.     

In-situ UV-Raman study on soot combustion over TiO2 or ZrO2-supported vanadium oxide catalysts

UV-Raman spectroscopy was used to study the molecular structures of TiO₂ or ZrO₂-supported vanadium oxide catalysts. The real time reaction status of soot combustion over these catalysts was detected by in-situ UV-Raman spectroscopy. The results indicate that TiO₂ undergoes a crystalline phase transformation from anatase to rutile phase with the increasing of reaction temperature. However, no obvious phase transformation process is observed for ZrO₂ support. The structures of supported vanadium oxides also depend on the V loading. The vanadium oxide species supported on TiO₂ or ZrO₂ attain monolayer saturation when V loading is equal to 4 (4 is the number of V atoms per 100 support metal ions). Interestingly, this loading ratio (V₄/TiO₂ and V₄/ZrO₂) gave the best catalytic activities for soot combustion reaction on both supports (TiO₂ and ZrO₂). The formation of surface oxygen complexes (SOC) is verified by in-situ UV Raman spectroscopy and the SOC mainly exist as carboxyl groups during soot combustion. The presence of NO in the reaction gas stream can promote the production of SOC.     

Effect of pretreatment conditions on the catalytic activity of coprecipitated Ce<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript> catalyst in soot oxidation

The temperature of soot oxidation and efficiency of Ce_0.5Zr_0.5O₂ catalyst depends on its morphology, which determines the area of intergranular contact between the solid substrate and the catalyst. The temperature-programmed reduction in hydrogen to 1000°C and oxidation at 500°C (redox cycles) cause the mobility of oxygen in oxide to be enhanced and decrease the temperature of soot combustion. Oxidation of soot in the air flow on the Ce_0.5Zr_0.5O₂ catalyst result in its activation. Reuse of the catalyst decreases the temperature of soot oxidation.     

Ceria–Zirconia Particles Wrapped in a 2D Carbon Envelope: Improved Low‐Temperature Oxygen Transfer and Oxidation Activity

Engineering the interface between different components of heterogeneous catalysts at nanometer level can radically alter their performances. This is particularly true for ceria‐based catalysts where the interactions are critical for obtaining materials with enhanced properties. Here we show that mechanical contact achieved by high‐energy milling of CeO₂–ZrO₂ powders and carbon soot results in the formation of a core of oxide particles wrapped in a thin carbon envelope. This 2D nanoscale carbon arrangement greatly increases the number and quality of contact points between the oxide and carbon. Consequently, the temperatures of activation and transfer of the oxygen in ceria are shifted to exceptionally low temperatures and the soot combustion rate is boosted. The study confirms the importance of the redox behavior of ceria‐zirconia particles in the mechanism of soot oxidation and shows that the organization of contact points at the nanoscale can significantly modify the reactivity resulting in unexpected properties and functionalities.     

Dynamics simulation and reaction pathway analysis of characteristics of soot particles in ethylene oxidation at high temperature

Soot particles characteristics were investigated numerically for high temperature oxidation of C₂H₄/O₂/N₂ (C/O ratio of 2.2) in a closed jet-stirred/plug-flow reactor (JSR/PFR) system. Based on the growth mechanism of polycyclic aromatic hydrocarbons (PAHs), two mechanisms were used to explore the formation pathways of soot precursors and soot. Numerical results were compared with the experimental and reference data. The simulation results show that the value predicted for small molecule intermediates within A1 gives a strong regularity, consistent trend with reference data. However, with the hydrogen-abstraction-carbon-addition (HACA) growth mechanism, the predicted value for beyond-A1 PAH macromolecules and soot volume fraction are smaller than the experimental data. The results also show that the predicted soot volume fraction is in good agreement with experimental data when a combination of the HACA and PAHs condensation (HACA + PAH-PAH) growth mechanisms is used. Analyses of the A1 sensitivity and reaction pathway elucidated that A1 are mainly formed from C₂H₃, C₂H₂, C₃H₃, C₆H₅OH, A1C₂H and A1-. The reaction 2C₃H₃ → A1 is the dominant route of benzene formation. The prediction results and an analysis of the A3 reaction pathway indicate that the growth process from benzene to larger aromatic hydrocarbons (beyond two-ring polycyclic aromatic hydrocarbons [PAHs]) goes by two pathways, i.e., HACA combined with the PAH-PAH radical recombination and addition reaction growth mechanisms.     

NO2 measurement artifacts in the presence of soot

Nitrogen dioxide is a regulated pollutant, which is measured routinely. Since it can be formed during combustion processes, it is often measured in the presence of soot. This study investigates the possible artifact formation due to the interaction of soot and NO₂ in the sampling lines and instrument prefilters. The transfer of varying NO₂ concentrations through filters and tubes coated with different kinds of soot was investigated by using a dedicated photoacoustic soot and NO₂ analyzer (TwinPAS). The effects of flow rate, temperature, relative humidity, tubing respectively filter material, soot reactivity, and passivation on the NO₂ measurement artifacts have been investigated. We found significant lags (up to 2 min) of the NO₂ transfer as well as total NO₂ losses of up 10 %.     

Benefits of <Emphasis Type="Italic">n</Emphasis>-butanol,as a biofuel,in reducing the levels of soot precursors issued from the combustion of benzene flames

Although oxygenated fuel additives are effective in reducing soot emissions, the extent to which molecular structure of the oxygenate plays a role in soot reduction has remained unclear and controversial. To gain a deeper insight in this field, a detailed chemical kinetic modeling approach was used to examine the phenomenon of suppression of sooting by the addition of oxygenated hydrocarbon species to the fuel. For this task, the PREMIX code in conjunction with Chemkin II and models resulting from the merging of validated kinetic schemes describing the oxidation of the components of the n-butanol-benzene mixtures were used to investigate the effect of n-butanol addition on the formation?depletion of acetylene recognized as soot precursor in flames under fuel-rich conditions. The first part of this study treats the dependence of the soot precursor amounts on n-butanol percentage in the fuel mixture, whereas the second part defines the key reaction mechanisms responsible for the observed reduction in C₂H₂ and consequently in polycyclic aromatic hydrocarbons and soot amounts induced by the oxygenate additive. The principal objective of the current study was to obtain fundamental understanding of the mechanisms through which the oxygenate compound affects the soot precursor amounts. The modeling results indicated that there was a dramatic decrease in the acetylene peak height with the addition of the oxygenated addtitive. This finding was found to be due to the increase in the C₂H₂ consumption rates induced by n-butanol addition. Finally, the modeling results provided evidence that n-butanol played a role in changing acetylene formation mechanism by enhancing the role of C₃H₄P, C₃H₄ and aC₃H₅ and by eliminating the role of C₆H₄, C₅H₅, C₅H₆, H₂CCCCH, C₄H₂, C₅H₄O, C₂H, CHCHCHO, H₂C₄O and C₄H₄.     

Photocatalytic Removal of Soot: Unravelling of the Reaction Mechanism by EPR and in situ FTIR Spectroscopy

Photocatalytic soot oxidation is studied on P25 TiO₂ as an important model reaction for self‐cleaning processes by means of electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) spectroscopy. Contacting of carbon black with P25 leads on the one hand to a reduction of the local dioxygen concentration in the powder. On the other hand, the weakly adsorbed radicals on the carbon particles are likely to act as alternative traps for the photogenerated conduction‐band electrons. We find furthermore that the presence of dioxygen and oxygen‐related radicals is vital for the photocatalytic soot degradation. The complete oxidation of soot to CO₂ is evidenced by in situ FTIR spectroscopy, no intermediate CO is detected during the photocatalytic process.     

Simultaneous effect of carbon and water on NOx adsorption on a stabilized Pt–Ba/Al2O3 catalyst

The influence of the presence of H₂O on the contact between carbon, used as model soot, and a model four-way catalyst (1% Pt–10% BaO/Al₂O₃) was investigated. NO_x adsorption/TPD cycles at 300 °C together with XRD, XPS and DRIFTS characterizations showed that only surface nitrate species are destabilized by the carbon present in the catalytic bed, leading to a decrease of the NO_x storage capacity and carbonate species formation. In another way, injection of water in the reactive gas flow decreases also the NO_x storage capacity of the catalyst, but promotes the formation of stable nitrate species. A non-cumulative effect of carbon and water was observed. It was proposed that a competition between the destabilization, by carbon, of weakly bonded surface nitrate species and the enhancement of bulk nitrate species formation in the presence of water occurs.     

Redox and Catalytic Properties of Copper Molybdates with Various Composition

Using XRD and temperature-programmed reduction (TPR), phase and structural transformations of copper molybdates Cu₃Mo₂O₉ and CuMoO₄ were investigated in the course of their treatment with hydrogen, carbon monoxide or soot. The catalytic properties of copper molybdates Cu₃Mo₂O₉ and CuMoO₄ were studied in model oxidation reactions of carbon monoxide and soot. Phase and structural transformations of the molybdates, in particular formation of Cu_4–xMo₃O₁₂ and Cu₆Mo₅O₁₈ phases, was shown to have a significant impact on the formation of active state of the catalysts in the model reactions considered.     

Decomposition of Chlorobenzene by Thermal Plasma Processing

Decomposition of chlorobenzene as a model molecule of aromatic chlorinated compounds was studied in radiofrequency thermal plasma both in neutral and oxidative conditions. Optical emission spectroscopy was applied for the evaluation of the plasma excitation and molecular rotational-vibrational temperature. Atomic (C, H, O) and molecular (CH, OH, C₂) radicals were identified, while the morphology of the formed soot was characterized by electron microscopy. Organic compounds adsorbed on the surface of the soot after plasma processing were comprised of various polycyclic aromatic hydrocarbons (PAH) and chlorinated PAH molecules. Their amount was greatly affected by experimental conditions, especially the oxygen content and plate power. The higher input power reduced the ring number of the PAH molecules. Addition of oxygen significantly reduced the amount of both PAHs chlorinated PAH molecules but enhanced the formation of polychlorinated benzene compounds.