Catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

A series of MnOx–CeO₂ mixed oxide catalysts with different compositions prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of volatile organic compounds of chlorinated aromatics. MnOx–CeO₂ catalysts with different ratios of Mn/Ce + Mn were found to possess high catalytic activity in the catalytic combustion of CB, and MnOx(0.86)–CeO₂ was identified as the most active catalyst, on which the temperature of complete combustion of CB was 254 °C. Effects of systematic variation of reaction conditions, including space velocity and inlet CB concentration on the catalytic combustion of CB were investigated. Additionally, the stability and deactivation of MnOx–CeO₂ catalysts were studied by various characterization methods and other assistant experiments. MnOx–CeO₂ catalysts with high Mn/Ce + Mn ratios present a stable high activity, which is related to their high ability to remove the adsorbed Cl species and a large amount of active surface oxygen.     

Soot combustion activity of NOx-sorbing Cs–MnOx–CeO2 catalysts

Activities of Cs-loaded MnO_x–CeO₂ for combustion of model diesel soot (carbon black) and sorptive NO uptake have been studied. MnO_x–CeO₂ is a pseudo-solid solution having redox properties favorable for soot oxidation. The addition of Cs not only lowered the temperature of soot ignition (T_i), but also increased oxidative NO_x adsorption to form nitrate on the surface. Soot ignition over Cs–MnO_x–CeO₂ was further promoted in a stream of NO/O₂, presumably because nitrate on the surface plays a role of an oxidizing agent. Soot ignition started just before sharp desorption of NO_x, suggesting that adsorbed nitrate species would directly interact with soot.     

Low-temperature catalytic combustion of methane over MnO x –CeO2 mixed oxide catalysts: Effect of preparation method

The effect of preparation method on MnO _x –CeO₂ mixed oxide catalysts for methane combustion at low temperature was investigated by means of BET, XRD, XPS, H₂-TPR techniques and methane oxidation reaction. The catalysts were prepared by the conventional coprecipitation, plasma and modified coprecipitation methods, respectively. It was found that the catalyst prepared by modified coprecipitation was the most active, over which methane conversion reached 90% at a temperature as low as 390 °C. The XRD results showed the preparation methods had no effect on the solid solution structure of MnO _x –CeO₂ catalysts. More Mn⁴⁺ and richer lattice oxygen were found on the surface of the modified coprecipitation prepared catalyst with the help of XPS analysis, and its reduction and BET surface area were remarkably promoted. These factors could be responsible for its higher activity for methane combustion at low temperature.     

Ceria modified MnOx/TiO2 as a superior catalyst for NO reduction with NH3 at low-temperature

A series of cerium modified MnOx/TiO₂ catalysts were prepared by sol–gel method and used for low-temperature selective catalytic reduction (SCR) of NOx with ammonia. The experimental results showed that NO conversion could be improved by doping Ce from 39% to 84% at 80 °C with a gas hourly space velocity (GHSV) of 40,000 h⁻¹. This activity improvement may be contributed to the increase of chemisorbed oxygen and acidity after Ce doping. TPR results also verified that the redox property of Ce modified MnOx/TiO₂ was enhanced at low-temperature.     

CO hydrogenation to iso-C4 hydrocarbons over CeO2–TiO2 catalysts

CeO₂–TiO₂ (Ce:Ti = 0.25–9, molar ratio) catalysts were synthesized by a sol–gel method and the catalytic performances were evaluated in the selective synthesis of isobutene and isobutane from CO hydrogenation under the reaction conditions of 673–748 K, 1–5 MPa and 720–3000 h⁻¹. The physical properties, such as specific surface area, cumulative pore volume, average pore diameter, crystal phase and size, of the catalysts were characterized by N₂ adsorption/desorption and XRD. All the CeO₂–TiO₂ composite oxides showed higher surface areas than pure TiO₂ and CeO₂. No TiO₂ phase was detected on the samples of CeO₂–TiO₂ in which TiO₂ contents were in the range of 10–50 mol%. Crystalline Ce₂O₃ was detected in CeO₂–TiO₂ (8:2). The reaction conditions, temperature, pressure and space velocity, had obvious influences on the CO conversion and distribution of the products over CeO₂–TiO₂ (8:2) catalyst.     

SOx storage and release kinetics for ceria-supported platinum

The SO_x storage and release kinetics on CeO₂ have been studied by lean SO_x adsorption and temperature programmed desorption for different pairwise configurations of individual monolith samples, i.e., Pt/CeO₂ + SiO₂, Pt/SiO₂ + CeO₂, CeO₂ + Pt/SiO₂ and CeO₂ + SiO₂. In the case of sole ceria, SO_x adsorption proceeds both via SO₂ and SO₃ adsorption although the latter channel is kinetically favored. Hence, the rate of SO₂ oxidation is crucial for the overall SO_x storage kinetics. It is also found that physical contact between Pt and ceria is important for the storage process. This is attributed to efficient transport routes for SO_x (surface diffusion and spill-over processes) and/or specific adsorption sites at the platinum–ceria interface. The main route for SO_x release is found to be thermal decomposition where the effect of platinum is minor, although an indirect effect cannot be ruled out. Different mechanistic scenarios for SO_x adsorption are discussed, which may serve as a guide for future experiments.     

Structure characterization and mechanical properties of CeO2–ZrO2 solid solution system

The measured and calculated lattice parameters, microstructures, and mechanical properties (fracture toughness and microhardness) of CeO₂–ZrO₂ system ceramics are investigated, using CeO₂–ZrO₂ solid solution powder prepared by a microwave-induced combustion process. The CeO₂–ZrO₂ solid solution ceramics were sintered at 1500 °C for 6 h in air; the density of all specimens was greater than 94% of the theoretical density. For Ce_1−xZr_xO₂ (0.00  x  0.50), the measured lattice parameter is in accordance with that of Kim's doped CeO₂ model_. On the other hand, for x  0.50, the measured values fit Kim's doped ZrO₂ model. The fracture toughness and microhardness of CeO₂–ZrO₂ system ceramics with various compositions were investigated with Vickers indentation. The results showed that the crack mode of CeO₂–ZrO₂ solid solution was Palmqvist cracks under loads of 1 kg. Generally, the fracture toughness should increase with grain size at the submicron scale. However, larger grains may lead to spontaneous transformation, which should decrease the potential toughening at room temperature. This behavior was observed in the Ce_0.25Zr_0.75O₂ ceramic, which demonstrated a high fracture toughness that may be ascribed to two causes: (1) fine grain size and (2) transformation toughening.     

Low-temperature catalytic combustion of methane over Pd/CeO2 prepared by deposition–precipitation method

Ceria supported 2 wt% Pd catalysts for low-temperature methane combustion were prepared by the impregnation (IM) and deposition–precipitation (DP) methods, which are denoted as Pd–IM and Pd–DP, respectively. DP was found to be an available method for achieving high activity and stability of the Pd/CeO₂ catalyst. The temperatures for methane ignition (T_10%) and total conversion (T_100%) over Pd–DP are 224 and 300 °C at GHSV of 50,000 h⁻¹, which are 83 and 110 °C lower than the corresponding temperatures of Pd/Al₂O₃. X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) analyses show that palladium species in Pd–DP is highly dispersed, positively charged and difficultly reduced. Raman spectra disclosed that the largest concentration of defects and/or oxygen vacancies was formed in Pd–DP catalyst. A kind of cationic PdO^δ+ sites with higher binding energies than PdO are in close vicinity to the oxygen vacancies in the CeO₂ support and might act as the active centers for methane oxidation. Furthermore, the deactivation and steam aging tests for Pd–DP showed that the performance of this type of palladium was very stable and could be repeatedly recovered after several long time aging tests.     

A comparative study of the selective oxidation of NH3 to N2 over gold, silver and copper catalysts and the effect of addition of Li2O and CeOx

This paper describes the selective oxidation of ammonia into nitrogen over copper, silver and gold catalysts between room temperature and 400 °C using different NH₃/O₂ ratios. The effect of addition of CeO_x and Li₂O on the activity and selectivity is also discussed. The results show that copper and silver are very active and selective toward N₂. However the multicomponent catalysts: M/Li₂O/CeO_x/Al₂O₃ (M: Au, Ag, Cu) perform the best. On all three metal containing catalysts the activity and selectivity is influenced by the particle size and the interaction between metal particles and support.     

Preparation of Ceria-Zeolite Catalysts by Different Techniques and Its Effect on Selective Catalytic Reduction of NO with NH3 at High Space Velocities

Several zeolite-based catalysts containing Ce³⁺ and/or CeO₂ were prepared by a variety of catalyst preparation techniques like ion exchange, solid-state ion exchange, impregnation and physical mixing and are characterised. Selective catalytic reduction was evaluated using simulated exhaust gas containing NO _x , NH₃, O₂ and H₂O at high space velocities (>180000 h^–1) in the temperature window 150–600 °C. The activity and selectivity in NO _x reduction was found to strongly depend on the charge compensating ions, crystallite size of the zeolite and CeO₂ content in the catalyst. CeO₂ mixed with zeolite having H⁺ or Ce³⁺ co-cations showed benificial effect and increased the NO _x conversion and selectivity. Among the different zeolite materials studied, the structure and the strength and amount of Brønsted acidity did not influence the NO _x conversion.     

Activity of oxygen reduction reaction on small amount of amorphous CeOx promoted Pt cathode for fuel cell application

Pt on ceria (CeO_x) particles supported on carbon black (CB) were synthesized using the combined process of hot precipitation and impregnation methods. During 30 cycles of cyclic voltammetry pre-treatment in the potential ranging from −0.2 to 1.3 V (V vs. Ag/AgCl), it was observed that a small amount of CeO_x, which consisted of the interface region between Pt and CeO_x, remained on Pt particles. Other free CeO_x particles were dissolved into H₂SO₄ aqueous solution. To develop the Pt-CeO_x/CB catalyst, the surface chemical states, the net chemical composition, morphology and electrochemical behavior in H₂SO₄ aqueous solution were characterized. Our microanalysis and electrochemical analysis indicate that the active CeO₂ with high specific surface area provides the continuous amorphous cerium oxide (Ce³⁺, Ce⁴⁺) layer with pores on the surface of Pt particles. It is concluded that the amorphous cerium oxide layer on Pt inhibits the oxidation of Pt surface and contributes to enhancement of the activity on Pt cathode. The single cell performance was also improved using the Pt-CeO_x/CB cathode. Based on all data, it is expected that the design based on characterization of the interface between Pt and small amount of amorphous cerium oxide layer could help in preparation of more active Pt catalyst.     

Influence of composition of MgAl2O4 supported NiCeO2ZrO2 catalysts on coke formation and catalyst stability for dry reforming of methane

Dry reforming of methane was studied over Ni catalysts supported on γAl₂O₃, CeO₂, ZrO₂ and MgAl₂O₄ (670 °C, 1.5 bar, 16–20 l CH₄ ml_catalyst⁻¹ h⁻¹). It is shown that MgAl₂O₄ supported Ni catalysts promoted with both CeO₂ and ZrO₂ are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO₂ and ZrO₂ has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline Ce_xZr_1−xO₂ mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO₂ fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.     

Oriented polycrystalline mesoporous CeO2 with enhanced pore integrity

Mesoporous CeO₂ particles are synthesized using a sol–gel method involving Pluronic P123 or F127 tri-block copolymer and cerium acetate hydrate. Transmission electron microscopy reveals well defined meso-channels of about 10 nm in diameter and a wall framework consisting of highly oriented polycrystalline CeO₂. The [0 0 1] axis of the crystals is found to be aligned parallel to the meso-channels, and lattice coherency of [1 0 0] or [0 1 0] also exists in perpendicular plane to the channel. A cooperative self-assembly of the tri-block copolymer and Ce⁴⁺ species is believed to occur, along with the precipitation of nano-crystalline CeO₂ in the sol–gel process. It is proposed that the preferential orientation may result from a favored linkage of the low-order Miller indices {0 0 1} planes of CeO₂ to the PEO segment in the PEO–PPO–PEO tri-block copolymer micelles. The unique structural characteristics of meso-CeO₂ appear to contribute to maintaining the pore integrity during the synthesis as well as in a post-fabrication in situ TEM heating test.     

Preferential oxidation of CO in excess hydrogen over a nanostructured CuO–CeO2 catalyst with high surface areas

CuO–CeO₂ is prepared by coprecipitation and ethanol washing and characterized using BET, HR-TEM, XRD and TPR techniques. The results show that CuO–CeO₂ is nanosized (r_TEM = 6.5 nm) and possesses high surface area (S_BET = 138 m² g⁻¹). Furthermore, some lattice defects in the surface of CuO–CeO₂ are found, which are beneficial to enhance catalytic performance of CuO–CeO₂ in preferential oxidation of CO in excess hydrogen (PROX). Consequently, the nanostructured CuO–CeO₂ exhibits perfect catalytic performance in PROX. Namely, CO content can be lowered to less than 100 ppm at 150 °C with 100% selectivity of O₂ in the presence of 8% CO₂ and 20% H₂O at .     

Effects of precursors on the surface Mn species and the activities for NO reduction over MnOx/TiO2 catalysts

TiO₂-supported manganese oxide catalysts were prepared from two different precursors, manganese nitrate (MN) and manganese acetate (MA), and these samples were characterized by BET, XRD, TG/DTA, XPS and FT–IR. The characterization results showed that the MN precursor resulted primarily in MnO₂, accompanied with some Mn-nitrate, while the MA precursor caused mainly Mn₂O₃ species. These two different precursors also led to different surface Mn atom concentrations indicated by XPS and NH₃ adsorption. Consequently, the higher low-temperature activity of MnO_x/TiO₂ from MA precursor was attributed to higher surface Mn concentration and the surface Mn₂O₃ species.     

Morphology-dependent redox and catalytic properties of CeO2 nanostructures: Nanowires, nanorods and nanoparticles

The redox features and the catalytic activities of ceria nanowires, nanorods and nanoparticles were comparatively studied. The morphology-dependent phenomenon is closely related to the nature of the exposed crystal planes. The CeO₂ nanoparticles mainly expose the stable {1 1 1} plane on the surface, whereas the rod-shaped nanostructures preferentially expose the reactive {1 1 0} and {1 0 0} planes, giving higher oxygen storage capacity and catalytic activity for CO oxidation. Although both the CeO₂ nanorods and the CeO₂ nanowires predominantly expose the reactive {1 1 0} and {1 0 0} planes, the CeO₂ nanowires favor to expose a large proportion of active planes on the surface, resulting in a much higher activity for CO oxidation than the nanorods.     

Synthesis of Highly Effective CeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>–MnO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>–BaO Catalysts for Direct NO Decomposition

Abstract  

Ce–Mn mixed oxides with a Mn/(Ce + Mn) molar ratio of 0.25 were prepared by solvothermal (ST-1) and co-precipitation (CP) methods, and Ba was loaded on the Ce–Mn oxides. In addition, CeO₂–MnO _x –BaO catalysts with various compositions were directly prepared by the solvothermal (ST-2) method. The NO decomposition activities of these catalysts were examined. Among the catalysts examined, the ST-2 catalyst having a nominal composition of Ce_0.8Mn_0.15Ba_0.05O _x exhibited the highest activity; 77% NO conversion to N₂ was attained at 800 °C. These catalysts were characterized by X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The Raman and XPS results indicate that the CP catalyst had larger amounts of the BaMnO_3-δ and/or Mn₃O₄ phases. The ST-1 and ST-2 catalysts had highly dispersed Ba species on the surface. The ST-2 catalyst had Mn species with the lowest binding energy of Mn 2p and also had a high population of oxygen vacancies in the ceria lattice, suggesting that Mn species with a low oxidation state contributes to the formation of oxygen vacancies, which play an important role in this reaction.     

In situ DRIFTS study of the effect of structure (CeO2–La2O3) and surface (Na) modifiers on the catalytic and surface behaviour of Pt/γ-Al2O3 catalyst under simulated exhaust conditions

The nature and relative populations of adsorbed species formed on the surface of un-promoted and sodium-promoted Pt catalysts supported either on bare Al₂O₃ or CeO₂/La₂O₃-modified Al₂O₃, were investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under simulated automobile exhaust conditions (CO + NO + C₃H₆ + O₂) at the stoichiometric point. The DRIFT spectra indicate that interaction of the reaction mixture with the Pt/Al₂O₃ catalyst leads mainly to formation of formates and acetates on the support and carbonyl species on partially positively charged Pt atoms (Pt^δ+). Although enrichment of Al₂O₃ with lanthanide elements (CeO₂ and La₂O₃) does not significantly modify the carboxylate species formed on the support, it causes significant modification of the oxidation state of Pt, as indicated by the appearance of a substantial population of carbonyl species on reduced Pt sites (Pt⁰–CO). This modification of the Pt component is enhanced when Na-promotion is used, leading to formation of carbonyl species only on electron enriched Pt (i.e., fully reduced Pt⁰ sites) and to the formation of NCO on these Pt entities (2180 cm⁻¹). The latter are thought to result from enhanced NO dissociation at Na-modified Pt sites. These results correlate well with observed differences in the catalytic performance of the three different systems.     

Ceria–zirconia-supported rhodium catalyst for NOx reduction from coal combustion flue gases

The catalytic activities of ceria–zirconia mixed oxides Ce_xZr_1−xO₂ (x = 0.17, 0.62 and 0.8) rhodium catalysts were determined by isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion. Results show that all supports are active in deNO_x reaction in the presence of the mentioned gas mixture. However, their catalytic activity varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NO_x consumption. The effect of rhodium on Ce_0.62Zr_0.38O₂ considerably improves the catalytic activity during the deNO_x process assisted by hydrocarbons. The rhodium addition decreases by about 34 °C the temperature of NO_x consumption, which goes up to 57%. A mechanism of hydrocarbon (HC) assisted reduction of NO is proposed on ceria–zirconia-supported rhodium catalysts. This mechanism is divided in three catalytic cycles involving (i) the oxidation of NO into NO₂, (ii) the reaction of NO₂ and the hydrocarbons leading to RNO_x species and C_xH_yO_z, and finally (iii) the decomposition of NO assisted by these latter C_xH_yO_z species.     

Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.