Preparation of M/Ce1–xTixO2 (M=Pt,Rh, Ru) from sol-gel method and their catalytic oxidation activity for diesel soot

A series of Ce_1–xTi_xO₂ mixed oxide catalysts were synthesized by sol-gel method and then loading of noble metal (M = Pt, Rh, Ru) was used for soot oxidation. Ti-doped Ce_1–xTi_xO₂ catalysts (x is the molar ratio of Ti/(Ti + Ce) and ranges from 0.1 to 0.5) exhibit much better oxidation performance than CeO₂ catalyst, and the Ce_0.9Ti_0.1O₂ catalyst calcined at 500 °C has the best catalysis activity. Each noble metal (1 wt%) was supported on Ce_0.9Ti_0.1O₂ (M/C9T1) and the properties of the catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, Brunauer–Emmett–Teller (BET) method, and H₂-temperature programmed reduction (H₂-TPR) results. Results show that the introduction of Ti into CeO₂ forming Ti-O-Ce structure enhances the catalytic activity and increases the number of oxygen vacancies at the catalyst surface. The noble metal is highly dispersed over Ce_0.9Ti_0.1O₂, and M/C9T1 catalysts present enhanced activity in comparison to Ce_0.9Ti_0.1O₂. It is found that noble metals can greatly increase the activity of the catalyst and the corresponding oxidation rate of soot can enhance the electron transfer capacity and oxygen adsorption capacity of the catalyst. A small amount of Ti doping in CeO₂ can significantly improve the activity of the catalyst, while a large amount of Ti reduces the performance of the catalyst because a large amount of Ti is enriched on the surface of the catalyst, which hinders the contact and reaction between the catalyst and the soot.     

Low-temperature catalytic combustion of trichloroethylene over MnOx-CeO2 mixed oxide catalysts

The cerium-based catalysts were investigated for the catalytic co mbustion of trichlo roethylene(TCE) and exhibit a surprising catalytic activity.MnO_x was doped into CeO₂ by a citric acid(CA) sol-gel method,and the effect of Mn content on the physicochemical properties and catalytic activities of MnO_x-CeO₂ mixed oxides was investigated systemically.The introduction of MnO_x into CeO₂ can evidently improve the catalytic activity and...     

Structure and catalytic property of CeO2-ZrO2-Fe2O3 mixed oxide catalysts for diesel soot combustion： Effect of preparation method

A series of Ce0.5Fe0.30Zr0.20O2 catalysts were prepared by different methods(co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrothermal method) and characterized by X-ray diffraction(XRD), Raman spectroscopy, Brunauer-Emmett-Teller(BET) and H2-TPR measurements. Potential of the catalysts in the soot oxidation was evaluated in a temperature-programmed oxidation(TPO) apparatus. The results showed that all the Fe3+ and Zr4+ were incorporated into ceria lattice to form a pure Ce-Fe-Zr-O solid solution for the co-precipitation sample, but two kinds of Fe phases existed in the Ce-Fe-Zr-O catalysts prepared by other methods: Fe3+ incorporated into CeO2 lattice and dispersed Fe2O3 clusters. The free Fe2O3 clusters could improve the activity of catalysts for soot oxidation comparing with the pure Ce-Fe-Zr-O solid solution owing to the synergetic effect between free Fe2O3 and surface oxygen vacancies. In addition, the activity of catalysts strongly relied on the surface reducibility of free Fe2O3 particles. Holding both abundant free Fe2O3 particles and high oxygen vacancy concentration, the hydrothermal Ce0.5Fe0.3Zr0.2O2 catalyst presented the lowest Ti(251 °C, ignition temperature of soot oxidation) and Tm(310 °C, maximum oxidation rate temperature) for soot combustion(with tight-contact between soot and catalysts) among the five samples. Even after aging at 800 °C for 10 h, the Ti and Tm were still relatively low, at 273 and 361 °C, respectively, indicating high catalytic stability.     

Effect of surface manganese oxide species on soot catalytic combustion of Ce–Mn–O catalyst

Constructing cerium and manganese bimetallic catalysts with excellent catalytic performance for soot combustion is the research frontier at present. In order to find out the key factors for catalytic soot combustion of Ce–Mn–O catalysts, a series of Ce–Mn–O catalysts with different Ce/Mn proportions were prepared by co-precipitation method. The activity test results show that it increases first and then decreases with the increase of Mn content. The best catalytic activity is obtained for Ce_0.64Mn_0.36 catalyst, which shows a maximum rate temperature (T_m) at 306 °C for CO₂ production in TPO curve. Compared with non-catalytic soot combustion, the T_m decreases by more than 270 °C. Systematical characterization results suggest that when the adsorbed surface oxygen, lattice oxygen, specific surface area and total reduction amount of the catalysts reach a certain value, the key factors leading to the difference of catalytic activity become the readily reducible and highly dispersed surface manganese oxide species and contact performance of the external surface. The surface manganese oxide species is beneficial to improving the low-temperature reducibility of catalysts and the porous surface is conducive to the contact between catalyst and soot. Furthermore, for the soot combustion reaction containing only O₂, the promoting effect of Mn⁴⁺ is not obvious.     

Rh/CeO2 composites prepared by combining dealloying with calcination as an efficient catalyst for CO oxidation and CH4 combustion

In this paper, a series of Rh/CeO₂ catalysts with three-dimensional porous nanorod frameworks and large specific surface area were prepared by chemical dealloying Al–Ce–Rh precursor alloys and then calcining in pure O₂. The effects of the Rh content and calcination temperature on CO oxidation and CH₄ combustion were studied, and the results reveal that the Rh/CeO₂ catalysts produced by dealloying melt-spun Al_91.3Ce₈Rh_0.7 alloy ribbons and then calcining at 500 °C exhibit the best catalytic activity, the reaction temperatures for the complete conversion of CO and CH₄ are as low as 90 and 400 °C, respectively. Furthermore, after 150 h of continuous testing at high concentrations of H₂O and CO₂, the nature of the catalyst is not irreversibly destroyed and can still return to its initial level of activity. This excellent catalytic activity is attributed to a portion of Rh being uniformly distributed on the CeO₂ nanorod surface in the form of nanoparticles, forming strong Rh–CeO₂ interfacial synergy. Another portion of Rh permeated into the CeO₂ lattice, which results in a significant increase in the number of oxygen vacancies in CeO₂, thus allowing more surface active oxygen to be adsorbed and converted from the gas phase. Moreover, the catalytic reaction can proceed even in an oxygen-free environment due to the excellent oxygen storage performance of the Rh/CeO₂ catalyst.     

Mechanism of CeO_2 synthesized by thermal decomposition of Ce-MOF and its performance of benzene catalytic combustion

In this paper,the formation mechanism of mesoporous CeO_2 synthesized by thermal decomposition of Ce-MOF and its performance of benzene catalytic combustion,as well as the structure-activity relationship between them were studied in depth.The self-assembly process and physicochemical properties of CeO_2 were characterized by thermogravimetry analysis,powder X-ray diffraction,N_2 adsorption/desorption,high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy techniques.Characterization results show that Ce-MOF is completely decomposed into pure mesoporous CeO_2 when the decomposition temperature is higher than 400℃.At this threshold temperature,CeO_2(400) has the largest specific surface area and pore volume of 114 m~2/g and 0.152 cm3/g,respectively.CeO_2(400) exhibits very high catalytic activity for benzene combustion,which can completely catalyze the degradation of benzene at 260℃.Meanwhile,the mesoporous CeO_2(400) supported Pt nanocrystalline catalysts were prepared by high temperature solution-phase reduction method.Pt/CeO_2(400)can completely degrade benzene at about 200℃ and represents high durability and good waterresistance for benzene combustion during 100 h of continuous reaction.     

Preparation and application of ZnO doped Pt-CeO2 nanofibers as electrocatalyst for methanol electro-oxidation

ZnO doped Pt/CeO₂ nanocomposites were prepared by electrospinning and reduction impregnation. X-ray diffraction (XRD), transmission electron microscopy (TEM), energy disperse spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the nanocomposites. It is observed that ZnO and CeO₂ form the hexagonal wurtzite phase and cubic fluorite phase in the nanocomposite, respectively, whilst Pt nanoparticles (NPs) with the number-averaged size of ca. 3.1 nm are uniformly distributed on the surface of nanofibers. The mass fraction of Pt NPs in the nanocomposites is about 10 wt%. The doping of ZnO is effective to promote reactive oxygen species, surface reaction sites and the interaction between Pt and oxides. The catalytic performance of nanocomposites was evaluated by the methanol electro-oxidation, indexed with the catalytic activity, stability of catalyst. As a result, it is found that the nanocomposite exhibits much higher activity and stability for methanol oxidation than the undoped Pt/CeO₂ catalyst.     

Catalytic combustion of VOCs on Pt/CuMnCe and Pt/CeY honeycomb monolithic catalysts

The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the deep oxidation of VOCs. In comparison with the Pt/CeY, CuMnCe, and CeY monolithic catalysts, the Pt/CuMnCe monolithic catalyst shows an excellent performance for toluene,ethyl acetate,and n-hexane oxidation and the T_(90%) is low to 216, 200 and 260 ℃,respectively. The active components Pt/PtO and CuMnCe result in a better synergetic interaction, which promote the catalyst reducibility, increase the oxygen mobility, and enhance the adsorption and activation of organic molecules.     

Catalytic wet oxidation of N,N-dimethyl formamide over ruthenium supported on CeO2 and Ce0.7Zr0.3O2 catalysts

A series of Ru supported on CeO₂ and Ce_0.7Zr_0.3O₂(CeZrO) was prepared by incipient-wet impregnation method and investigated in the catalytic wet oxidation of N,N-dimethyl formamide (DMF) in batch reactor. The physicochemical property of the catalysts was characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG). Compared with 3%Ru/CeO₂, 3%Ru/Ce_0.7Zr_0.3O₂ catalyst exhibits much higher performance for DMF degradation due to the promotion of Ru dispersion and the transfer of active oxygen, and 99% DMF conversion and 97% COD elimination are obtained at 453 K, 2.5 MPa oxygen pressure after 5 h. The reaction mechanism of DMF degradation was suggested. The carbonaceous species deposition and oxidation of Ru can be responsible for catalyst deactivation. And the catalyst activity can be recovered by air calcination and H₂ reduction.     

CeO2-x modified Ru/γ-Al2O3 catalysts for ammonia decomposition reaction

Developing high-performance ammonia decomposition catalysts for preparing CO_x-free hydrogen shows great practical significance.Herein,CeO₂ is used as a promoter to modulate the metal-support interaction to enhance the catalytic performance of Ru/Al₂O₃ catalysts.A series of 1Ru/xCe-10AI(x=0.5,1,or 3)catalysts was prepared by a facile colloidal deposition method.We find that the optimized 1 Ru/1Ce-10Al catalyst exhibits excellent activity for the decompo...     

Controllable synthesis of argentum decorated CuOx@CeO2 catalyst and its highly efficient performance for soot oxidation

In this paper, CuO_x@Ag/CeO₂ catalysts were synthesized by simple wet-chemical method and equal volume impregnation method. The obtained catalysts were subjected to soot temperature programmed oxidation (soot-TPO) activity tests and were further characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy/high-resolution transmission electron microscopy (TEM/HR-TEM), N₂ physisorption, X-ray photoelectron spectroscopy (XPS) and H₂-temperature programmed reduction (H₂-TPR). The results show that CuO_x@Ag/CeO₂ synthesized presents well controlled core-shell structures, with nano-cube like Cu₂O as the core and Ag decorated polycrystalline CeO₂ grafting layers as the shell. Such core-shell structured CuO_x@Ag/CeO₂ can successfully construct a secondary oxygen delivery channel (CuO_x → CeO₂ → Ag) to effectively transfer bulk oxygen of the catalyst to the soot, resulting in its excellent soot oxidation activity compared to CuO_x@CeO₂. The potential benefiting effect by Ag introduction over Cu@Ag/Ce can be concluded as: (i) pumping lattice oxygen and accelerating gaseous O₂ dissociation to generate significantly increased active surface oxygen content; (ii) modulating a moderate surface oxygen vacancies concentration to maintain more highly active O₂^– species.     

Lanthanum-doped Cu-Mn composite oxide catalysts for catalytic oxidation of toluene

CuMn mixed oxides catalysts doped with La were prepared following a co-precipitation method and used for the catalytic oxidation of toluene. Catalysts properties of the catalysts were investigated by X-ray diffraction, N_2 adsorption/desorption,scanning electron microscopy, H_2-temperature-programmed reduction(H_2-TPR), O_2-temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy techniques. Characterization data reveal that the phase change and decrease in crystallinity of the La-doped catalysts increase the number of oxygen vacancies. Improvements in reducibility and an increase in the amount of chemisorbed oxygen of the La-doped catalysts were also verified by H_2-TPR and O_2-TPD. The activity of the CuMn mixed oxides catalysts is significantly improved by the addition of a nominal amount of La. The CuMn/La-4 mol% catalyst exhibits the best catalytic activity, with a 90%conversion temperature of 255 ℃,attributed to a high Mn~(3+)ratio, superficial chemisorbed oxygen,and high surface area. This study indicates La to be a promising dopant for Cu-Mn catalysts toward toluene oxidation.     

A mechanic insight into low-temperature catalytic combustion toward ethylene oxide over Pt-Ru/CuCeOx bimetallic catalyst

The catalytic oxidation performance toward ethylene oxide(EO) and the consequent mechanism were investigated on the Pt-Ru/CuCeO_x bimetallic catalyst,which was prepared by a distinct method combining stepwise adsorption and subsequent impregnation.The catalytic tests show that the introduction of Ru into the Pt catalyst,so as to form Pt-Ru bimetallic active sites,can greatly increase the oxidation activity of the catalyst,as evidenced by the extremely lower full oxidation temperature(1...     

Effect of calcination process on performance of 3DOM CeMnO_3 catalysts

A series of 3DOM CeMnO_3 perovskite catalysts were prepared by poly(methyl methacrylate) hardtemplating-excessive impregnation method at calcination temperature of x℃(x=600,700,800) and the heating rate of y ℃/min(y=1,2,5,10).The samples were characterized by Brunauer-Emmett-Teller method,scanning electron microscopy,transmission electron microscopy,H_2-temperature programmed reduction,X-ray photoelectron spectroscopy,X-ray diffraction,moreover,the effect of the calcination process on the catalytic activity of the samples were discussed by the catalytic combustion of toluene.The results show that the 3DOM CeMnO_3 catalysts calcined at 600℃ promote the formation of a perovskite structure,inhibit the reduction of the Mn~(4+) species in the catalyst with high temperature.The catalyst expresses the complete macroporous structure,large specific surface area(38.8 m~2/g),higher adsorption oxygen concentration and Mn~(4+) substance concentration,with a low T_(90%)=172℃.By preparing the catalysts at different calcination heating rates,it can be concluded that the catalyst possesses a high concentration of adsorbed oxygen and a low reduction temperature and a large specific surface area(40.42 m~2/g) greatly promotes adsorption stage catalytic oxidation reaction and catalytic combustion of toluene at low temperature under the heating rate of 5℃/min.When the heating rate is 1 ℃/min,the catalyst has a complete macroporous structure(250 nm),which is beneficial to the exchange of macromolecular substances during the catalytic reaction and the catalyst has a high concentration of lattice oxygen suitable for the catalysis of toluene in high temperature flue gas combustion.     

Effect of coating modification of cordierite carrier on catalytic performance of supported NiMnO3 catalysts for VOCs combustion

NiMnO_3 perovskite catalysts supported on cordierite modified by Ce_xZr_(1-x)O_2 coatings were prepared using impregnation and sol-gel methods for catalytic combustion of single/double component VOCs at different concentrations and GHSV of 15,000 h~(-1), which were characterized by BET, XRD, SEM, FT-IR, H_2-TPR and O_2-TPD. After coating modification, the specific surface area of catalysts is improved obviously.Among the catalysts, the Ce_(0.75)Zr_(0.25)O_2 coating modified NiMnO_3 catalyst exhibits the best catalytic activity for VOCs combustion with 95.6% conversion at 275 ℃ and has stable activity when catalyst is embalmed at 800 ℃. In addition, the catalyst also presents the excellent water-resistant and conversion stability over time-on-stream condition. The reason is that Ce_(0.75)Zr_(0.25)O_2 coating can promote more lattice distortion and defects and smaller crystal size, which improve oxygen transfer capability and dispersion of active component.     

Rare earth metal modified three dimensionally ordered macroporous MnOx-CeO2 catalyst for diesel soot combustion

Three dimensionally ordered macroporous(3 DOM) Ce-based catalysts were successfully prepared via a surfactant-assisted colloidal crystal template(CCT) route. The as-synthesized catalysts showed wellordered structures with macropores and small interconnected pore windows. The Raman results indicate that the catalyst persists pure fluorite cubic phases until the molar ratio of Mn exceeds 0.3, therefore MnO_x particles form and impede the contact of the active site and the reagent and restraining soot combustion. The doping of Nd into MnO_x-CeO_2 enhances the catalytic activity because of increased oxygen vacancy, Mn~(4+)content and stronger redox ability. Nd-doping also improves thermal stability of the catalyst due to less sintering and none phase separation after thermal aging. The fresh and aged Mn_(0.3)Ce_(0.6)Nd_(0.1)O_2 catalysts show the maximum oxidation rate for soot at 331 and 355 ℃ in the O_2/N_2 atmosphere, achieving a nearly 100% CO_2 selectivity.     

Effects of precursor moisture and inert N_2 atmosphere calcinations on structure and properties of alumina modified CeZrLaNd mixed oxides

CeO_2-ZrO_2 mixed oxides are widely used in the three-way catalysts due to their unique reversible oxygen storage and release capacity. Large surface area, high oxygen storage capacity and good thermal stability of cerium zirconium mixed oxides are the key properties for the automotive catalysts so as to meet the strict emission regulations. In this work, alumina modified CeZrLaNd mixed oxides were prepared by a co-precipitation method. The effects of moisture in precursor and inert N2 atmosphere during calcinations on the structure and properties were investigated by Brunauer-Emmett-Teller(BET) surface area measurements, X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), hydrogen temperature-programmed reduction(H_2-TPR), oxygen storage capacity(OSC), Raman spectroscopy, and X-ray photoelectron spectroscopy(XPS). The results show that the moisture in precursor during calcinations increases the crystal grain size of the cerium zirconium mixed oxides, improving the thermal stability. And the aged surface area of sample after being calcined at1000 ℃ for 4 h reaches 68.8 m~2/g(5.7% increase compared with the common sample). The inert N2 atmosphere endows a great pore-enlarging effect, which leads to high fresh surface area of 148.9 m2/g(13.5% increase compared with the common sample) and big pore volume of 0.5705 mL/g. The redox and oxygen storage capacity are also improved by inert N2 atmosphere with high OSC value of 241.06μmolO_2/g(41.3% increase compared with the common calcination), due to the abundant formation of the crystal defects and oxygen vacancies.     

Double perovskite anti-supported rare earth oxide catalyst CeO_2/La_2CoFeO_6 for efficient ventilation air methane combustion

Ventilation air methane is one of available resources with a massive reserve.However,most of ventilation air methane is discharged into the air and pollutes the environment.Catalysts with high temperature resistance(>800℃)for ventilation air methane are very essential for utilization of the ventilation air methane.We mainly prepared catalysts CeO₂/La₂CoFeO₆and La₂CoFeO₆/CeO₂and comparative samples CeO₂and La₂CoFeO₆by the simple sol-gel method and calcined them under 9000C,and tested the catalytic performance of ventilation air methane combustion under the condition of 5 vol%H₂O.The experimental results show that the light-off temperature(T_1O)and complete combustion temperature(T₉₀)of the ventilation air methane combustion reaction of CeO₂/La₂CoFeO₆catalyst are 417.4 and 587.7℃,respectively.T_1Oand Tgo of La₂CoFeO₆/CeO₂only reach 425.5 and 615.8℃.The T₁₀and T_9Oof CeO₂/La₂CoFeO₆are 417.4 and 587.7℃,which are lower than those of La₂CoFeO₆[T₁₀=452.4℃and T₉₀=673.0℃)and La₂CoFeO₆/CeO₂(T₁₀=425.5℃and T₉₀=615.8℃).Therefore,the catalytic performance of the anti-supported rare earth oxide catalyst CeO₂/La₂CoFeO₆is better than that of La₂CoFeO₆and supported catalyst La₂CoFeO₆/CeO₂.     

Effect of CuO species and oxygen vacancies over CuO/CeO2 catalysts on low-temperature oxidation of ethyl acetate

The catalytic oxidation of ethyl acetate(EA) was studied over CuO/CeO₂ catalysts which were prepared by ball milling with different precursors(copper oxide,cerium acetate,cerium dioxide,copper acetate and cerium hydroxide).The CuO/CeO₂ catalyst(O-A) prepared with copper oxide and cerium acetate as precursors shows very high catalytic activity that 100% EA conversion is achieved at low temperature of 220℃.It is found that specific surface area(112.8 m²/g),particle...     

Chemical interaction of Ce-Fe mixed oxides for methane selective oxidation

Chemical interaction of Ce-Fe mixed oxides was investigated in methane selective oxidation via methane temperature programmed reduction and methane isothermal reaction tests over Ce-Fe oxygen carriers. In methane temperature programmed reduction test, Ce-Fe oxide behaved complete oxidation at the lower temperature and selective oxidation at higher temperatures. Ce-Fe mixed oxides with the Fe content in the range of 0.1–0.5 was able to produce syngas with high selectivity in high-temperature range(800–900 °C), and a higher Fe amount over 0.5 seemed to depress the CO formation. In isothermal reaction, complete oxidation occurred at beginning following with selective oxidation later. Ce1–xFexO2–δ oxygen carriers(x≤0.5) were proved to be suitable for the selective oxidation of methane. Ce-Fe mixed oxides had the well-pleasing reducibility with high oxygen releasing rate and CO selectivity due to the interaction between Ce and Fe species. Strong chemical interaction of Ce-Fe mixed oxides originated from both Fe*activated CeO2 and Ce3+ activated iron oxides(FeOm), and those chemical interaction greatly enhanced the oxygen mobility and selectivity.