Role of Surface Adsorption in Fast Oxygen Storage/Release of CeO2 -ZrO2 Mixed Oxides

Four kinds of CeO2-ZrO2 mixed oxides, i.e., a physical mixture of ceria and zirconia （CZP）, zirconia-coated ceria （ZCC）, ceria-coated zirconia （CCZ） and a chemical mixture of celia and zirconia （CZC）, were prepared. The oxygen storage capacity （OSC） measurements at 500℃ were performed under transient and stationary reaction conditions. All the curves of CO2 evolution during CO-O2 cycles presented a bimodal shape. The fast peak was primarily the result of the reaction of CO with the oxygen from the oxides, which was mainly determined by the nature of the material The sec- ond peak was mostly related to the CO2 adsorption behavior and was highly influenced by the surface area and the number of surface active sites. As a result, OSC activity of the samples followed in the order of CZC 〉 CCZ 〉 ZCC=CZP.     

Structure and oxygen storage capacity of Pd/Pr/CeO_2-ZrO_2 catalyst:effects of impregnated praseodymia

Praseodymium(Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method.The as-obtained Pr modified CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts.The structure and reducibility of the fresh and hydrothermally aged catalysts were characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),CO chemisorption and H2 temperature-programmed reduction(H2-TPR).The oxygen storage capacity(OSC) was evaluated with CO serving as probe gas.Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated.The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones.The scheme of structural evolutions of the catalysts with and without Pr was also established.Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing,which inhibited the sintering,and increased the amount of oxygen vacancies in CeO2-ZrO2 support.Furthermore,those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.     

Dynamic Oxygen Storage Capacity Measurements on Ceria-Based Material

The constant increase in the number of environ-mental protection regulations worldwide has broughtabout significant restrictions onthe nature and quantityof exhaust gases originating from mobile sources suchas automobile emissions .These increasingly dema…     

Effect of yttrium addition on water-gas shift reaction over CuO/CeO2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction (XRD), Raman spectroscopy, H2-TPR, cyclic voltammetry (CV) and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity (CO conversion reaches 93.4% at 250℃) and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak y of H2-TPR profile (I.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C2 and A1 (Cu0→Cu2+ in cyclic voltammetry process), respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.     

Effect of water vapor on the CO and CH4 catalytic oxidation over CeO2-Mox (M=Cu,Mn,Fe,Co,and Ni) mixed oxide

CeO2-MOx (M=Cu, Mn, Fe, Co, and Ni) mixed oxide catalysts were prepared by a citric acid complexation-combustion method. CeO2-MOx solid solutions could be formed with M cations doping into CeO2 lattice, while NiO and Co3O4 phases were detected on the surface of CeO2-NiO and CeO2-Co3O4 by Raman spectroscopy. The presence of M in CeO2 could obviously promote its catalytic activity for CH4 catalytic combustion and CO oxidation. Among the prepared samples, CeO2-CuO exhibited the best performance for CO oxidatio...     

Oxygen Storage Capacity of Pt-, Pd-, Rh/CeO2-Based Oxide Catalyst

CZO （CeO2-ZrO2） and CZYO （CeO2-ZrO2-Y2O3） series of mixed oxides were prepared by coprecipitaion, and a part of these oxides were loaded with precious metals （PM）. XRD, BET, and oxygen storage capacity （OSC） investigations were performed on samples aged at 750, 900, and 1050 ℃. It was observed that BET surface area and OSC showed a marked decrease in CeO2 aged at high temperature, and the erystallite size showed an obvious increase. The CZO samples consist of cubic- and tetragonal crvstal phases, and their crystallite size increase rapidly when aged at high temperature. The CZYO samples consist of single crystal phase when the content of Y exceeds 0.15 mol, and their erystallite size increases slowly during high-temperature aging. It is concluded that additive Y can stabilize the performance of CZYO oxides. In the aged CZO and CZYO mixed-oxide systems, addition of a small amount of precious metals （Pt, Pd, Rh） increased the rate of reduction and led to an obvious improvement in OSC. OSC of CZO and CZYO with precious metals are related to their composition and the type of precious metal.     

Structures and oxygen storage capacities of CeO2-ZrO2-Al2O3 ternary oxides prepared by a green route： supercritical anti-solvent precipitation

CeO2-ZrO2-Al2O3 ternary oxides were successfully prepared by a green route of supercritical anti-solvent precipitation with supercritical CO2 as anti-solvent and methanol as solvent.The structures and oxygen storage capacities of these ternary oxides were characterized by XRD,Raman spectra and oxygen storage capacity measurements.It was found that Al 3+ and Zr 4+ inserted into CeO2 lattice,forming CeO2-ZrO2-Al2O3 solid solution.The concentration of aluminium isopropoxide in the solution affected the concentration of oxygen vacancy and the distortion of oxygen sublattice which were responsible for the oxygen storage capacity.The rapidest oxygen uptake/release rate and maximum total oxygen storage capacity(122.0 mmolO2/molCeO2)were obtained with the aluminium isopropoxide concentration at 0.2 wt.% in the solution.     

Reverse water gas shift reaction over Co-precipitated Ni-CeO2 catalysts

The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.     

Synthesis of Ti-Ce-Si Binary and Ternary Nanocomposite Photocatalyst by Supercritical Fluid Drying Technology

Recently,photodegratation of various organiccontaminants with powdered semiconductors as cata-lysts has received much attention for their potential inthe utilization of light energy.TiO2is one of the mostwidely used photocatalysts due toits relatively nontox-ic,high activity,strong oxidizing property,and excel-lent stability.However,some weaknesses such as poormechanic strength,compressive strength and thermalstability have li mited its industrial applications.Therefore,it is necessary to i mp…     

A comparative study of formaldehyde and carbon monoxide complete oxidation on MnOx-CeO2 catalysts

MnOx-CeO2 composite catalysts were prepared by a coprecipitation method and tested for formaldehyde (HCHO) and carbon monoxide (CO) oxidation. X-ray photon spectroscopy (XPS) results indicated that the average oxidation state of surface Mn species in CeMn composite catalyst was higher compared to the pure MnOx. The enhancement of reactivity for HCHO oxidation was due to the activation of the lattice oxygen species in MnOx by the addition of CeO2, which was confirmed by the H2 temperature programmed reduction (H2-TPR) results. The remarkable enhancement of reactivity for CO oxidation by the addition of CeO2 was due to the active oxygen species generated on the CeO2 surface which directly participated in the reaction.     

Preparation and characteristics of nano-crystalline Cu-Ce-Zr-O composite oxides via a green route: supercritical anti-solvent process

The nano-crystalline Cu-Ce-Zr-O composite oxides were successfully prepared by the supercritical anti-solvent (SAS) process. The physicochemical properties and catalytic performances were investigated by X-ray diffraction (XRD), Raman spectroscopy, H2 temperature-programmed reduction (H2 -TPR), oxygen storage capacity (OSC) measurement and catalytic activity evaluation. It was found that Cu2+ ions incorporated into CeO2 -ZrO2 lattice to form Cu-Ce-Zr-O solid solution associated with the formation of oxygen vacancies. The Cu-Ce-Zr-O catalysts prepared via the SAS process with the Cu content 2.63 mol.% showed the highest OSC index of 636.9 μmol/g. Compared with the samples prepared by impregnation method, Cu doping using SAS process could improve the dispersion of Cu2+ in the composite oxide, enhance the interaction between Cu2+ and CeO2-ZrO2 , improve the reducibility of catalyst, and thus improve the OSC performance and increase the catalytic activity for CO oxidation at low temperature.     

Effects of La_2O_3 contents on the Pd/Ce_（0.8）Zr_（0.2）O_2-La_2O_3 catalysts for methanol decomposition

The catalytic behaviors of Pd (1.4 wt.%) catalysts supported on CeO2-ZrO2 promoted with La2O3 were investigated for methanol decomposition. The measurements of inductively coupled plasma emission spectroscopy (ICP), N2 adsorption-desorption (BET), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and oxygen storage capacity (OSC) were used to characterize the properties of catalysts. The catalysts' activities were tested in a fixed bed continuous ...     

钇掺杂对Ce0.33Zr0.67O2储氧性能的影响

采用柠檬酸溶胶凝胶法制备了一系列钇掺杂的富锆铈锆复合氧化物Ce0.33YxZr0.67-xO2,并通过XRD,BET,OSC,XPS,in-situ CO-FTIR等测试,系统研究了钇掺杂后铈锆复合氧化物储放氧性能的变化规律及其影响因素。结果表明,钇离子能够进入铈锆晶格形成固溶体,并提高铈锆体系的结构热稳定性。对于新鲜样,钇掺杂可大幅提升Ce0.33Zr0.67O2材料的比表面积,提高单位质量铈锆材料的储氧能力;但老化后,钇掺杂样品的储氧性能随着掺杂量的增加而减小。通过XPS及原位红外吸附性能测试证实,钇在Ce0.33Zr0.67O2材料表面主要取代锆离子,其掺杂会降低样品的表面吸附能力,抑制铈的氧化还原反应,从而导致该体系储氧性能的下降。     

Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

Cu-Ce-La mixed oxides were prepared by three precipitation methods （coprecipitation, homogeneous precipitation, and deposition precipitation） with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 （111） framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3＋ or Ce^4＋ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide （crystalline） and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.     

Preparation and characterization of Ce-Fe-Zr-O(x)/MgO complex oxides for selective oxidation of methane to synthesize gas

A series of Ce-Fe-Zr-O(x)/MgO(x denotes the mass fraction of Ce-Fe-Zr-O,x=10%,15%,20%,25%,30%) complex oxide oxygen carriers for selective oxidation of methane to synthesis gas were prepared by the co-precipitation method.The catalysts were characterized by means of X-ray diffraction and H2-TPR.The XRD measurements showed that MgFeO4 particles were formed and Fe2O3 particles well dispersed on the oxygen carriers.The reactions between methane diluted by argon(10% CH4) and oxygen carriers were investigated.Suitable content of CeO2/Fe2O3/ZrO2 mixed oxides could promote the reaction between methane and oxygen carriers.There are mainly two kinds of oxygen of carriers:surface lattice oxygen which had higher activity but lower selectivity,and bulk lattice oxygen which had lower activity but higher selectivity.Among all the catalysts,Ce-Fe-Zr-O(20%)/MgO exhibited the best catalytic performance.The conversion of the methane was above 56%,and the selectivity of the H2 and CO were both above 93%,the ratio of H2/CO was stable and approached to 2 for a long time.     

Effect of metal doping into Ce0.5Zr0.5O2 on catalytic activity of MnOx/Ce0.5-xZr0.5-xM0.2xOy/Al2O3 for benzene combustion

The research investigated the effect of doping two metals separately or together into Ce0.5Zr0.5O2 on the catalytic activity of MnOx/Ce0.5–xZr0.5–xM0.2xOy/Al2O3 (M=Y, Mn, Y and Mn) for catalytic combustion of benzene. The prepared catalysts were characterized by X-ray diffraction (XRD), surface area analysis, oxygen storage capacity (OSC), and H2-temperature programmed reduction (H2-TPR). Cata-lytic test was performed on a conventional fixed bed flow reactor. The characterization results revealed that Y and Mn ions entered into the ceria-zirconia mixed oxides framework, which improved the textural properties and greatly promoted the MnOx dispersion on the support surface. The complete conversion temperature of benzene on MnOx/Ce0.4Zr0.4Y0.1Mn0.1Oy /Al2O3 was 563 K, and the selectivity of carbon dioxides was 99%. This catalyst could be applied in a wide range of GHSV and wide concentration condition, showing great potential for application.     

Redox behaviors and structural characteristics of Mn0.1Ce0.9Ox and Mn0.1Ce0.6Zr0.3Ox

Mn0.1Ce0.9Ox and Mn0.1Ce0.6Zr0.30x samples synthesized by sol-gel method were tested for redox properties through the dynamic oxygen storage measurement and characterized using X-ray diffraction, BET, electron paramagnetic resonance, and X-ray photoelectron spectroscopy. The results showed that redox performances of ceria-based materials could be enhanced by synergetic effects between Mn-O and Ce-O. Fresh and aged samples were characterized with the fluorite-type cubic structure similar to CeO2, and furthermore, the thermal stability of Mn0.1Ce0.9Ox materials was improved by the introduction of some Zr atoms. From XPS, it could be concluded that Mn^2＋/Mn^3＋ redox couples existed on the surface of Mn0.1Ce0.9Ox and Mn0.1Ce0.6Zr0.3Ox samples. Electron paramagnetic resonance researches revealed that there were three types of Mn^2＋ species： isolated Mn^2＋ substituting for Ce^4＋ ions in the lattice with a cubic symmetry, ones in defect with a noncubic symmetry, and at the surface of samples.     

Structure and oxygen storage capacity of Pd/Pr/CeOe-ZrO2 catalyst： effects of impregnated praseodymia

Praseodymium （Pr） was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction （XRD）, Raman, X-ray photoelectron spectroscopy （XPS）, CO chemi- sorption and H2 temperature-programmed reduction （H2-TPR）. The oxygen storage capacity （OSC） was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.     

Effects of loading transition metal(Mn,Cr,Fe,Cu) oxides on oxygen storage/release properties of CeO_2-ZrO_2 solid solution

Cerium zirconium-based(CZ) oxygen storage materials(OSMs) play a crucial role in three-way catalysts(TWCs),while CZ needs to be modified to satisfy more rigorous emission standard.In this study,transition metal(TMs=Mn,Cr,Fe,Cu) oxides modified CZ were prepared by incipient wetness impregnation method to improve the oxygen storage capacity of CZ-based materials.To clearly illustrate the influence of TM oxides,N_2 adsorption-desorption,X-ray diffraction(XRD),oxygen storage capacity(OSC),temperature programmed reduction by H_2(H_2-TPR) and X-ray photoelectron spectroscopy(XPS) were used to characterize the physical and chemical properties of samples.It is found that,all modified CZ have higher OSC,lower reduction temperatures than those of pristine CZ.Interaction between TMOs and CZ take precedence over specific surface to influence OSC.Notably,FeO_x/CZ has the highest OSC,which is about 1.9 times that of CZ and it could be attributed to synergistic effect between FeO_x and CZ;CuO_x/CZ has the lowest reduction temperature which is 168℃lower than that of CZ,and it can be explained by hydrogen spillover effect.     

Preparation and characterization of Ce1-xFexO2 complex oxides and its catalytic activity for methane selective oxidation

A series of Ce1-xFexO2 （x=0, 0.2, 0.4, 0.6, 0.8, 1） complex oxide catalysts were prepared using the coprecipitation method. The catalysts were characterized by means of XRD and H2-TPR. The reactions between methane and lattice oxygen from the complex oxides were investigated. The characteristic results revealed that the combination of Ce and Fe oxide in the catalysts could lower the temperature necessary to reduce the cerium oxide. The catalytic activity for selective CH4 oxidation was strongly influenced by dropped Fe species. Adding the appropriate amount of Fe2O3 to CeO2 could promote the action between CH4 and CeO2. Dispersed Fe2O3 first returned to the original state and would then virtually form the Fe species on the catalyst, which could be considered as the active site for selective CH4 oxidation. The appearance of carbon formation was significant and the oxidation of carbon appeared to be the rate-determining step; the amounts of surface reducible oxygen species in CeO2 were also relevant to the activity. Among all the catalysts, Ce0.6Fe0.402 exhibited the best activity, which converted 94.52% of CH4 at 900 ℃.