Modified-EISA synthesis of mesoporous high surface area CeO_2 and catalytic property for CO oxidation

Mesoporous CeO2 particles with high surface area were synthesized using a modified evaporation-induced self assembly(EISA) method which combined citric acid as complexing agent.As-prepared powder and further thermal treatment samples were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),selected area electron diffraction(SAED),Fourier transform infrared spectrometer(FTIR),thermogravimetry and differential thermal analysis(TG-DTA),Brunauer-Emmett-Teller(BET) and Barrett-Joyner-Ha...     

Synthesis of La_xK_(1–x)CoO_3 nanorod and their catalytic performances for CO oxidation

A series of Lax K1–x CoO3 nanorod oxides with perovskite structure were synthesized by sol-gel method using polyvinyl alcohol(PVA) as additive.These perovskite-type complex oxide catalysts were characterized by the techniques of X-ray diffraction(XRD),infrared(IR),Brumauer-Emmett-Teller(BET) and scanning electron microscopy(SEM).And the results showed that nanorods of La1–x Kx CoO3 perovskite-type complex oxides were fabricated by sol-gel method when the mass concentration of PVA was 4% and the calcined temperature kept at 700 ℃ for 4 h.The catalytic results of CO oxidation showed that the Lax K1–x CoO3 catalysts had high activity.LaCoO3 nanorods exposed more {110} plane than LaCoO3 nanoparticles,which was beneficial to the catalytic oxidation of CO.LaCoO3 nanorods had the best catalytic performance for the oxidation of CO.At 200 oC,the CO conversion could reach 100%.     

Influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 for NO reduction by CO

In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO,two series of catalysts(xCuyMn/Ce and xCu/yMn/Ce) were prepared by co-impregnation and stepwise-impregnation methods,and characterized by means of X-ray diffraction(XRD),Raman spectra,H2-temperature programmed reduction(H2-TPR),in situ diffuse reflectance infrared Fourier transform spectra(in situ DRIFTS) techniques.Furthermore,the catalytic performances of these catalysts were evaluated by NO+CO model reaction.The obtained results indicated that:(1) The catalysts acquired by co-impregnation method exhibited stronger interaction owing to the more sufficient contact among each component of the catalysts compared with the catalysts obtained by stepwise-impregnation method,which was beneficial to the improvement of the reduction behavior;(2) The excellent reduction behavior was conducive to the formation of low valence state copper species(Cu+/Cu0) and more oxygen vacancies(especially the surface synergetic oxygen vacancies(SSOV,Cu+-□-Mn(4–x)+)) during the reaction process,which were beneficial to the adsorption of CO species and the dissociation of NO species,respectively,and further promoted the enhancement of the catalytic performance.Finally,in order to further understand the difference between the catalytic performances of these catalysts prepared by co-impregnation and stepwise-impregnation methods,a possible reaction mechanism(schematic diagram) was tentatively proposed.     

Catalytic Behavior of CO Oxidization over Pd/ZrO2 - CeO2 Catalyst

The effects of Pd loading, cerium content, the special surface area of the support and calcination temperature on the catalytic properties of Pd-loaded zirconia-ceria mixed oxide were studied.The results show that loading Pd and increasing cerium content in the mixed oxides can enhance the catalytic activity.There is a little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.     

Synthesis of lathanum or La-B doped KIT-6 mesoporous materials and their application in the catalytic oxidation of styrene

La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method and characterized by X-ray diffractometer(XRD),nitrogen sorption,FT-IR,UV-Vis,X-ray photoelectron spectroscopy(XPS) and ICP-AES.The catalytic performance for the oxidation of styrene by hydrogen peroxide,tert-butyl hydroperoxide or oxygen was investigated.The results showed that the introduction of heteroatoms did not destroy the mesostructure of KIT-6 with cubic Ia3d space group.La or ...     

Synthesis of Ln-doped MCM-41 mesoporous materials and their catalytic performance in oxidation of styrene

Using cetyl-trimethyl-ammonium bromide （CTMAB） as the template agent and tetraethylorthosilicate （TEOS） as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the framework under hydrothermal conditions. The structure and the state of La or Ce were investigated through the analyses of XRD, nitrogen adsorption-desorption, FT-IR, and UV-Vis. XRD and N2 adsorption-desorption results showed that Ln-MCM-41 exhibited the loss of the lattice ordering of the MCM-41 construct, and larger unit cell parameter and pore diameter than pure silica MCM-41. The FT-IR and UV-Vis results indicated the presence of isolated tetra-coordinated La or Ce ions in the framework and other Ln species dispersed highly on the Ln-MCM-41 surface simultaneously. Furthermore, their catalytic behaviors in the oxidation of styrene were studied using H2O2 as the oxidant. The La-MCM-41 catalysts exhibited high reactivity and the reactivity increased with the increase of the La content in the La-MCM-41 samples. On the contrary, Ce-MCM-41 catalysts showed low reactivity in the oxidation of styrene and the conversion of styrene decreased with the increase of the Ce content in the Ce-MCM-41 samples.     

Synthesis and Characterization of Y-Doped Mesoporous CeO2 Using A Chemical Precipitation Method

Using cetyltrimethylammonium bromide （CTAB） as the template agent, cerium nitrate as the cerium resource, yttrium nitrate as the yttrium resource, and ammonium carbonate as the precipitating agent, mesoporous CeO2 powders doped with different yttrium contents were successfully synthesized using a chemical precipitation method, under an alkalescent condition. Properties of the obtained samples were characterized and analyzed with X-ray diffraction （XRD）, energy dispersive analysis of X-rays （EDAX）, transmission electron microscopy （TEM）, infrared （IR） absorbance, and the BET method. For the prepared samples with 20% （molar ratio） Y-doped content, a BET specific surface area of 106. 6 m^2 · g^- 1, with an average pore size of3~27 nm were obtained. XRD patterns showed that the doped samples were with a cubic fluorite structure. TEM micrographs revealed that the doped samples showed a spherical morphology with a diameter ranging from 20 to 30 nm and a round pore shape. IR results indicated that the Ce-O-Ce vibration intensity decreased as the Y-doped content increased. N2 adsorption-desorption isotherms showed that the samples possessed typical mesopore characteristics. The average pore size of the samples decreased alter mesoporous CeO2 was doped with yttrium, and the average pore size decreased largely as the Y-doped content increased.     

Synergistic effects of CeO2/Cu2O on CO catalytic oxidation: Electronic interaction and oxygen defect

For CO catalytic oxidation, Cu and Ce species are of great importance, between which the synergistic effect is worth investigating. In this work, CeO₂/Cu₂O with Cu₂O {111} and {100} planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects. The activity result demonstrates that CeO₂/o-Cu₂O {111} has superior performance compared with CeO₂/c-Cu₂O {100}. Credit to the coordination unsaturated copper atoms (Cu_CUS) on o-Cu₂O {111} surface, the interfacial electronic interactions on CeO₂/o-Cu₂O {111} are more obvious than those on CeO₂/c-Cu₂O {100}, leading to richer oxygen defect generation, better redox and activation abilities of CO and O₂ reactants. Furthermore, the reaction mechanism of CeO₂/o-Cu₂O {111} on CO oxidation is revealed, i.e., CO and O₂ are adsorbed on the Cu_CUS on Cu₂O {111} and oxygen defect of CeO₂, respectively, and then synergistically promote the CO oxidation to CO₂. The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.     

Low-temperature catalytic oxidation of NO over Mn-Ce-O_x catalyst

A series of manganese-cerium oxide catalysts were prepared by different methods and used for low-temperature catalytic oxidation of NO in the presence of excess O2.Their surface properties were evaluated by means of BET and were characterized by using scanning electron microscopy(SEM) and X-ray diffractometer(XRD).The activity test of Mn-Ce-Ox catalysts showed that addition of Ce enhanced the activities of NO oxidation.The most active catalysts with a molar Ce/(Mn+Ce) ratio of 0.3 were prepared by co-precipitation method.The results showed that NO conversion reached 60% at 150 °C with a high space velocity of 50902 h-1.The effect of doping different rare earth oxides was also investigated and the addition of small amount of Ce not only increased the surface area of MnOx but also enhanced the dispersion of Mn species in the catalyst shown by BET,SEM and XRD.     

Preparation of Au/CeO2 catalyst and its catalytic performance for HCHO oxidation

Aqueous precipitation and deposition-precipitation method were used to prepare CeO2 supports and Au/CeO2 catalysts, respectively. The effect of preparation condition of support on the catalyst activity was investigated. The catalytic combustion of HCHO was considered as the probe reaction for comparing the catalyst activity. The BET, X-ray diffraction, X-ray photoelectron spectroscopy （XPS）, and reduction （TPR） were carried out to analyze the influence factor on the catalysts activity. The results showed that the addition of dispersant and use of microwave in the support preparation procedure could be beneficial for enhancing the interaction of supports and gold species and thus improved the catalytic activity. The total conversion temperature for HCHO was 146 ℃ over AC400. With the modification during supports preparation process, the catalytic activity increased with total conversion temperature decreasing to 98 ℃. The results of XPS indicated that Au^0 and Au^＋1 species coexisted in these catalysts and the activity of catalyst correlated with Au^＋1/Au^0 ratio. Temperature-programmed reduction results demonstrated that the reduction peak appeared between 100-170 ℃ with the inducing of gold. The dependence of activity on the reduction peak temperature implied that ionic gold was catalytic activity component for HCHO oxidation.     

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.     

Preparation of hierarchical layer-stacking Mn-Ce composite oxide for catalytic total oxidation of VOCs

Hierarchical layer-stacking Mn-Ce composite oxide with mesoporous structure was firstly prepared by a simple precipitation/decomposition procedure with oxalate precursor and the complete catalytic oxidation of VOCs(benzene, toluene and ethyl acetate) were examined. The Mn-Ce oxalate precursor was obtained from metal salt and oxalic acid without any additives. The resulting materials were characterized by X-ray diffraction(XRD), Brunauer-Emmett-Teller(BET), scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDX), hydrogen temperature programmed reduction(H2-TPR) and X-ray photoelectron spectroscopy(XPS). Compared with Mn-Ce composite oxide synthesized through a traditional method(Na2CO3 route), the hierarchical layer-stacking Mn-Ce composite oxide exhibited higher catalytic activity in the complete oxidation of volatile organic compounds(VOCs). By means of testing, the data revealed that the hierarchical layer-stacking Mn-Ce composite oxide possessed superior physiochemical properties such as good low-temperature reducibility, high manganese oxidation state and rich adsorbed surface oxygen species which resulted in the enhancement of catalytic abilities.     

Promotional effect of CO pretreatment on CuO/CeO2 catalyst for catalytic reduction of NO by CO

The CuO/CeO2 catalysts were investigated by means of X-ray diffraction(XRD),laser Raman spectroscopy(LRS),X-ray photoelectronic spectroscopy(XPS),temperature-programmed reduction(TPR),in situ Fourier transform infrared spectroscopy(FTIR) and NO+CO reaction.The results revealed that the low temperature(150 °C) catalytic performances were enhanced for CO pretreated samples.During CO pretreatment,the surface Cu+/Cu0 and oxygen vacancies on ceria surface were present.The low valence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation.These effects in turn led to higher activities of CuO/CeO2 for NO reduction.The current study provided helpful understandings of active sites and reaction mechanism in NO+CO reaction.     

Study on ceria-modified SnO2 for CO and CH4 oxidation

Sn-Ce-O binary catalysts with different Sn/Ce molar ratios were prepared with co-precipitation method and applied for CO and CH4 oxidation. The catalysts were characterized by means of N2-BET, XRD and H2-TPR techniques. It was found that for those Sn rich samples such as SnCe91 and SnCe73, Ce cations were doped into the matrix of tetragonal rutile SnO2 to form SnO2 -based solid solution. As a consequence, the oxidation activity as well as the thermal stability was significantly improved compared with pure SnO2 . In contrast, for Ce rich samples such as SnCe19, SnCe37 and SnCe55, though the thermal stability was improved, the activity was worse than SnO2,due to the presence of much less amount of active oxygen species. Co-precipitation was found to be the best method to prepare Sn-Ce binary catalysts among all of the methods tried in this study.     

Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane

Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.     

Low temperature catalytic oxidation of NO over different-shaped CeO2

To investigate the effect of CeO₂ nanomaterial morphology on its performance for NO catalytic oxidation. Three kinds of CeO₂ nanomaterials including CeO₂ nanorods, nanospheres and nanoparticles were prepared by hydrothermal method and used for catalytic oxidation of NO at low temperature. The experimental results show that CeO₂ nanorods are of the best catalytic performance. Characterization techniques including TEM, XRD, H₂-TPR, NO-TPD and XPS were used to determine the relationship between the morphology of CeO₂ nanomaterial and its catalytic performance. TEM images show that CeO₂ nanorods predominantly exposed (110) and (1 0 0) planes, while CeO₂ nanospheres and CeO₂ nanoparticles predominantly exposed (1 1 1) plane. The excellent catalytic performance of CeO₂ nanorods could be ascribed to the low crystallinity, high reducibility, strong NO adsorption ability and the presence of more surface chemisorbed oxygen.     

CeO2-Co3O4 Catalysts for CO Oxidation

CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （TPR）, and FT-IR, the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated. The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4. The catalyst with the Ce/Co atomic ratio 1 ： 16 exhibits the best activity, which converts 77% of CO at room temperature and completely oxidizes CO at 45 ℃.     

Catalytic performance of Zr-doped CuO-CeO_2 oxides for CO selective oxidation in H_2-rich stream

Zr-doped CuO-CeO_2 catalysts for CO selective oxidation were designed and prepared by the hydrothermal method and coprecipitation. The experimental samples were characterized by means of N_2 adsorption-desorption isotherms, powder X-ray diffraction, temperature-programmed reduction and Xray photoelectron spectroscopy. It is observed that the catalyst prepared by hydrothermal method exhibits larger specific surface area, smaller crystalline size and higher dispersion of active components compared with those of the catalyst obtained by coprecipitation. Meanwhile, redox properties of copper oxide are improved significantly and highly dispersed copper species providing CO oxidation sites are present on the surface. Furthermore, adsorptive centers of CO and active oxygen species increase on the copper-ceria interfaces. The Zr-doped CuO-CeO_2 catalyst prepared by hydrothermal method possesses superior catalytic activity and selectivity for selective oxidation of CO at low temperature compared with those of the sample prepared by coprecipitation. The temperature corresponding to 50% CO conversion is only 73 ℃ and the temperature span of total CO conversion is expanded from 120 to 160 ℃.     

Effects of water on CO catalytic oxidation over Pd/CeO_2

The role of water in CO oxidation was investigated on Pd/CeO_2 with different morphologies(rods(R),cubes(C) and octahedrons(O)).Compared with the absence of water,CO oxidation activity increases 2 times in the presence of water on Pd/CeO_2-C;but a decrease is found on Pd/CeO_2-R.Catalyst characterization reveals that Pd is mainly in the form of solid solution(Pd_xCe_(1-x)O_(2-σ)) on Pd/CeO_2-R and a mixture of metal and Pd_xCe_(1-x)O_(2-σ) solid solution on Pd/CeO_2-C.The strong interaction between Pd and CeO_2-R results in the form of stable bidentate carbonates species;while the relatively weak interaction between Pd and CeO_2-C leads to the produce of unstable monodentate carbonates species.The effects of water on CO oxidation activity closely relate with the Pd chemical state and the types of carbonates species.Water restrains CO adsorption on Pd_xCe_(1-x)O_(2-σ) solid solution,but it has negligent effects on metallic Pd species.In the presence of water,bidentate carbonates species remains stable but the decrease in the amount of monodentate carbonates species is observed.     

Catalytic oxidation of CO on mesoporous codoped ceria catalysts:Insights into correlation of physicochemical property and catalytic activity

Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts. In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe_(1-x-y)O_2,Cu_xCe_(1-x)O_2,Mn_xCe_(1-x)O_2 and pure CeO_2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD, SEM, EDS, BET, Raman, H2-TPR, XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity. The doped samples maintain the cubic fluorite structure of CeO_2 with high crystallinity and small crystallite size, forming Ce-based solid solutions. The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm. The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids. The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies, pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst, thereby enhancing the catalytic activity for CO oxidation. Besides, the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.