Catalytic reduction of SO_2 by CO over CeO_2-TiO_2 mixed oxides

The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n（Ce）：n（Ti） is 5：5 or greater, and the most suitable n（Ce）：n（Ti） isdetermined as 7：3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 （n（Ce）：n（Ti）=7：3） without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2＋CO reaction show that CeO2 is the active component that offers the redox couple Ce4＋/Ce3＋ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.

A rationale for the development of thermally stable nanostructured CeO_2-ZrO_2-containing mixed oxides

CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.

Morphology and crystal-plane effects of Zr-doped CeO2 nanocrystals on the epoxidation of styrene with tert-butylhydroperoxide as the oxidant

The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanorods exhibited the highest catalytic performance（yield of styrene oxide and TOF value）followed by nanoparticles and nanocubes. For the Zr-doped CeOnanorods, the apparent activation energy is 56.3 k J/mol, which is much lower than the values of catalysts supported on nanoparticles and nanocubes（73.3 and 93.4 k J/mol）. The high resolution transmission electron microscopy results indicated that（100） and（110） crystal planes are predominantly exposed for Zr-doped CeOnanorods while（100）and（111） for nanocubes,（111） for nanoparticles. The remarkably increased catalytic activity of the Zrdoped CeOnanorods is mainly attributed to the higher percentage of Cespecies and more oxygen vacancies, which are associated with their exposed（100） and（110） crystal planes. Furthermore, recycling studies proved that the heterogeneous Zr-doped CeOnanorods did not lose its initial high catalytic activity after five successive recycles.

CeO_2-ZrO_2-La_2O_3-Al_2O_3 composite oxide and its supported palladium catalyst for the treatment of exhaust of natural gas engined vehicles

Composite supports CeO2-ZrO2-Al2O3（CZA） and CeO2-ZrO2-Al2O3-La2O3（CZALa） were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles （NGVs） operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction （XRD） and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperatnre-programmed reduction （H2-TPR） and oxygen storage capacity （OSC） measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.

Preferential Oxidation of Carbon Monoxide in Excess Hydrogen over Au/Co_3O_4-CeO_2 Catalysts

Au/Co3O4-CeO2 mixed-oxide catalysts were shown tion of CO in hydrogen-rich mixture. Activity was markedly experimentally to be highly active and selective for the oxidainfluenced by the composition of the support, aging temperature and Au-loading temperature. It provided that single-step removal of CO from hydrogen-rich stream both in the absence and presence of CO2 and H2O to a PEMFC tolerant level. It was found that catalytic activity is greatly affected by adding CO2 in the mixture and increased by farther adding H2O. It recants H2O has the effect to rise catalytic activity. Moreover, it shows better stability with reaction time for the preferential CO oxidation.

Preparation of M2O3-CeO2(M=La,Fe,and Al) Compoundoxide Catalyst and Its Degradation Performance

As one of the most active rare earths,CeO2 has caused extensive concern due to its multifunctional properties.CeO2-based compound oxide of M2O3-CeO2(M=La,Fe,and Al)were prepared by coprecipitation and impregnation methods.The photocatalytic performance of the samples for the degradation methylene blue was studied under UV and visible light irradiation.The effects of constituents on the properties of the CeO2-based catalysts were investigated by XRD,TEM,BET,and UV-Vis spectrophotometer.The highest degradation of methylene blue under 230W UV light was almost 100%at 50 min by La2O3/Fe2O3-CeO2/γ-Al2O3 catalyst and 99.42%at 50 min by Fe2O3-CeO2/γ-Al2O3 catalyst.The methylene blue removal efficiency under indoor natural light reaches 93.81%by La2O3/Fe2O3-CeO2/γ-Al2O3 catalyst and 92.34%by Fe2O3-CeO2/γ-Al2O3 catalyst at 50 min.The order of catalytic degradation activity is La2O3/Fe2O3-CeO2/γ-Al2O3>Fe2O3-CeO2/γ-Al2O3>La2O3-CeO2/γ-Al2O3>Al2O3,owing to their structural features.The doping of La^3+or Fe3+onto CeO2/γ-Al2O produced much more oxygen vacancies under light irradiation and reduced the energy laps of CeO2 with value of 2.86 ev,which improved the photocatalytic redox performance of the composite oxide.

Catalytic Performance of CeO_2/ZnO Nanocatalysts on the Oxidative Coupling of Methane with Carbon Dioxide and their Fractal Features

CeO2/ZnO nanocatalysts were prepared from the coupling route of homogeneous precipita-tion with microemulsion and the impregnation method. The catalytic performance of these two kinds of catalysts on the oxidative coupling of methane with carbon dioxide was tested and compared; the frac-tal behavior of the nanocatalysts was analyzed using fractal theory. The CeO2/ZnO nanocatalysts had much higher activity than the catalysts prepared by impregnation method. There was no regular relation-ship between the average size of CeO2/ZnO nanocatalysts and their catalytic performance; however, the conversion of methane increased with the increase of the fractal dimension of CeO2/ZnO nanocatalysts.

Influence of CeO2 on Properties and Activity of Oxide Catalysts in Carbon Monoxide Oxidation

A series of catalysts on the basis of 10 wt.% CuO/y-AI203, 10 wt.% CuO ＋ 10 wt.% Cr2O3/y-AI203 and 15 wt.% MnO2/y -A1203 have been prepared and modified by CeO2 with contents up to 20 wt.%. Physico-chemical properties of the catalysts were determined by the methods of BET Adsorption, XRD, and TPR. Oxidative activity of the catalysts was studied at the temperature range 90-220 ℃and CO concentration of 3 mol.%. Addition of CeO2 led to changes in physico-chemical properties of the catalysts and formation of novel active centres that increased the activity of CuO and Cr203 containing catalysts, but decreased the activity of those, containing MnO2. The catalyst sample containing 10 wt.% CuO and 15 wt.% CeO2 has been shown to be the best one for complete conversion of CO. At the given conditions on this catalyst the complete oxidation of CO to CO2 occurred at 130 ~C during more than 500 h.

Removal of Carbon Monoxide from Hydrogen-rich Fuels over CeO₂-promoted Pt/Al₂O₃

A comparative study of catalytic CO oxidation and selective CO oxidation over Pt/Al2O3 and CeO2-promoted Pt/Al2O3 catalysts has been investigated for the removal of a trace amount of CO from the reformed gas. The catalysts were prepared by sol gel and incipient wetness impregnation. CO oxidation and selective CO oxidation were carried out with a 5%Pt/Al2O3 and a 5%Pt/15%CeO2/Al2O3. The presence of 15%CeO2 inthe 5%Pt/Al2O3 dramatically improves the activities to CO oxidation and selective CO oxidation at low temperature (0℃). FTIR results indicate that CO could react with lattice oxygen from ceria and release CO2 as a product. Low space velocity would obtain high CO conversion at low temperatures while high space velocity would obtain high CO conversion at high temperatures. The results also show that a 5%Pt/15%CeO2/Al2O3 can completely oxidize 1% CO at180℃with selectivity of 52% and space velocity of70,000 cm3·g-1·h-1. Under the realistic gas feed with 1%O2, this catalyst is very stable and retains its activity and selectivity at180℃during 72 h.

Enhanced ethanol electro-oxidation on CeO_2-modified Pt/Ni catalysts in alkaline solution

Pt/Ni catalysts modified with CeO2 nanoparticles were prepared by simple composite electrodeposition of Ni and CeO2,and spontaneous Ni partial replacement by Pt processes.The as-prepared CeO2-modified Pt/Ni catalysts showed enhanced catalytic performance for ethanol electro-oxidation compared with pure Pt/Ni,and acetate species were proposed to be the main products of the oxidation when using these catalysts.The content of CeO2 in the as-prepared catalysts influenced their catalytic activity,with Pt/NiCe2（obtained from an electrolyte containing 100 mg/L CeO2 nanoparticles） exhibiting higher activity and relatively better stability in ethanol electro-oxidation.This was mainly due to the oxygen storage capacity of CeO2,the interaction between Pt and CeO2/Ni,and the relatively small contact and charge transfer resistances.The results of this work thus suggest that electrocatalysts with low price and high activity can be rationally designed and produced by a simple route for use in direct ethanol fuel cells.

Preparation and oxidation behavior of a novel CeO_2-modified chromizing coating

By using CeO2 particles instead of part of Al2O3 particles as filler, the CeO2 was successfully entrapped into the outer layer of the chromizing coatings on the as-deposited nanocrystalline （NC） and microcrystalline （MC） Ni films using a conventional pack-cementation method at 800 °C. For comparison, chromizing was also performed under the same condition on MC Ni film using Al2O3 as filler without CeO2 particles. SEM/EDX and TEM results indicate that the refinement of Ni grain and CeO2 entrapped into the chromizing coatings refine the grain of the chromizing coating. Oxidation at 900 °C indicates that compared with the CeO2-free chromizing coating, the CeO2-dispersed chromizing coating exhibits an increased oxidation resistance. For the CeO2-dispersed chromizing coating, the refinement of Ni grain size significantly decreases the transient-oxidation scaling rate of the chromizing coatings. Together with this, the CeO2-dispersed chromizing coating formed on NC Ni exhibits a better oxidation resistance.

Preparation, Characterization of CuO/CeO_2 and Cu/CeO_2 Catalysts and Their Applications in Low-Temperature CO Oxidation

CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.

Preparation of Au/CeO_2 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.

Catalytic Partial Oxidation of Methane over Ni/CeO_2-ZrO_2-Al_2O_3

Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction（XRD）,BET areas,H2 temperature-programmed reduction（H2-TPR）,and X-ray photoelectron spectroscopy（XPS）.Through the test of catalytic partial oxidation of methane（CPOM）,Ni/CeO2-ZrO2-Al2O3 displayed the highest activity,which resulted from its largest BET area and best NiO dispersion.Furthermore,Ni/CeO2-ZrO2-Al2O3 maintained a long-time stability in CPOM,which was attributed to its best coking resistance among all the prepared catalysts.

CeO_2-Co_3O_4 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 ℃.

Preparation and characterization of Cu-doped mesoporous CeO_2 for CO oxidation

Mesoporous CeO2 was first synthesized by hydrothermal method,and then used to synthesize different contents of CuO)x/CeO2(x:molar ratio of Cu to Ce) by deposition-precipitation method.These materials were characterized by X-ray diffraction(XRD),N2 adsorption and desorption,H2 temperature programmed reduction(H2-TPR) and O2 temperature programmed desorption(O2-TPD) to study the crystal structure,surface area,and the mechanism of CO oxidation.The results show that,on XRD patterns,no evidence of CuO diffraction peaks is present until Cu loading is increased to 20%.The BET surface area decreases noticeably with the increase of Cu content.Compared with other samples,the better reducibility and activity oxygen species of(CuO)10%/CeO2coincide with its better catalytic activity.

Effect of Addition of Base on Ceria and Reactivity of CuO/CeO_2 Catalysts for Low-Temperature CO Oxidation

In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction （XRD）, high resolution transmission electron microscopy （HRTEM）, and temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.

Effect of Cu Loading to Catalytic Selective CO Oxidation of CuO/CeO₂–Co₃O₄

This work studied CuO/CeO2-Co3O4 with wt% Ce:Co ratio 95:5 for selective CO oxidation with effect of? wt% Cu loading. The catalysts were prepared by co-precipitation. Characterizations of catalysts were carried out by XRD and BET techniques. The results showed a good dispersion of CuO for 5 wt% Cu loading catalysts and showed high specific surface area of catalyst. For selective CO oxidation, both 5CuO and 30CuO catalysts could remove completely CO in the presence of excess hydrogen at 423 K and 20CuO could eliminate CO completely at 443 K. Moreover, considering the selectivity to CO oxidation, the 5CuO catalyst has shown the highest selectivity of 85% while the 30CuO catalyst obtains the selectivity of 65% at the reaction temperature of 423 K.

Photo-Electrochemical Studies on TiO₂-Doped Ce (III/IV) Oxides Nanoparticles in Aqueous Electrolytes

Photoelectrochemical studies on TiO2 doped with Ce2O3 or CeO2 took place in aqueous solutions of [Fe(CN)6]4- as the source of hydrated electrons. Our studies show that doping TiO2 with CeO2 gave better photocatalytic reduction of [Fe(CN)6]3- than TiO2 doped with Ce2O3. However the TiO2 assemblies doped with either Ce(III) or Ce(IV) oxides give less photochemical reduction of [Fe(CN)6]3- that the oxides of pure metals (Ti or Ce). In both cases a lowering of the band gaps of TiO2 was noticed. Immobilized TiO2 doped with Ce oxides on a FTO (Fluorine Ten Oxide) surface gave greater photocurrent with I2/I3– than that recorded for [Fe(CN)6]3-/4- redox systems. Our studies indicate that the TiO2 doped with Ce2O3 or CeO2 maintained photoactivity after being immobilized in thin solid sheets and can be used in all solid state photoelectron-chemical cells.