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. Acco...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.展开更多
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...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.展开更多
ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered d...ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.展开更多
Samples of cerium-manganese oxides supported on modified glass-fiber with different Ce/Mn molar ratios （Ce-Mn/GF） were prepared by an impregnation method and tested for low-temperature （80 180 ℃） selective cataly...Samples of cerium-manganese oxides supported on modified glass-fiber with different Ce/Mn molar ratios （Ce-Mn/GF） were prepared by an impregnation method and tested for low-temperature （80 180 ℃） selective catalytic reduction （SCR） of NO with ammonia. This brand-new technology could remove NO and particles matter from coal-fired flue gas. The surface properties of the catalysts were examined by means of Bmnauer-Emmett-Teller （BET）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and scanning electron microscopy （SEM）. The experimental results showed that the catalyst with a Ce/Mn molar ratio of 0.2 obtained high activity of 87.4% NO conversion at 150 ℃ under a high space velocity of 50000 h1. Deactivation poisoned by SO2 still occurred, but the Ce-Mn/GF（0.2） catalyst performed desirable tolerance to SO2 with decreasing 50% in 40 min and then maintaining at about 30% NO conversion. Characterization results indicated that the excellent low-temperature catalytic activity was related to the high specific surface area, pore structure, and amorphous phase.展开更多
CeO2-ZrO2-MnOx mixed oxide series were prepared by sol-gel method. CO pulse and CO-O2 cycle measurements were carried out to examine the oxygen storage complete capacity （OSCC） and dynamic oxygen storage capacity （...CeO2-ZrO2-MnOx mixed oxide series were prepared by sol-gel method. CO pulse and CO-O2 cycle measurements were carried out to examine the oxygen storage complete capacity （OSCC） and dynamic oxygen storage capacity （OSC） of the samples. The doping method brought about strong interactions between manganese oxide and ceria, both in the bulk and on the surface. Only a small part of Mn cations are incorporated into the ceria lattice to form solid solutions and the remaining are left on the surface as finely dispersed Mn3O4. The OSC behaviors of the materials are influenced by the doping amount of Mn and the solubility of Mn in the CeO2 lattice. The OSC is more easily affected by available contents of oxygen storage components when the measurement frequency is low. Comparatively, the concentration of lattice defects, which affects the mobility of bulk oxygen, is the determining factor under high frequency.展开更多
A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption （BET）, X-ray diffraction （XRD）, l...A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption （BET）, X-ray diffraction （XRD）, laser Raman spectrum （LRS）, and temperature programmed reduction （TPR） techniques. The XRD and LRS results confirmed the high dispersion of active components or formation of solid solution between manganese and cerium oxides in the bulk and on the surface of mixed oxide catalysts. The reducibility was remarkably promoted by the stronger synergistic interaction between the two oxides from H2-TPR measurements. As expected, all the experimental mixed oxide catalysts showed excellent activity for methane combustion at low temperature. Especially, for the catalyst with Mn-Ce ratio 3：7, methane conversion reached 92% at a temperature as low as 470 ℃.展开更多
We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete diesel combustion. Here, we proposed that ceria（CeO2）-based catalysts could lower the temperature a...We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete diesel combustion. Here, we proposed that ceria（CeO2）-based catalysts could lower the temperature at which soot combustion occurred from 610 oC to values included in the operation range of diesel exhausts（270–400 oC）. Here, we used the sol-gel method to synthesize catalysts based on mixed oxides（ZnO：CeO2） deposited on cordierite substrates, and modified by ruthenium nanoparticles. The presence of ZnO in these mixed oxides produced defects associated with oxygen vacancies, improving thermal stability, redox potential, sulfur resistance, and oxygen storage. We evaluated the morphological and structural properties of the material by X-ray diffraction（XRD）, Brumauer-emmett-teller method（BET）, temperature programmed reduction（H2-TPR）, scanning electron microscopy（SEM）, and transmission electron microscopy（TEM）. We investigated how the addition of Ru（0.5 wt.%） affected the catalytic activity of ZnO：CeO2 in terms of soot combustion. Thermogravimetric analysis（TG/DTA） revealed that presence of the catalyst decreased the soot combustion temperature by 250 oC, indicating that the oxygen species arose at low temperatures, which was the main reason for the high reactivity of the oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy（DRS） showed that the catalyst containing Ru on the mixed oxide-impregnated cordierite samples efficiently oxidized soot in a diesel stationary motor： soot emission decreased 80%.展开更多
Ceria-zirconia based mixed oxides(CZs)have been applied in three-way catalysts(TWCs)for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0....Ceria-zirconia based mixed oxides(CZs)have been applied in three-way catalysts(TWCs)for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0.12)O_(2)mixed oxides was realized via a facile and scalable approach,namely,sulfateaided coprecipitation method was labelled as CZ-S.Sulfate ion(SO_(4)^(2-))was added into raw solution in the form of sulfuric acid and acted as coordination agent.The control sample was prepared by conventional coprecipitation method without sulfuric acid added and labelled as CZ.The promotion effect of sulfate ion was analyzed systematically by X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),N_(2)adsorption-desorption,Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),OSC and hydrogen temperatureprogrammed reduction(H_(2)-TPR)analysis.XRD and high resolution TEM results reveal that CZ-S have homogeneous distributions of elements.TEM and SEM images show that fresh samples of CZ-S have narrower distributions of grain sizes and larger pore sizes than those of CZ.Through cross analysis of structure and morphology of CZ and CZ-S,we find that the introduction of sulfate ions results in uniform distributions of elements,narrows distributions of grain sizes,and enables the formation of secondary loose packing of sub-particles,which lead to enhanced thermal stability of the samples of CZ-S upon aging process at high temperature.After aging treatment at 1100℃for 10 h,aged samples of CZ-S present larger specific surface areas and pore volumes than the aged sample prepared by conventional coprecipitation method without sulfate ions added.Furthermore,the aged sample of CZ-S2(SO_(4)^(2-)/Zr=1)possesses the highest specific surface area of 21.9 m2/g and the biggest pore volume of 0.035 mL/g among all aged samples.展开更多
A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxi...A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxides.The catalyst with a Co/Cr molar ratio of 1:2(1 Co2 Cr)and a spinel structure has the best activity(with a reaction rate of 1.38μmol g^–1 s^–1 at 250℃),which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility,as evidenced by the temperature-programmed desorption of ammonia,reduction of hydrogen,and surface reaction of propane.Kinetic study shows that the reaction orders of propane and oxygen on the 1 Co2 Cr catalyst(0.58±0.03 and 0.34±0.05,respectively)are lower than those on the 2 Co1 Cr catalyst(0.77±0.02 and 0.98±0.16,respectively)and 1 Co5 Cr(0.66±0.05 and 1.30±0.11,respectively),indicating that the coverages of propane and oxygen on 1 Co2 Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility.In addition,in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1 Co2 Cr during the reaction are polydentate carbonate species,which accumulate on the surface at low temperatures(<250℃)but decompose at relatively high temperatures.展开更多
Mesoporous cerium-zirconium mixed oxides were prepared by hydrothermal method using cetyl trimethyl ammonium bromide (CTAB) as template. The effects of amount of template, pH value of solution and hydrothermal tempera...Mesoporous cerium-zirconium mixed oxides were prepared by hydrothermal method using cetyl trimethyl ammonium bromide (CTAB) as template. The effects of amount of template, pH value of solution and hydrothermal temperature on mesostructure of samples were systematically investigated. The final products were characterized by XRD, TEM, FT-IR, and BET. The results indicate that all the cerium-zirconium mixed oxides present a meso-structure. At molar ratio of n(CTAB)/n((Ce)+(Zr))= 0.15, pH value of 9, and hydrothermal temperature of 120 ℃, the samples obtained possess a specific surface area of 207.9 m2/g with pore diameter of 3.70 nm and pore volume of 0.19 cm3/g.展开更多
Due to the oxygen storage and release properties,cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts.To reveal the effects of co-precipitation temperature on structure,ph...Due to the oxygen storage and release properties,cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts.To reveal the effects of co-precipitation temperature on structure,physical and chemical properties of multi-doped cerium zirconium mixed oxides,a series of La and Y doped cerium zirconium mixed oxides(CZLYs)were synthesized via a co-precipitation method,and the physical and chemical properties of CZLYs were systemically characterized by XRD,N_(2) adsorption−desorption,TEM,XPS,oxygen storage capacity(OSC)and hydrogen temperature programmed reduction(H_(2)-TPR).The results show that co-precipitation temperature is an important parameter to influence the crystal size,oxygen storage capacity and thermal stability of CZLYs.When the co-precipitation temperature was 60℃,the best redox properties and thermal stability of CZLYs were obtained.After thermal treatment at 1100℃for 10 h,the specific surface area and oxygen storage capacity of the corresponding aged sample were 15.42 m^(2)/g and 497.7μmol/g,respectively.In addition,a mechanism was proposed to reveal the effects of co-precipitation temperature on the structure and properties of CZLYs.展开更多
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 temp...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~）.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 oc- curred at beginning following with selective oxidation later. Ce~_xFexO2~ oxygen carriers （x5_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 selec- tivity 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.展开更多
Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. T...Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria （CeO2） makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610℃ to values included in the diesel exhausts operation range （300-450℃）. The sol-gel method was used to synthesize mixed oxide-based catalysts （CeO2：ZnO）; the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric （TG/DTA） analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200℃ on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy （DRS） showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor： soot emission decreased by more than 70%.展开更多
Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effe...Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.展开更多
The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation.In this work,we found that ZnO-CuO mixed oxides supported gold...The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation.In this work,we found that ZnO-CuO mixed oxides supported gold catalysts showed much better catalytic activity for base-free aerobic oxidation of benzyl alcohol than Au/ZnO and Au/CuO catalysts,and among them Au/Zn0.7Cu0.3O displayed the best catalytic performance.In addition,the Au/Zn0.7Cu0.3O catalyst could selectively catalyze the aerobic oxidation of a wide range of alcohols to produce the corresponding carbonyl compounds with high yields under mild conditions without base.Further characterizations indicated that the outstanding catalytic performance of Au/Zn0.7Cu0.3O was correlated with the small size of Au nanoparticles(NPs),good low-temperature reducibility,high concentration of surface oxygen species,and collaborative interaction between Au NPs and mixed oxide.展开更多
The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have...The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have been correlated with the surface electron donor properties of these mixed oxides展开更多
The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability...The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.展开更多
A series of CexPr1-xO2-δ (x=0, 0.5, 0.9, 1.0) mixed oxide calcined at different temperatures were synthesized by sol-gel method and characterized by Raman, XRD and O2-TPD techniques. When x=0.9, only a cubic phase Ce...A series of CexPr1-xO2-δ (x=0, 0.5, 0.9, 1.0) mixed oxide calcined at different temperatures were synthesized by sol-gel method and characterized by Raman, XRD and O2-TPD techniques. When x=0.9, only a cubic phase CeO2 is observed. When x=0.5, the compound was combined by Pr6O11 and CeO2 mixed oxides. For CexPr1-xO2-δ (x=0.5, 0.9)samples 465 cm-1 Raman peak is attributed to the Raman active F2g mode of CeO2. The broad peak at about 570 cm-1 can be linked to lattice defects resulting in oxygen vacancies. The crystallite size of the samples increased as increasing the calcined temperature. But the increased value of Ce0.9Pr0.1O2-δ and Ce0.5Pr0.5O2-δ is smaller than single CeO2 and Pr6O11 obviously. It reveals that the insertion of Pr atom into the ceria lattice could enhance the sintering resistance and thermal stability of the mixed oxides. Calcination temperatures had great effect on the peak intensity for CeO2 but less effect on Ce0.8Pr0.2O2-δ in Raman spectra, and it may be caused by the colors transformation of the mixed oxides. The result of O2-TPD experiment indicates that the formation of solid solution has elevation the stabilization and thermal stability of the mixed oxides.展开更多
A series of cerium zirconium mixed oxides were prepared by two co-precipitation methods using magnesium hydrogen carbonate （MHC） and mixed ammonia-ammonia hydrogen carbonate （AAHC） as precipitant respectively. The...A series of cerium zirconium mixed oxides were prepared by two co-precipitation methods using magnesium hydrogen carbonate （MHC） and mixed ammonia-ammonia hydrogen carbonate （AAHC） as precipitant respectively. The crystal structure, BET surface area and morphology of the produced cerium zirconium mixed oxides were characterized by X-ray diffraction （XRD）, Bru- mauer-Emmett-Teller （BET） and scanning electron microscopy （SEM） techniques. The reduction-oxidation behavior and oxygen storage capacity （OSC） performance were also studied by temperature programmed reduction （TPR） and oxygen pulse chemical adsorption methods. The XRD results demonstrated that the cerium zirconium mixed oxides obtained by both methods possessed struc ture of cubic solid solution phase. The fresh surface area calcinated at 600 ℃, aged surface area after 1000 ℃and OSC at 500 ℃ of cerium zirconium mixed oxides were determined to be 89.337, 34.784 ma/g, and 567 pmol O2/g for MHC method and 122.010, 46.307 m2/g, and 665 pmol O2/g for AAHC method, respectively.展开更多
To enhance the hydrogen release during hydrogen storage,several Pt-Ir supported on Mg-Al mixed oxide catalysts were prepared and then applied into the dehydrogenation of methylcyclohexane(MCH)in this study.The effects...To enhance the hydrogen release during hydrogen storage,several Pt-Ir supported on Mg-Al mixed oxide catalysts were prepared and then applied into the dehydrogenation of methylcyclohexane(MCH)in this study.The effects of iridium content,reduction temperature on the activity and stability of the catalysts were studied in detail.In the presence of Ir,metal particle size was decrea sed and electron transfer between Ir and Pt was observed.High reduction temperature increased the metallic Ir content but enlarged the particle size of active site s.During the dehydrogenation reaction on Pt-Ir bimetallic catalyst,MCH was efficiently converted into toluene and PtIr-5/Mg-Al-275 exhibited the highe st activity.After prolonging the residence time and raising the reaction temperature to 350℃the conversion and hydrogen evolution rate were increased to 99.9%and 578.7 mmol·(g Pt)^-1·min^-1,respectively.Moreover,no carbon deposition was observed in the spent catalyst,presenting a high anti-coking ability and good potential for industrial application.展开更多
文摘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.
基金PRIN 2006, "Caratterizzazione spettroscopica e morfologica di Me-POSS eterogeneizzati", MEL Chemicals
文摘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.
基金Project(21306041)supported by the National Natural Science Young Foundation of ChinaProject(21271071)supported by the National Natural Science Foundation of ChinaProject(15A076)supported by the Scientific Research Foundation of Hunan Provincial Education Department of China
文摘ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.
基金Project supported by the National High Technology Research and Development Program of China(863 Program)(2008AA05Z305)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry(201109)+2 种基金the Master Dissertation Innovation Funded Projects(EG2013015)the Fundamental Research Funds for the Central Universities Special Fund Project(11D11315)Program of Shanghai Subject Chief Scientist(14XD1424700)
文摘Samples of cerium-manganese oxides supported on modified glass-fiber with different Ce/Mn molar ratios （Ce-Mn/GF） were prepared by an impregnation method and tested for low-temperature （80 180 ℃） selective catalytic reduction （SCR） of NO with ammonia. This brand-new technology could remove NO and particles matter from coal-fired flue gas. The surface properties of the catalysts were examined by means of Bmnauer-Emmett-Teller （BET）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and scanning electron microscopy （SEM）. The experimental results showed that the catalyst with a Ce/Mn molar ratio of 0.2 obtained high activity of 87.4% NO conversion at 150 ℃ under a high space velocity of 50000 h1. Deactivation poisoned by SO2 still occurred, but the Ce-Mn/GF（0.2） catalyst performed desirable tolerance to SO2 with decreasing 50% in 40 min and then maintaining at about 30% NO conversion. Characterization results indicated that the excellent low-temperature catalytic activity was related to the high specific surface area, pore structure, and amorphous phase.
基金Project supported by the National "973"Project (2004CB719503)Project supported by the National Natural ScienceFoundation of China (50502023)
文摘CeO2-ZrO2-MnOx mixed oxide series were prepared by sol-gel method. CO pulse and CO-O2 cycle measurements were carried out to examine the oxygen storage complete capacity （OSCC） and dynamic oxygen storage capacity （OSC） of the samples. The doping method brought about strong interactions between manganese oxide and ceria, both in the bulk and on the surface. Only a small part of Mn cations are incorporated into the ceria lattice to form solid solutions and the remaining are left on the surface as finely dispersed Mn3O4. The OSC behaviors of the materials are influenced by the doping amount of Mn and the solubility of Mn in the CeO2 lattice. The OSC is more easily affected by available contents of oxygen storage components when the measurement frequency is low. Comparatively, the concentration of lattice defects, which affects the mobility of bulk oxygen, is the determining factor under high frequency.
基金supported by the New Century Excellent Talent Project of China (NCET-05-0783)
文摘A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption （BET）, X-ray diffraction （XRD）, laser Raman spectrum （LRS）, and temperature programmed reduction （TPR） techniques. The XRD and LRS results confirmed the high dispersion of active components or formation of solid solution between manganese and cerium oxides in the bulk and on the surface of mixed oxide catalysts. The reducibility was remarkably promoted by the stronger synergistic interaction between the two oxides from H2-TPR measurements. As expected, all the experimental mixed oxide catalysts showed excellent activity for methane combustion at low temperature. Especially, for the catalyst with Mn-Ce ratio 3：7, methane conversion reached 92% at a temperature as low as 470 ℃.
基金Project supported by the National Council for Scientific and Technological Development(CNPq)(105477/2012-5)
文摘We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete diesel combustion. Here, we proposed that ceria（CeO2）-based catalysts could lower the temperature at which soot combustion occurred from 610 oC to values included in the operation range of diesel exhausts（270–400 oC）. Here, we used the sol-gel method to synthesize catalysts based on mixed oxides（ZnO：CeO2） deposited on cordierite substrates, and modified by ruthenium nanoparticles. The presence of ZnO in these mixed oxides produced defects associated with oxygen vacancies, improving thermal stability, redox potential, sulfur resistance, and oxygen storage. We evaluated the morphological and structural properties of the material by X-ray diffraction（XRD）, Brumauer-emmett-teller method（BET）, temperature programmed reduction（H2-TPR）, scanning electron microscopy（SEM）, and transmission electron microscopy（TEM）. We investigated how the addition of Ru（0.5 wt.%） affected the catalytic activity of ZnO：CeO2 in terms of soot combustion. Thermogravimetric analysis（TG/DTA） revealed that presence of the catalyst decreased the soot combustion temperature by 250 oC, indicating that the oxygen species arose at low temperatures, which was the main reason for the high reactivity of the oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy（DRS） showed that the catalyst containing Ru on the mixed oxide-impregnated cordierite samples efficiently oxidized soot in a diesel stationary motor： soot emission decreased 80%.
基金Project supported by Beijing Nova Program(Z181100006218030)。
文摘Ceria-zirconia based mixed oxides(CZs)have been applied in three-way catalysts(TWCs)for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0.12)O_(2)mixed oxides was realized via a facile and scalable approach,namely,sulfateaided coprecipitation method was labelled as CZ-S.Sulfate ion(SO_(4)^(2-))was added into raw solution in the form of sulfuric acid and acted as coordination agent.The control sample was prepared by conventional coprecipitation method without sulfuric acid added and labelled as CZ.The promotion effect of sulfate ion was analyzed systematically by X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),N_(2)adsorption-desorption,Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),OSC and hydrogen temperatureprogrammed reduction(H_(2)-TPR)analysis.XRD and high resolution TEM results reveal that CZ-S have homogeneous distributions of elements.TEM and SEM images show that fresh samples of CZ-S have narrower distributions of grain sizes and larger pore sizes than those of CZ.Through cross analysis of structure and morphology of CZ and CZ-S,we find that the introduction of sulfate ions results in uniform distributions of elements,narrows distributions of grain sizes,and enables the formation of secondary loose packing of sub-particles,which lead to enhanced thermal stability of the samples of CZ-S upon aging process at high temperature.After aging treatment at 1100℃for 10 h,aged samples of CZ-S present larger specific surface areas and pore volumes than the aged sample prepared by conventional coprecipitation method without sulfate ions added.Furthermore,the aged sample of CZ-S2(SO_(4)^(2-)/Zr=1)possesses the highest specific surface area of 21.9 m2/g and the biggest pore volume of 0.035 mL/g among all aged samples.
基金financially supported by the National Natural Science Foundation of China(21773212,21872124)~~
文摘A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxides.The catalyst with a Co/Cr molar ratio of 1:2(1 Co2 Cr)and a spinel structure has the best activity(with a reaction rate of 1.38μmol g^–1 s^–1 at 250℃),which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility,as evidenced by the temperature-programmed desorption of ammonia,reduction of hydrogen,and surface reaction of propane.Kinetic study shows that the reaction orders of propane and oxygen on the 1 Co2 Cr catalyst(0.58±0.03 and 0.34±0.05,respectively)are lower than those on the 2 Co1 Cr catalyst(0.77±0.02 and 0.98±0.16,respectively)and 1 Co5 Cr(0.66±0.05 and 1.30±0.11,respectively),indicating that the coverages of propane and oxygen on 1 Co2 Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility.In addition,in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1 Co2 Cr during the reaction are polydentate carbonate species,which accumulate on the surface at low temperatures(<250℃)but decompose at relatively high temperatures.
基金Project(CHCL0501) supported by Hubei Provincial Open Fund of Key Laboratory of Catalytic Material Science and Technology
文摘Mesoporous cerium-zirconium mixed oxides were prepared by hydrothermal method using cetyl trimethyl ammonium bromide (CTAB) as template. The effects of amount of template, pH value of solution and hydrothermal temperature on mesostructure of samples were systematically investigated. The final products were characterized by XRD, TEM, FT-IR, and BET. The results indicate that all the cerium-zirconium mixed oxides present a meso-structure. At molar ratio of n(CTAB)/n((Ce)+(Zr))= 0.15, pH value of 9, and hydrothermal temperature of 120 ℃, the samples obtained possess a specific surface area of 207.9 m2/g with pore diameter of 3.70 nm and pore volume of 0.19 cm3/g.
基金the Hebei Key Research and Development Program,China(No.20374202D)the Hebei High Level Talent Team Building,China(No.205A1104H).
文摘Due to the oxygen storage and release properties,cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts.To reveal the effects of co-precipitation temperature on structure,physical and chemical properties of multi-doped cerium zirconium mixed oxides,a series of La and Y doped cerium zirconium mixed oxides(CZLYs)were synthesized via a co-precipitation method,and the physical and chemical properties of CZLYs were systemically characterized by XRD,N_(2) adsorption−desorption,TEM,XPS,oxygen storage capacity(OSC)and hydrogen temperature programmed reduction(H_(2)-TPR).The results show that co-precipitation temperature is an important parameter to influence the crystal size,oxygen storage capacity and thermal stability of CZLYs.When the co-precipitation temperature was 60℃,the best redox properties and thermal stability of CZLYs were obtained.After thermal treatment at 1100℃for 10 h,the specific surface area and oxygen storage capacity of the corresponding aged sample were 15.42 m^(2)/g and 497.7μmol/g,respectively.In addition,a mechanism was proposed to reveal the effects of co-precipitation temperature on the structure and properties of CZLYs.
基金Project supported by National Natural Science Foundation of China(51204083,51374004,51104074,51174105,51306084)the Applied Basic Research Program of Yunnan Province(2012FD016)the Candidate Talents Training Fund of Yunnan Province(2012HB009)
文摘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~）.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 oc- curred at beginning following with selective oxidation later. Ce~_xFexO2~ oxygen carriers （x5_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 selec- tivity 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.
文摘Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria （CeO2） makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610℃ to values included in the diesel exhausts operation range （300-450℃）. The sol-gel method was used to synthesize mixed oxide-based catalysts （CeO2：ZnO）; the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric （TG/DTA） analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200℃ on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy （DRS） showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor： soot emission decreased by more than 70%.
文摘Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.
基金supported by the National Natural Science Foundation of China(21606219)the “Transformational Technologies for Clean Energy and Demonstration”,Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21030900)~~
文摘The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation.In this work,we found that ZnO-CuO mixed oxides supported gold catalysts showed much better catalytic activity for base-free aerobic oxidation of benzyl alcohol than Au/ZnO and Au/CuO catalysts,and among them Au/Zn0.7Cu0.3O displayed the best catalytic performance.In addition,the Au/Zn0.7Cu0.3O catalyst could selectively catalyze the aerobic oxidation of a wide range of alcohols to produce the corresponding carbonyl compounds with high yields under mild conditions without base.Further characterizations indicated that the outstanding catalytic performance of Au/Zn0.7Cu0.3O was correlated with the small size of Au nanoparticles(NPs),good low-temperature reducibility,high concentration of surface oxygen species,and collaborative interaction between Au NPs and mixed oxide.
文摘The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have been correlated with the surface electron donor properties of these mixed oxides
基金Project supported by Yunnan Province Science Technology Program (2002C001Z) the National High Technology Research and Development Program ( 863 ) of China ( 2002AA321060 ) Yunnan Province Science Technology Program (2004B0028Q)
文摘The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.
文摘A series of CexPr1-xO2-δ (x=0, 0.5, 0.9, 1.0) mixed oxide calcined at different temperatures were synthesized by sol-gel method and characterized by Raman, XRD and O2-TPD techniques. When x=0.9, only a cubic phase CeO2 is observed. When x=0.5, the compound was combined by Pr6O11 and CeO2 mixed oxides. For CexPr1-xO2-δ (x=0.5, 0.9)samples 465 cm-1 Raman peak is attributed to the Raman active F2g mode of CeO2. The broad peak at about 570 cm-1 can be linked to lattice defects resulting in oxygen vacancies. The crystallite size of the samples increased as increasing the calcined temperature. But the increased value of Ce0.9Pr0.1O2-δ and Ce0.5Pr0.5O2-δ is smaller than single CeO2 and Pr6O11 obviously. It reveals that the insertion of Pr atom into the ceria lattice could enhance the sintering resistance and thermal stability of the mixed oxides. Calcination temperatures had great effect on the peak intensity for CeO2 but less effect on Ce0.8Pr0.2O2-δ in Raman spectra, and it may be caused by the colors transformation of the mixed oxides. The result of O2-TPD experiment indicates that the formation of solid solution has elevation the stabilization and thermal stability of the mixed oxides.
基金Project supported by Twelfth Five-Year National Science and Technology Pillar Program (2012BAE01B02)Eleventh Five-Year National 863 Program (2010AA03A405)
文摘A series of cerium zirconium mixed oxides were prepared by two co-precipitation methods using magnesium hydrogen carbonate （MHC） and mixed ammonia-ammonia hydrogen carbonate （AAHC） as precipitant respectively. The crystal structure, BET surface area and morphology of the produced cerium zirconium mixed oxides were characterized by X-ray diffraction （XRD）, Bru- mauer-Emmett-Teller （BET） and scanning electron microscopy （SEM） techniques. The reduction-oxidation behavior and oxygen storage capacity （OSC） performance were also studied by temperature programmed reduction （TPR） and oxygen pulse chemical adsorption methods. The XRD results demonstrated that the cerium zirconium mixed oxides obtained by both methods possessed struc ture of cubic solid solution phase. The fresh surface area calcinated at 600 ℃, aged surface area after 1000 ℃and OSC at 500 ℃ of cerium zirconium mixed oxides were determined to be 89.337, 34.784 ma/g, and 567 pmol O2/g for MHC method and 122.010, 46.307 m2/g, and 665 pmol O2/g for AAHC method, respectively.
基金supported by the National Natural Science Foundation of China(Nos.21676225 and 21776236)Natural Science Foundation of Hunan Province(2018JJ2384)+2 种基金Fund of Hunan Provincial Education Department(19A478)Collaborative Innovation Centre of New Chemical Technologies for Environmental Benignity and Efficient Resource UtilizationEngineering Research Centre of Chemical Process Simulation and Optimization of Ministry of Education。
文摘To enhance the hydrogen release during hydrogen storage,several Pt-Ir supported on Mg-Al mixed oxide catalysts were prepared and then applied into the dehydrogenation of methylcyclohexane(MCH)in this study.The effects of iridium content,reduction temperature on the activity and stability of the catalysts were studied in detail.In the presence of Ir,metal particle size was decrea sed and electron transfer between Ir and Pt was observed.High reduction temperature increased the metallic Ir content but enlarged the particle size of active site s.During the dehydrogenation reaction on Pt-Ir bimetallic catalyst,MCH was efficiently converted into toluene and PtIr-5/Mg-Al-275 exhibited the highe st activity.After prolonging the residence time and raising the reaction temperature to 350℃the conversion and hydrogen evolution rate were increased to 99.9%and 578.7 mmol·(g Pt)^-1·min^-1,respectively.Moreover,no carbon deposition was observed in the spent catalyst,presenting a high anti-coking ability and good potential for industrial application.
