Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 a...Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 and CeO2 exhibit better activity and selectivity than pure Cu catalyst due to Cu-support(ZrO2 and CeO2)interaction.Combining the structural characterizations with in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS),Cu/CeO2 shows the higher methanol selectivity due to the formation of main carbonates intermediates,which are closely related with the oxygen vacancies over Cu/CeO2.In contrast,bicarbonate and carboxyl species are observed on Cu/ZrO2,which originates from the hydroxyl groups presented on catalyst surfaces.Difference in CO2 adsorption intermediates results in the distinct methanol selectivity over the two catalysts.展开更多
A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydrothermal method. The influence of calcination temperature on the catalytic activity, microstructure...A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydrothermal method. The influence of calcination temperature on the catalytic activity, microstructure, surface acidity and redox behavior of CeO2-ZrO2-WO3 catalyst was investigated using various characterization methods. It was found that the CeO2-ZrO2-WO3 catalyst calcined at 600 ℃ showed the best catalytic performance and excellent N2 selectivity, and yielded more than 90% NO conversion in a wide temperature range of 250-500 ℃ with a space velocity (GHSV) of 60000 131. As the calcination temperature was increased from 400 to 600 ℃, the NO conversion obviously increased, but decreased at higher calcination temperature. The results implied that the higher surface area, the strongest synergistic interaction, the superior redox property and the highly dispersed or amorphous WO3 species contributed to the excellent SCR activity of the CeO2-ZrO2-WO3 catalyst calcined at 600℃.展开更多
Praseodymium (Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibilit...Praseodymium (Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), CO chemi- sorption and H2 temperature-programmed reduction (H2-TPR). The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.展开更多
A series of praseodymium added CeO2(ZrO2)/TiO2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction (XRD)...A series of praseodymium added CeO2(ZrO2)/TiO2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction (XRD), N2-brumauer-emmett-teller (N2-BET), NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), PL spectra, Ra-man spectra, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS), respectively. Influence of prepara-tion method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO2(ZrO2)/TiO2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO2 forming the struc-ture of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce3+ species, which was favourable for higher catalytic activity.展开更多
Nickel and sulfate co-modified CeO2-ZrO2 catalysts were prepared by sol-gel method. The catalysts were characterized by XRD, FTIR, XPS, NH3 chemisorption and NH3-SCR activity tests. The results showed that the enhance...Nickel and sulfate co-modified CeO2-ZrO2 catalysts were prepared by sol-gel method. The catalysts were characterized by XRD, FTIR, XPS, NH3 chemisorption and NH3-SCR activity tests. The results showed that the enhanced acidity of CeO2-ZrO2 catalysts by nickel and sulfate co-modification was responsible for the broadened temperature window and improved the selectivity to N2 in NH3-SCR deNOx. The introduction of nickel to CeO2-ZrO2 solid solutions resulted in more Ce3+ on surface of catalyst, leading to an in...展开更多
CeO2-based oxygen materials were prepared with co-precipitation method and characterized via Brunauer-Emmet Teller(BET)method,X-ray diffraction(XRD)and temperature-programmed reduction(H2-TPR).This paper revealed that...CeO2-based oxygen materials were prepared with co-precipitation method and characterized via Brunauer-Emmet Teller(BET)method,X-ray diffraction(XRD)and temperature-programmed reduction(H2-TPR).This paper revealed that three CeO2-based oxygen storage materials are all forming homogeneous solid solution.Among the samples,CeO2-ZrO2-Al2O3(CZA)has the best textural properties and excellent thermal stability.The specific surface area and pore volume of aged CZA are 90 m2/g and 0.29 mL/g.We proposed a viewpoint:Al3+ might insert among the interspace of fluorite structure or highly dispersal in solid solutions.展开更多
The electrocatalytic activity and stability of Pt/C catalyst modified by using CeO_2-ZrO_2 mixed oxides for the alcohols electrochemical oxidation as probes were investigated. The catalyst samples were characterized b...The electrocatalytic activity and stability of Pt/C catalyst modified by using CeO_2-ZrO_2 mixed oxides for the alcohols electrochemical oxidation as probes were investigated. The catalyst samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The electrochemical properties were measured by a three electrode system on electrochemical workstation(IVIUM). The results showed that the presence of CeO_2-ZrO_2 might be associated with the presence of Pt, which indicated that possibly there was synergistic effect between CeO_2-ZrO_2 and Pt nanoparticles. The electrocatalytic activity and stability of Pt-MO_x/C(M=Ce, Zr) for methanol and ethanol oxidation was better than that of Pt-CeO_2/C, which was attributed to that CeO_2-ZrO_2 composited oxides enhanced oxygen mobility and promoted oxygen storage capacity(OSC). Furthermore, the best performance was found when the molar ratio of CeO_2 to ZrO_2 was 2:1 for the oxidation of methanol and ethanol. The forward peak current density of Pt-MO_x/C(M=Ce, Zr, Ce:Zr=2:1) towards the methanol electrooxidation was about 3.8 times that of Pt-CeO_2/C. Pt-MO_x/C(M=Ce, Zr) appeared to be a promising and less expensive methanol oxidation anode catalyst.展开更多
A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method.The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determi...A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method.The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determine the appropriate Er dosage.The catalysts were characterized using X-ray diffraction,N2 adsorption,NH3 temperature-programmed desorption,H2 temperature-programmed reduction,photoluminescence spectroscopy,electron paramagnetic resonance spectroscopy,and X-ray photoelectron spectroscopy.The results showed that the optimum Er/Ce molar ratio was 0.10;this catalyst had excellent resistance to catalyst poisoning caused by vapor and sulfur and gave more than 90% NO conversion at 220–395 ℃ and a gas hourly space velocity of 71 400 h^-1.Er incorporation increased the Ti^3+ concentrations,oxygen storage capacities,and oxygen vacancy concentrations of the catalysts,resulting in excellent catalytic performance.Er incorporation also decreased the acid strength and inhibited growth of TiO2 and CeO2 crystal particles,which increased the catalytic activity.The results show that high oxygen vacancy concentrations and oxygen storage capacities,large amounts of Ti^3+,and low acid strengths give excellent SCR activity.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
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 sp...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.展开更多
The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aqueous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-tem...The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aqueous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-temperature-programmed reduction (H2-TPR) methods. The XRD result indicated that the CeO2-ZrO2-Al2O3 compound prepared by co-precipitation formed a single solid solution and had good thermal stability, and Pd phase was not observed in all catalysts. The TPR results showed that the reduction temperature of Pd/CeO2-ZrO2-Al2O3 catalyst was lower than that of Pd/CeO2-ZrO2+Al2O3 catalyst whether they were fresh or aged catalysts. The Pd/CeO2-ZrO2-Al2O3 exhibited high three-way catalytic activity at low temperature, high thermal stability, and wide working window, suggesting a great potential for applications.展开更多
基金financially supported by the National Natural Science Foundation of China (21577014, 21876019, 21825203, 21688102)Programme of Introducing Talents of Discipline to Universities (B13012)the fund of the State Key Laboratory of Catalysis in DICP (Y401010502)
摘要Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 and CeO2 exhibit better activity and selectivity than pure Cu catalyst due to Cu-support(ZrO2 and CeO2)interaction.Combining the structural characterizations with in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS),Cu/CeO2 shows the higher methanol selectivity due to the formation of main carbonates intermediates,which are closely related with the oxygen vacancies over Cu/CeO2.In contrast,bicarbonate and carboxyl species are observed on Cu/ZrO2,which originates from the hydroxyl groups presented on catalyst surfaces.Difference in CO2 adsorption intermediates results in the distinct methanol selectivity over the two catalysts.
基金Project supported by the National Natural Science Foundation of China(21377048,21307047)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(LYJ1309)
摘要A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydrothermal method. The influence of calcination temperature on the catalytic activity, microstructure, surface acidity and redox behavior of CeO2-ZrO2-WO3 catalyst was investigated using various characterization methods. It was found that the CeO2-ZrO2-WO3 catalyst calcined at 600 ℃ showed the best catalytic performance and excellent N2 selectivity, and yielded more than 90% NO conversion in a wide temperature range of 250-500 ℃ with a space velocity (GHSV) of 60000 131. As the calcination temperature was increased from 400 to 600 ℃, the NO conversion obviously increased, but decreased at higher calcination temperature. The results implied that the higher surface area, the strongest synergistic interaction, the superior redox property and the highly dispersed or amorphous WO3 species contributed to the excellent SCR activity of the CeO2-ZrO2-WO3 catalyst calcined at 600℃.
基金supported by National Natural Science Foundation of China(51202116)Ministry of Science and Technology,China(2010CB732304,2013AA065302)
摘要Praseodymium (Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), CO chemi- sorption and H2 temperature-programmed reduction (H2-TPR). The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.
基金supported by National Key Research and Development Program of China(2016YFC0205500)National Natural Science Foundation of China(51272105)+1 种基金Jiangsu Provincial Science and Technology Supporting Program(BE2013718)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
摘要A series of praseodymium added CeO2(ZrO2)/TiO2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction (XRD), N2-brumauer-emmett-teller (N2-BET), NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), PL spectra, Ra-man spectra, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS), respectively. Influence of prepara-tion method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO2(ZrO2)/TiO2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO2 forming the struc-ture of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce3+ species, which was favourable for higher catalytic activity.
基金Project supported by the "863 Project" (2009AA06Z304 and 2009AA064801)
摘要Nickel and sulfate co-modified CeO2-ZrO2 catalysts were prepared by sol-gel method. The catalysts were characterized by XRD, FTIR, XPS, NH3 chemisorption and NH3-SCR activity tests. The results showed that the enhanced acidity of CeO2-ZrO2 catalysts by nickel and sulfate co-modification was responsible for the broadened temperature window and improved the selectivity to N2 in NH3-SCR deNOx. The introduction of nickel to CeO2-ZrO2 solid solutions resulted in more Ce3+ on surface of catalyst, leading to an in...
摘要CeO2-based oxygen materials were prepared with co-precipitation method and characterized via Brunauer-Emmet Teller(BET)method,X-ray diffraction(XRD)and temperature-programmed reduction(H2-TPR).This paper revealed that three CeO2-based oxygen storage materials are all forming homogeneous solid solution.Among the samples,CeO2-ZrO2-Al2O3(CZA)has the best textural properties and excellent thermal stability.The specific surface area and pore volume of aged CZA are 90 m2/g and 0.29 mL/g.We proposed a viewpoint:Al3+ might insert among the interspace of fluorite structure or highly dispersal in solid solutions.
基金supported by National Natural Science Foundation of China(51474133,21407084)Talent Incubation Funding of School of Materials and Metallurgy(2014CY012)
摘要The electrocatalytic activity and stability of Pt/C catalyst modified by using CeO_2-ZrO_2 mixed oxides for the alcohols electrochemical oxidation as probes were investigated. The catalyst samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The electrochemical properties were measured by a three electrode system on electrochemical workstation(IVIUM). The results showed that the presence of CeO_2-ZrO_2 might be associated with the presence of Pt, which indicated that possibly there was synergistic effect between CeO_2-ZrO_2 and Pt nanoparticles. The electrocatalytic activity and stability of Pt-MO_x/C(M=Ce, Zr) for methanol and ethanol oxidation was better than that of Pt-CeO_2/C, which was attributed to that CeO_2-ZrO_2 composited oxides enhanced oxygen mobility and promoted oxygen storage capacity(OSC). Furthermore, the best performance was found when the molar ratio of CeO_2 to ZrO_2 was 2:1 for the oxidation of methanol and ethanol. The forward peak current density of Pt-MO_x/C(M=Ce, Zr, Ce:Zr=2:1) towards the methanol electrooxidation was about 3.8 times that of Pt-CeO_2/C. Pt-MO_x/C(M=Ce, Zr) appeared to be a promising and less expensive methanol oxidation anode catalyst.
基金supported by the National Natural Science Foundation of China(51272105)Jiangsu Provincial Science and Technology Supporting Program(BE2013718)+1 种基金Research Subject of Environmental Protection Department of Jiangsu Province of China(2013006)Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)~~
摘要A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method.The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determine the appropriate Er dosage.The catalysts were characterized using X-ray diffraction,N2 adsorption,NH3 temperature-programmed desorption,H2 temperature-programmed reduction,photoluminescence spectroscopy,electron paramagnetic resonance spectroscopy,and X-ray photoelectron spectroscopy.The results showed that the optimum Er/Ce molar ratio was 0.10;this catalyst had excellent resistance to catalyst poisoning caused by vapor and sulfur and gave more than 90% NO conversion at 220–395 ℃ and a gas hourly space velocity of 71 400 h^-1.Er incorporation increased the Ti^3+ concentrations,oxygen storage capacities,and oxygen vacancy concentrations of the catalysts,resulting in excellent catalytic performance.Er incorporation also decreased the acid strength and inhibited growth of TiO2 and CeO2 crystal particles,which increased the catalytic activity.The results show that high oxygen vacancy concentrations and oxygen storage capacities,large amounts of Ti^3+,and low acid strengths give excellent SCR activity.
基金PRIN 2006, "Caratterizzazione spettroscopica e morfologica di Me-POSS eterogeneizzati", MEL Chemicals
摘要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 supported by State Key Fundamental Research Project(G1999022400)
摘要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.
基金supported by the National Natural Science Foundation of China(21173153)National Hi-tech Research and Development Program of China(863)(2015AA034603)Opening Project of Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education,China(LYJ1407)~~
基金Project supported by the National High Technology Research and Development Program of China (863 Program,2006AA06Z347)the Specialized Research Fund for the Doctoral Program of Higher Education (20070610026)
摘要The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aqueous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-temperature-programmed reduction (H2-TPR) methods. The XRD result indicated that the CeO2-ZrO2-Al2O3 compound prepared by co-precipitation formed a single solid solution and had good thermal stability, and Pd phase was not observed in all catalysts. The TPR results showed that the reduction temperature of Pd/CeO2-ZrO2-Al2O3 catalyst was lower than that of Pd/CeO2-ZrO2+Al2O3 catalyst whether they were fresh or aged catalysts. The Pd/CeO2-ZrO2-Al2O3 exhibited high three-way catalytic activity at low temperature, high thermal stability, and wide working window, suggesting a great potential for applications.