Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large partic...Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large particle size(>20 nm)and less surface defects,however,hinder further application of ceria materials.Herein,an alternative strategy involving lactic acid(LA)assisted hydrothermal method was developed to synthesize active,selective and durable cubic ceria of<6 nm for dehydrogenation reactions.Detailed studies of growth mechanism revealed that,the carboxyl and hydroxyl groups in LA molecule synergistically manipulate the morphological evolution of ceria precursors.Carboxyl groups determine the cubic shape and particle size,while hydroxyl groups promote compositional transformation of ceria precursors into CeO_(2) phases.Moreover,enhanced oxygen vacancies(Vo)on the surface of CeO_(2) were obtained owing to continuous removal of O species under reductive atmosphere.Cubic CeO_(2) catalysts synthesized by the LA-assisted method,immobilized with bimetallic PtCo clusters,exhibit a record high activity(TOF:29,241 h^(-1))and Vo-dependent synergism for dehydrogenation of bio-derived polyols at 200℃.We also found that quenching Vo defects at air atmosphere causes activity loss of PtCo/CeO_(2) catalysts.To regenerate Vo defects,a simple strategy was developed by irradiating deactivated catalysts using hernia lamp.The outcome of this work will provide new insights into manufacturing durable catalyst materials for aqueous phase dehydrogenation applications.展开更多
The catalytic properties of electrode materials Ni/Ce1-xYxO2-δ （x = 0.05, 0.10, 0.15 and 0.20） were investigated for partial oxidation of methane （POM）. The CeO2-Y2O3 solid solutions were prepared by co-precipita...The catalytic properties of electrode materials Ni/Ce1-xYxO2-δ （x = 0.05, 0.10, 0.15 and 0.20） were investigated for partial oxidation of methane （POM）. The CeO2-Y2O3 solid solutions were prepared by co-precipitaion method. The Ni-based catalysts supported on the solid solutions were obtained using the impregnation method. Structural, surface and redox characteristics of the prepared catalysts were system- atically examined by means of X-ray diffraction （XRD）, N2 adsorption-desorption （Brunauer-Emmet-Teller BET method）, H2 temperature- programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS） methods. The results indicated that yttria doped in the ceria system, forming a good solid solution, readily induced more defects and oxygen vacancies that favored the improvement of catalytic activity and coking resistance. In the temperature range of 600-850 ℃, Ni/Ce0.90Y0.10O1.950 catalyst exhibited the best catalytic activity among the four tested catalysts, with the CH4 conversion, CO selectivity and H2 selectivity of 78.8%, 90.6% and 89.8%, respectively, at 850 ℃. And the H2/CO molar ratio in products of Ni/Ce0.90Y0.10O1.950 catalyst was closer to the theoretical value of 2.0. The excellent coking resistant behaviors for all catalysts were clearly manifested by thermal analysis.展开更多
A series of H3PO4-modified CeO2 samples were prepared by impregnation of CeO2 with H3PO4solution,and evaluated for the selective catalytic reduction of NOx by NH3.The samples were characterized by X-ray diffraction,N2...A series of H3PO4-modified CeO2 samples were prepared by impregnation of CeO2 with H3PO4solution,and evaluated for the selective catalytic reduction of NOx by NH3.The samples were characterized by X-ray diffraction,N2 adsorption-desorption,infrared spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy,temperature-programmed desorption of NH3,and temperature-programmed reduction of H2.The results showed that more than 80%NO conversion was achieved in the temperature range 250-550℃ over the H3PO4-CeO2 catalyst.The enhanced catalytic performance could be ascribed to the increase in acidic strength,especially Bronsted acidity,and reduction in redox properties of the CeO2 after H3PO4 modification.展开更多
The preferential oxidation of CO （CO‐PROX） is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells （PEMFCs）. Au catalysts are highly active in CO oxidation. Howev‐er, their activities ...The preferential oxidation of CO （CO‐PROX） is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells （PEMFCs）. Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 ＆#176;C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction （H2‐TPR）, Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions （＆gt;97%） and CO2 selectivities （＆gt;50%） in the temperature range 80–150 ＆#176;C.展开更多
Ceria nanotubes with high CO conversion activity by means of carbon nanotubes as removable templates in the simple liquid phase process were fabricated under moderate conditions. The pristine CNTs were first pretreate...Ceria nanotubes with high CO conversion activity by means of carbon nanotubes as removable templates in the simple liquid phase process were fabricated under moderate conditions. The pristine CNTs were first pretreated by refluxing in a 30% nitric acid solution at 140 ℃ for 24 h, then dispersed in an ethanolic Ce（NO3）3.6H2O solution with ultrasonic radiation at room temperature for 1 h. Under vigorous stirring, NaOH solution was added drop by drop into the above ethanolic solution until the pH value was 10. The product was collected and repeatedly washed with ethanol and on drying at 60 ℃, the CeO2/CNT composites were obtained. Then, the as-prepared composites were heated at 450 ℃ in an air atmosphere for 30 min to remove CNTs. The ceria nanotubes were characterized by X-Ray Diffraction （XRD）, Transmission Electron Microscopy （TEM）, and X-Ray Photoelectron Spectrum （XPS）. The results showed that the ceria nanotubes were polycrystalline face-centered cubic phase and were composed of lots of dense cefia nanoparficles. The diameter of cefia nanotubes was about 40-50 nm. Catalytic activity of the product for CO oxidation was carded out at the region of 30-300 ℃ in a U-shaped quartz reactor with feeding about 0.15 g of the catalyst, which was loaded on Al2O3 carder. The inlet gas composition was 1.0% CO and 28% O2 with N2 as balance, and the rate of flow was kept at 40 ml/min. The catalytic products were analyzed by gas chromatography. The as-repared CeO2 nanotubes showed higher CO oxidation activity, which indicated that the morphology of ceria products affected the catalytic performance. The ceria nanotubes supported on Al2O3 demonstrated that conversion temperature for CO oxidation to CO2 was lower than that for bulk catalysts.展开更多
Solid oxide fuel cell(SOFC) electrodes,after a high temperature sintering,may be impregnated to deposit nanoparticles within their pores to enhance the catalytic function.Samarium doped CeO2(SDC) nanoparticles were in...Solid oxide fuel cell(SOFC) electrodes,after a high temperature sintering,may be impregnated to deposit nanoparticles within their pores to enhance the catalytic function.Samarium doped CeO2(SDC) nanoparticles were infiltrated into(Pr0.7Ca0.3)0.9MnO3-δ(PCM) cathode of anode supported SOFC cells.The cell with 2.6 mg/cm2 SDC impregnated in cathode showed the maximum power density of 580 mW/cm2 compared with 310 mW/cm2 of the cell without impregnation at 850 °C.The cells were also characterized with the impeda...展开更多
Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by sc...Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy（SEM）, X-ray diffractometer（XRD）, high-resolution transmission electron microscopy（HRTEM） and temperature programmed reducfion（TPR） techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift （WGS） reaction in a wide temperature range （180-360 ℃）. The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.展开更多
Fine spherical particle sized ceria (CeO_2) was prepared by homogeneous precipitation method with ammonium bicarbonate as precipitant. The prepared CeO_2 has the primary particle size of 10～50 nm when calcined betwee...Fine spherical particle sized ceria (CeO_2) was prepared by homogeneous precipitation method with ammonium bicarbonate as precipitant. The prepared CeO_2 has the primary particle size of 10～50 nm when calcined between 400～700 ℃ analyzed by XRD and the aggregated particle size is about 300 nm measured by LASER particle sizer. SEM, TG-DTA and Zeta-potential analyzer were employed individually to study the morphology and the formation of CeO_2 product. It was found that excess NH_4NO_3 can serve as an sphericallization agent to prepare spherical CeO_2 powder by precipitation method.展开更多
Isothermal and cyclic oxidation behaviors of chromium samples with and without nanometric CeO2 coating were studied at 900℃ in air. Scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and ...Isothermal and cyclic oxidation behaviors of chromium samples with and without nanometric CeO2 coating were studied at 900℃ in air. Scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and high-resolution electron microscopy （HREM） were used to examine the morphology and microstructure of the oxide film. It was found that ceria coating greatly improved the oxidation resistance of Cr both in isothermal and cyclic oxidizing experiments. Acoustic emission （AE） technique was used in situ to monitor the cracking and spalling of oxide film, and AE signals were analyzed in time-domain and number-domain according to related oxide fracture model. Laser Raman spectrometer was also used to study the stress of oxide film formed on Cr with and without ceria. The improvement in oxidation resistance of chromium is believed mainly due to that ceria greatly reduced the growth speed and grain size of Cr2O3. This fine grained Cr2O3 oxide film might have better high temperature plasticity and could relieve parts of the compressive stress by means of creeping and maintained ridge character and relatively lower level of internal stress. Meanwhile, ceria application reduced the size and number of interfacial defects, remarkably enhanced the adhesive property of Cr2O3 oxide scale formed on Cr substrate.展开更多
As a mixed ion-electronic conductor, doped ceria, especially rare earth doped ceria, were used as anodes or components of anodes in SOFCs. In this work, calcium doped ceria （CCO） was synthesized to be used in interm...As a mixed ion-electronic conductor, doped ceria, especially rare earth doped ceria, were used as anodes or components of anodes in SOFCs. In this work, calcium doped ceria （CCO） was synthesized to be used in intermediate-temperature SOFCs （IT-SOFCs） anodes in order to reduce the cost of anode-supported SOFCs. Electrical conductivity of 20% calcium doped ceria （20CCO） reached 0.209 S·cm^-1 in hydrogen at 850 ℃, and 0.041 S·cm^-1 in air at 800℃, which is about 0.04 S·cm^-1 lower than that of conventional samaria-doped ceria （0.079 S·cm^-1）. Electrochemical performance of Ni-20CCO cermet as anode was investigated using a fuel cell with 35μm-thick SDC electrolyte and Sm0.5Sr0.5 Co-SDC cathode. Maximum power density was 623 mW·cm^-2 under humidified （3% H2O） hydrogen at 650 ℃, inferring high catalytic activity of the Ni-20CCO anode.展开更多
A series of gold-based catalysts were prepared by deposition precipitation or incipient wetness impregnation on CexZ1-xO2 solid solutions （0.28≤x≤1.00）. The morphological and structural characterization of these c...A series of gold-based catalysts were prepared by deposition precipitation or incipient wetness impregnation on CexZ1-xO2 solid solutions （0.28≤x≤1.00）. The morphological and structural characterization of these catalysts were carried out with X-ray diffraction, trans- mission electron microscopy （TEM） analysis and physical adsorption technique, and their redox properties were studied by temperature programmed reduction using both H2 and CO as probe molecules. Two cycles of oxidation/reduction were carried out in order to evaluate the effects of redox aging and gold sintering on the oxygen exchange capability. As observed with other noble metals, gold enhanced and promoted the ceria reduction at lower temperatures. Reduction by CO was shown to be dependent on the fine dispersion of gold and to be nega- tively affected by the ageing process more than reduction with hydrogen. This might have implications in reactions like water gas shift and CO-PROX which involve CO as a main reactant.展开更多
A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite ...A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved展开更多
The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO2/CeO2-δ) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and meth...The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO2/CeO2-δ) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and methane to syngas in the temperature range 900–1050 °C. Experiments were carried out with different ceria shapes via two-step redox cycling composed of endothermic partial reduction of ceria with methane and complete exothermic re-oxidation of reduced ceria with H2 O/CO2 at the same operating temperature, thereby demonstrating the capability to operate the cycle isothermally. A parametric study considering different ceria macrostructure variants(ceria packed powder, ceria packed powder mixed with inert Al2 O3 particles, and ceria reticulated porous foam) and operating parameters(methane flow-rate, reduction temperature, or sintering temperature) was conducted in order to unravel their impact on the bed-averaged oxygen non-stoichiometry(δ), syngas yield, methane conversion, and solar reactor performance. The ceria cycling stability was also experimentally investigated to demonstrate repeatable syngas production by alternating the flow between CH4 and H2 O(or CO2). A decrease in sintering temperature of the ceria foam was beneficial for increasing syngas selectivity, methane conversion,and reactor performance. Increasing both CH4 concentration and reduction temperature enhanced δ with the maximum value up to 0.41 but concomitantly favored CH4 cracking reaction. The ceria reticulated porous foam showed better performance in terms of effective heat transfer, due to volumetric absorption of concentrated solar radiation and uniform heating with lower solar power consumption, thereby promoting the solar-to-fuel energy conversion efficiency that reached up to 5.60%. The energy upgrade factor achieved during cycle was up to 1.19. Stable patterns in the δ and syngas yield for consecutive cycles with the ceria foam validated material performance stability.展开更多
基金financial supports National Natural Science Foundation of China(22078365,21706290)Natural Science Foundation of Shandong Province(ZR2017MB004)+2 种基金Innovative Research Funding from Qingdao City,Shandong Province(17-1-1-80-jch)“Fundamental Research Funds for the Central Universities”and“the Development Fund of State Key Laboratory of Heavy Oil Processing”(17CX02017A,20CX02204A)Postgraduate Innovation Project(YCX2021057)from China University of Petroleum.
文摘Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large particle size(>20 nm)and less surface defects,however,hinder further application of ceria materials.Herein,an alternative strategy involving lactic acid(LA)assisted hydrothermal method was developed to synthesize active,selective and durable cubic ceria of<6 nm for dehydrogenation reactions.Detailed studies of growth mechanism revealed that,the carboxyl and hydroxyl groups in LA molecule synergistically manipulate the morphological evolution of ceria precursors.Carboxyl groups determine the cubic shape and particle size,while hydroxyl groups promote compositional transformation of ceria precursors into CeO_(2) phases.Moreover,enhanced oxygen vacancies(Vo)on the surface of CeO_(2) were obtained owing to continuous removal of O species under reductive atmosphere.Cubic CeO_(2) catalysts synthesized by the LA-assisted method,immobilized with bimetallic PtCo clusters,exhibit a record high activity(TOF:29,241 h^(-1))and Vo-dependent synergism for dehydrogenation of bio-derived polyols at 200℃.We also found that quenching Vo defects at air atmosphere causes activity loss of PtCo/CeO_(2) catalysts.To regenerate Vo defects,a simple strategy was developed by irradiating deactivated catalysts using hernia lamp.The outcome of this work will provide new insights into manufacturing durable catalyst materials for aqueous phase dehydrogenation applications.
基金supported by the National Basic Research Program of China (973 Program) (No. 2005CB221404)
文摘The catalytic properties of electrode materials Ni/Ce1-xYxO2-δ （x = 0.05, 0.10, 0.15 and 0.20） were investigated for partial oxidation of methane （POM）. The CeO2-Y2O3 solid solutions were prepared by co-precipitaion method. The Ni-based catalysts supported on the solid solutions were obtained using the impregnation method. Structural, surface and redox characteristics of the prepared catalysts were system- atically examined by means of X-ray diffraction （XRD）, N2 adsorption-desorption （Brunauer-Emmet-Teller BET method）, H2 temperature- programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS） methods. The results indicated that yttria doped in the ceria system, forming a good solid solution, readily induced more defects and oxygen vacancies that favored the improvement of catalytic activity and coking resistance. In the temperature range of 600-850 ℃, Ni/Ce0.90Y0.10O1.950 catalyst exhibited the best catalytic activity among the four tested catalysts, with the CH4 conversion, CO selectivity and H2 selectivity of 78.8%, 90.6% and 89.8%, respectively, at 850 ℃. And the H2/CO molar ratio in products of Ni/Ce0.90Y0.10O1.950 catalyst was closer to the theoretical value of 2.0. The excellent coking resistant behaviors for all catalysts were clearly manifested by thermal analysis.
基金supported by the National Natural Science Foundation of China(21177120)the Open Fund of Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education~~
文摘A series of H3PO4-modified CeO2 samples were prepared by impregnation of CeO2 with H3PO4solution,and evaluated for the selective catalytic reduction of NOx by NH3.The samples were characterized by X-ray diffraction,N2 adsorption-desorption,infrared spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy,temperature-programmed desorption of NH3,and temperature-programmed reduction of H2.The results showed that more than 80%NO conversion was achieved in the temperature range 250-550℃ over the H3PO4-CeO2 catalyst.The enhanced catalytic performance could be ascribed to the increase in acidic strength,especially Bronsted acidity,and reduction in redox properties of the CeO2 after H3PO4 modification.
基金supported by the National Basic Research Program of China (973 Program, 2013CB934104)the National Natural Science Founda-tion of China (21225312, U1303192)~~
文摘The preferential oxidation of CO （CO‐PROX） is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells （PEMFCs）. Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 ＆#176;C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction （H2‐TPR）, Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions （＆gt;97%） and CO2 selectivities （＆gt;50%） in the temperature range 80–150 ＆#176;C.
基金Fundamental Research Key Project of Shanghai (06JC14060)
文摘Ceria nanotubes with high CO conversion activity by means of carbon nanotubes as removable templates in the simple liquid phase process were fabricated under moderate conditions. The pristine CNTs were first pretreated by refluxing in a 30% nitric acid solution at 140 ℃ for 24 h, then dispersed in an ethanolic Ce（NO3）3.6H2O solution with ultrasonic radiation at room temperature for 1 h. Under vigorous stirring, NaOH solution was added drop by drop into the above ethanolic solution until the pH value was 10. The product was collected and repeatedly washed with ethanol and on drying at 60 ℃, the CeO2/CNT composites were obtained. Then, the as-prepared composites were heated at 450 ℃ in an air atmosphere for 30 min to remove CNTs. The ceria nanotubes were characterized by X-Ray Diffraction （XRD）, Transmission Electron Microscopy （TEM）, and X-Ray Photoelectron Spectrum （XPS）. The results showed that the ceria nanotubes were polycrystalline face-centered cubic phase and were composed of lots of dense cefia nanoparficles. The diameter of cefia nanotubes was about 40-50 nm. Catalytic activity of the product for CO oxidation was carded out at the region of 30-300 ℃ in a U-shaped quartz reactor with feeding about 0.15 g of the catalyst, which was loaded on Al2O3 carder. The inlet gas composition was 1.0% CO and 28% O2 with N2 as balance, and the rate of flow was kept at 40 ml/min. The catalytic products were analyzed by gas chromatography. The as-repared CeO2 nanotubes showed higher CO oxidation activity, which indicated that the morphology of ceria products affected the catalytic performance. The ceria nanotubes supported on Al2O3 demonstrated that conversion temperature for CO oxidation to CO2 was lower than that for bulk catalysts.
文摘Solid oxide fuel cell(SOFC) electrodes,after a high temperature sintering,may be impregnated to deposit nanoparticles within their pores to enhance the catalytic function.Samarium doped CeO2(SDC) nanoparticles were infiltrated into(Pr0.7Ca0.3)0.9MnO3-δ(PCM) cathode of anode supported SOFC cells.The cell with 2.6 mg/cm2 SDC impregnated in cathode showed the maximum power density of 580 mW/cm2 compared with 310 mW/cm2 of the cell without impregnation at 850 °C.The cells were also characterized with the impeda...
基金supported by the Ministry of Sciences and Technology of China (863 Programs) (2006AA05Z115, 2007AA05Z104)
文摘Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy（SEM）, X-ray diffractometer（XRD）, high-resolution transmission electron microscopy（HRTEM） and temperature programmed reducfion（TPR） techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift （WGS） reaction in a wide temperature range （180-360 ℃）. The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.
基金Project supported by Rare Earth Department of National Development Committee Preparation of High Quality Polishing Powder
文摘Fine spherical particle sized ceria (CeO_2) was prepared by homogeneous precipitation method with ammonium bicarbonate as precipitant. The prepared CeO_2 has the primary particle size of 10～50 nm when calcined between 400～700 ℃ analyzed by XRD and the aggregated particle size is about 300 nm measured by LASER particle sizer. SEM, TG-DTA and Zeta-potential analyzer were employed individually to study the morphology and the formation of CeO_2 product. It was found that excess NH_4NO_3 can serve as an sphericallization agent to prepare spherical CeO_2 powder by precipitation method.
基金Project supported by the National Natural Science Foundation of China (29231011)the Natural Science Foundation ofJiangsu Province (04KJD460010)
文摘Isothermal and cyclic oxidation behaviors of chromium samples with and without nanometric CeO2 coating were studied at 900℃ in air. Scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and high-resolution electron microscopy （HREM） were used to examine the morphology and microstructure of the oxide film. It was found that ceria coating greatly improved the oxidation resistance of Cr both in isothermal and cyclic oxidizing experiments. Acoustic emission （AE） technique was used in situ to monitor the cracking and spalling of oxide film, and AE signals were analyzed in time-domain and number-domain according to related oxide fracture model. Laser Raman spectrometer was also used to study the stress of oxide film formed on Cr with and without ceria. The improvement in oxidation resistance of chromium is believed mainly due to that ceria greatly reduced the growth speed and grain size of Cr2O3. This fine grained Cr2O3 oxide film might have better high temperature plasticity and could relieve parts of the compressive stress by means of creeping and maintained ridge character and relatively lower level of internal stress. Meanwhile, ceria application reduced the size and number of interfacial defects, remarkably enhanced the adhesive property of Cr2O3 oxide scale formed on Cr substrate.
基金Project supported bythe National Natural Science Foundation of China (20271047)
文摘As a mixed ion-electronic conductor, doped ceria, especially rare earth doped ceria, were used as anodes or components of anodes in SOFCs. In this work, calcium doped ceria （CCO） was synthesized to be used in intermediate-temperature SOFCs （IT-SOFCs） anodes in order to reduce the cost of anode-supported SOFCs. Electrical conductivity of 20% calcium doped ceria （20CCO） reached 0.209 S·cm^-1 in hydrogen at 850 ℃, and 0.041 S·cm^-1 in air at 800℃, which is about 0.04 S·cm^-1 lower than that of conventional samaria-doped ceria （0.079 S·cm^-1）. Electrochemical performance of Ni-20CCO cermet as anode was investigated using a fuel cell with 35μm-thick SDC electrolyte and Sm0.5Sr0.5 Co-SDC cathode. Maximum power density was 623 mW·cm^-2 under humidified （3% H2O） hydrogen at 650 ℃, inferring high catalytic activity of the Ni-20CCO anode.
文摘A series of gold-based catalysts were prepared by deposition precipitation or incipient wetness impregnation on CexZ1-xO2 solid solutions （0.28≤x≤1.00）. The morphological and structural characterization of these catalysts were carried out with X-ray diffraction, trans- mission electron microscopy （TEM） analysis and physical adsorption technique, and their redox properties were studied by temperature programmed reduction using both H2 and CO as probe molecules. Two cycles of oxidation/reduction were carried out in order to evaluate the effects of redox aging and gold sintering on the oxygen exchange capability. As observed with other noble metals, gold enhanced and promoted the ceria reduction at lower temperatures. Reduction by CO was shown to be dependent on the fine dispersion of gold and to be nega- tively affected by the ageing process more than reduction with hydrogen. This might have implications in reactions like water gas shift and CO-PROX which involve CO as a main reactant.
基金supported by the National Natural Science Foundation of China(21276041,U1610104)the Chinese Ministry of Education via the Program for New Century Excellent Talents in University(NCET-12-0079)~~
文摘A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved
基金The King Mongkut’s Institute of Technology Ladkrabang(KMITL),Thailandthe Franco-Thai scholarship program。
文摘The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO2/CeO2-δ) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and methane to syngas in the temperature range 900–1050 °C. Experiments were carried out with different ceria shapes via two-step redox cycling composed of endothermic partial reduction of ceria with methane and complete exothermic re-oxidation of reduced ceria with H2 O/CO2 at the same operating temperature, thereby demonstrating the capability to operate the cycle isothermally. A parametric study considering different ceria macrostructure variants(ceria packed powder, ceria packed powder mixed with inert Al2 O3 particles, and ceria reticulated porous foam) and operating parameters(methane flow-rate, reduction temperature, or sintering temperature) was conducted in order to unravel their impact on the bed-averaged oxygen non-stoichiometry(δ), syngas yield, methane conversion, and solar reactor performance. The ceria cycling stability was also experimentally investigated to demonstrate repeatable syngas production by alternating the flow between CH4 and H2 O(or CO2). A decrease in sintering temperature of the ceria foam was beneficial for increasing syngas selectivity, methane conversion,and reactor performance. Increasing both CH4 concentration and reduction temperature enhanced δ with the maximum value up to 0.41 but concomitantly favored CH4 cracking reaction. The ceria reticulated porous foam showed better performance in terms of effective heat transfer, due to volumetric absorption of concentrated solar radiation and uniform heating with lower solar power consumption, thereby promoting the solar-to-fuel energy conversion efficiency that reached up to 5.60%. The energy upgrade factor achieved during cycle was up to 1.19. Stable patterns in the δ and syngas yield for consecutive cycles with the ceria foam validated material performance stability.
