All-solid-state electrolytes are exceedingly attractive because of the outstanding inherent safety and energy density compared to liquid electrolytes.Whereas,it is still formidable to simultaneously design solid elect...All-solid-state electrolytes are exceedingly attractive because of the outstanding inherent safety and energy density compared to liquid electrolytes.Whereas,it is still formidable to simultaneously design solid electrolytes with favorable electrode/electrolyte interface compatibility and high ionic conductivity in a simple and scalable manner.Hence,the oxygen-vacancy-rich Gd-doped SnO_(2) nanotubes(GDS NTs)are innovatively prepared and applied to the electrolyte of all-solid-state lithium metal batteries for the first time.The addition of GDS NTs can validly construct long-range co ntinuous ion transport networks in the poly(ethylene oxide)(PEO)-based system and greatly improve the mechanical properties of the electrolyte.Compared to the PEO-based electrolyte,the composite electrolyte displays a higher lithium ion conductivity of 2.41×10^(-4) S cm^(-1) at 30℃,a higher lithium ion transference number up to 0.62 and a wider electrochemical window of 5 V at 50℃.In addition,the composite electrolyte manifests outstanding compatibility with high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)cathode,LiFePO4 cathode and lithium metal anode.The assembled Li/Li symmetric battery exhibits stable Li plating/stripping cycling performance,which can cycle steadily for 1500 h at a capacity of 0.3 mA h cm^(-2).And Li/LiFePO4 battery still maintains a high capacity of 131.54 mA h g^(-1) at 0.5C after 800 cycles,which has a superior capacity retention rate of 93.2%.The obtained novel composite electrolyte has promising application prospects in the field of all-solid-state lithium metal cells.展开更多
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
A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structur...A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structure, morphology, and the magnetic properties of the samples were characterized by powder X-ray diffraction （XRD）, atomic force microscopy （AFM） and a vibrating sample magnetometer （VSM）. A single spinel phase was obtained in the range of x = 0.00 - 0.04. The lattice parameters of the Gd-doped samples were larger than that of pure Li-Ni ferrite, and increased in the range of 0.00 ≤ x ≤ 0.04, then decreased up to x = 0.08, because of the formation of the secondary phase （Gd- FeO3）. All samples were spheric particles with an average size of about 100 nm, but agglomerated to some extent. The hysteresis loops indicated that the saturation magnetization decreased gradually with increasing Gd content, while the variation of coercivity was related to the microstructure of the Gd-doped samples.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
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
Ischemia/reperfusion is known to greatly increase oxidative stress in the penumbra,which results in brain damage.Integrin αvβ3 is selectively up-regulated with ischemic injury to the brain and remains elevated throu...Ischemia/reperfusion is known to greatly increase oxidative stress in the penumbra,which results in brain damage.Integrin αvβ3 is selectively up-regulated with ischemic injury to the brain and remains elevated throughout reperfusion.We determined whether or not a new compound biotinylated-LXW7-ceria nanoparticle（Ce NP）（b LXW7-Ce NP） plays a role in brain protection in the rat model of middle cerebral artery occlusion/reperfusion and shows better effects than Ce NPs alone in improving the outcomes of focal oxidative stress and apoptosis more effectively.Male Sprague-Dawley rats were subjected to focal cerebral ischemia for 2 h followed by a 24-h reperfusion.Drug treatment was intravenously administered via the caudal vein 1 h after occlusion.Rats were randomly divided into the following 4 groups：b LXW7-Ce NP treatment group（0.5 mg/kg）;Ce NP treatment group（0.5 mg/kg）;control saline group;and sham group.Brains were harvested 24 h after reperfusion,and the neurologic deficit scores,infarction volume,blood-brain barrier（BBB） disruption,and the level of oxidative stress and apoptosis were determined.Results showed that the b LXW7-Ce NP and Ce NP treatments could improve neurologic deficit scores,infarction volume,BBB disruption,and the level of oxidative stress and apoptosis.Compound b LXW7-Ce NP treatment exhibited better effects than Ce Np treatment and showed remarkable statistical differences in the infarction volume,the degree of BBB breakdown,the apoptosis and oxidative stress,apart from neurologic deficit scores.Thus,we concluded that b LXW7-Ce NP protects against acute cerebral ischemia/reperfusion injury.BLXW7,as a ligand of integrin αvβ3,may be able to effectively localize the anti-oxidant Ce NPs to the ischemic penumbra region,which may provide more adequate opportunities for Ce NPs to exert anti-oxidative stress effects and subsequently reduce apoptosis in acute cerebral ischemia/reperfusion.展开更多
In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow ...In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow method techniques, XRD and TPD-MS. Experimental results indicated that (1) the addition of CeO2 improving disperse degree of CuO on CuO/γ-Al2O3 catalysts which caused a large increase in activity; (2) the addition of CeO2 may increase oxygen supplying ability and oxygen recovery ability of catalyst surface.展开更多
By synthesizing reactive powders via a self-sustaining combustion synthesis, the glycine-nitrate process, the gadolinium-doped celia （GDC） with the chemical formula Ce0.8Gd0.2O1.9 was prepared. The resultant powders...By synthesizing reactive powders via a self-sustaining combustion synthesis, the glycine-nitrate process, the gadolinium-doped celia （GDC） with the chemical formula Ce0.8Gd0.2O1.9 was prepared. The resultant powders were dispersed with the terpineol as the dispersant through different methods such as ball milling and high-shear dispersing. Coagulation factor （CF） was used to mark the degree of agglomeration on the nano-scale GDC in this work. The effect of agglomeration on the densification behavior at different sintering temperatures was investigated. The studies indicated that agglomeration retarded the densification at the sintering stage. The powders with better dispersion exhibited a higher sintered density at the same temperature. After effective dispersion treatment, GDC could be fully densified at the sintering temperature of 1300 ℃. The densification temperature was significantly lower than those reported previously. The high sintering kinetics of the ceramics was obtained based on the agglomeration control.展开更多
A novel salt-assisted combustion process with ethylene glycol as a fuel and nitrate as an oxidant to synthesize high surface area celia nanopowders was reported. The effects of various tunable conditions, such as fuel...A novel salt-assisted combustion process with ethylene glycol as a fuel and nitrate as an oxidant to synthesize high surface area celia nanopowders was reported. The effects of various tunable conditions, such as fuel-to-oxidant ratio, type of salts, and amount of added salts, on the characteristics of the as-prepared powders were investigated by X-ray diffraction, transmission electron microscopy and BET surface area measurement. A mechanism scheme was proposed to illustrate the possible formation processes of well-dispersed ceria nanoparticles in the salt-assisted combustion synthesis. It was verified that the simple introduction of leachable inert inorganic salts as an excellent agglomeration inhibitor into the redox mixture precursor leads to the formation of well-dispersed ceria particles with particle size in the range of 4 ～6 nm and a drastic increase in the surface area. The presence of KCl results in an over ten-fold increment in specific surface area from 14.10 m^2·g^-1 for the produced ceria powders via the conventional combustion synthesis process to 156.74 m^2·g^-1 for the product by the salt-assisted combustion synthesis process at the same molar ratio of ethylene glycol-nitrate.展开更多
In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Further...In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction （XRD）, high resolution transmission electron microscopy （HRTEM）, and temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.展开更多
基金supported by the National Natural Science Foundation of China(52203066,51973157,61904123,51873152)the Tianjin Natural Science Foundation(18JCQNJC02900)+3 种基金the Science and Technology Plans of Tianjin(19PTSYJC00010)the Tianjin Research Innovation Project for Postgraduate Students(2021YJSB234)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘All-solid-state electrolytes are exceedingly attractive because of the outstanding inherent safety and energy density compared to liquid electrolytes.Whereas,it is still formidable to simultaneously design solid electrolytes with favorable electrode/electrolyte interface compatibility and high ionic conductivity in a simple and scalable manner.Hence,the oxygen-vacancy-rich Gd-doped SnO_(2) nanotubes(GDS NTs)are innovatively prepared and applied to the electrolyte of all-solid-state lithium metal batteries for the first time.The addition of GDS NTs can validly construct long-range co ntinuous ion transport networks in the poly(ethylene oxide)(PEO)-based system and greatly improve the mechanical properties of the electrolyte.Compared to the PEO-based electrolyte,the composite electrolyte displays a higher lithium ion conductivity of 2.41×10^(-4) S cm^(-1) at 30℃,a higher lithium ion transference number up to 0.62 and a wider electrochemical window of 5 V at 50℃.In addition,the composite electrolyte manifests outstanding compatibility with high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)cathode,LiFePO4 cathode and lithium metal anode.The assembled Li/Li symmetric battery exhibits stable Li plating/stripping cycling performance,which can cycle steadily for 1500 h at a capacity of 0.3 mA h cm^(-2).And Li/LiFePO4 battery still maintains a high capacity of 131.54 mA h g^(-1) at 0.5C after 800 cycles,which has a superior capacity retention rate of 93.2%.The obtained novel composite electrolyte has promising application prospects in the field of all-solid-state lithium metal cells.
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Project supported by the Natural Science Foundation of China (Y405038) Science and Technology Key Project of ZhejiangProvince (2006C21080)
文摘A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structure, morphology, and the magnetic properties of the samples were characterized by powder X-ray diffraction （XRD）, atomic force microscopy （AFM） and a vibrating sample magnetometer （VSM）. A single spinel phase was obtained in the range of x = 0.00 - 0.04. The lattice parameters of the Gd-doped samples were larger than that of pure Li-Ni ferrite, and increased in the range of 0.00 ≤ x ≤ 0.04, then decreased up to x = 0.08, because of the formation of the secondary phase （Gd- FeO3）. All samples were spheric particles with an average size of about 100 nm, but agglomerated to some extent. The hysteresis loops indicated that the saturation magnetization decreased gradually with increasing Gd content, while the variation of coercivity was related to the microstructure of the Gd-doped samples.
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.
基金supported by grants from Shenzhen Science and Technology Innovation Committee(No.JCYJ20140415162543033)Startup Fund Project of Inner Mongolia University(No.21300-5145152)+1 种基金Key Project of Education Department of Inner Mongolia(No.NJZZ16015)the Natural Science Foundation of Inner Mongolia(No.2016MS0216)
文摘Ischemia/reperfusion is known to greatly increase oxidative stress in the penumbra,which results in brain damage.Integrin αvβ3 is selectively up-regulated with ischemic injury to the brain and remains elevated throughout reperfusion.We determined whether or not a new compound biotinylated-LXW7-ceria nanoparticle（Ce NP）（b LXW7-Ce NP） plays a role in brain protection in the rat model of middle cerebral artery occlusion/reperfusion and shows better effects than Ce NPs alone in improving the outcomes of focal oxidative stress and apoptosis more effectively.Male Sprague-Dawley rats were subjected to focal cerebral ischemia for 2 h followed by a 24-h reperfusion.Drug treatment was intravenously administered via the caudal vein 1 h after occlusion.Rats were randomly divided into the following 4 groups：b LXW7-Ce NP treatment group（0.5 mg/kg）;Ce NP treatment group（0.5 mg/kg）;control saline group;and sham group.Brains were harvested 24 h after reperfusion,and the neurologic deficit scores,infarction volume,blood-brain barrier（BBB） disruption,and the level of oxidative stress and apoptosis were determined.Results showed that the b LXW7-Ce NP and Ce NP treatments could improve neurologic deficit scores,infarction volume,BBB disruption,and the level of oxidative stress and apoptosis.Compound b LXW7-Ce NP treatment exhibited better effects than Ce Np treatment and showed remarkable statistical differences in the infarction volume,the degree of BBB breakdown,the apoptosis and oxidative stress,apart from neurologic deficit scores.Thus,we concluded that b LXW7-Ce NP protects against acute cerebral ischemia/reperfusion injury.BLXW7,as a ligand of integrin αvβ3,may be able to effectively localize the anti-oxidant Ce NPs to the ischemic penumbra region,which may provide more adequate opportunities for Ce NPs to exert anti-oxidative stress effects and subsequently reduce apoptosis in acute cerebral ischemia/reperfusion.
文摘In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow method techniques, XRD and TPD-MS. Experimental results indicated that (1) the addition of CeO2 improving disperse degree of CuO on CuO/γ-Al2O3 catalysts which caused a large increase in activity; (2) the addition of CeO2 may increase oxygen supplying ability and oxygen recovery ability of catalyst surface.
基金Project supported by the Key Research Programof the National Natural Science Foundation (90610035)
文摘By synthesizing reactive powders via a self-sustaining combustion synthesis, the glycine-nitrate process, the gadolinium-doped celia （GDC） with the chemical formula Ce0.8Gd0.2O1.9 was prepared. The resultant powders were dispersed with the terpineol as the dispersant through different methods such as ball milling and high-shear dispersing. Coagulation factor （CF） was used to mark the degree of agglomeration on the nano-scale GDC in this work. The effect of agglomeration on the densification behavior at different sintering temperatures was investigated. The studies indicated that agglomeration retarded the densification at the sintering stage. The powders with better dispersion exhibited a higher sintered density at the same temperature. After effective dispersion treatment, GDC could be fully densified at the sintering temperature of 1300 ℃. The densification temperature was significantly lower than those reported previously. The high sintering kinetics of the ceramics was obtained based on the agglomeration control.
基金Project supported bythe National Natural Science Foundation of China (50306008) andthefundfromthe Preli minary ResearchProject of General Equipment Ministry (41328030507)
文摘A novel salt-assisted combustion process with ethylene glycol as a fuel and nitrate as an oxidant to synthesize high surface area celia nanopowders was reported. The effects of various tunable conditions, such as fuel-to-oxidant ratio, type of salts, and amount of added salts, on the characteristics of the as-prepared powders were investigated by X-ray diffraction, transmission electron microscopy and BET surface area measurement. A mechanism scheme was proposed to illustrate the possible formation processes of well-dispersed ceria nanoparticles in the salt-assisted combustion synthesis. It was verified that the simple introduction of leachable inert inorganic salts as an excellent agglomeration inhibitor into the redox mixture precursor leads to the formation of well-dispersed ceria particles with particle size in the range of 4 ～6 nm and a drastic increase in the surface area. The presence of KCl results in an over ten-fold increment in specific surface area from 14.10 m^2·g^-1 for the produced ceria powders via the conventional combustion synthesis process to 156.74 m^2·g^-1 for the product by the salt-assisted combustion synthesis process at the same molar ratio of ethylene glycol-nitrate.
文摘In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction （XRD）, high resolution transmission electron microscopy （HRTEM）, and temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.
