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
Ceria-based heterostructure composite(CHC)has become a new stream to develop advanced low-temperature(300–600°C)solid oxide fuel cells(LTSOFCs)with excellent power outputs at 1000 mW cm−2 level.The state-ofthe-a...Ceria-based heterostructure composite(CHC)has become a new stream to develop advanced low-temperature(300–600°C)solid oxide fuel cells(LTSOFCs)with excellent power outputs at 1000 mW cm−2 level.The state-ofthe-art ceria–carbonate or ceria–semiconductor heterostructure composites have made the CHC systems significantly contribute to both fundamental and applied science researches of LTSOFCs;however,a deep scientific understanding to achieve excellent fuel cell performance and high superionic conduction is still missing,which may hinder its wide application and commercialization.This review aims to establish a new fundamental strategy for superionic conduction of the CHC materials and relevant LTSOFCs.This involves energy band and built-in-field assisting superionic conduction,highlighting coupling effect among the ionic transfer,band structure and alignment impact.Furthermore,theories of ceria–carbonate,e.g.,space charge and multi-ion conduction,as well as new scientific understanding are discussed and presented for functional CHC materials.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 impedance spectra,and the SDC impregnation significantly reduced the polarization resistance.After performance test the cells were characterized with scanning electron microscopy(SEM),and the cathode morphology showed the impregnated SDC particles were nanosized and were deposited on the surface of the PCM framework.The possible mechanism for the performance improvement was discussed.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
Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals.In this context,catalytic steam reforming of glycerol(SRG) was proposed as a promisi...Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals.In this context,catalytic steam reforming of glycerol(SRG) was proposed as a promising and sustainable alternative for producing renewable hydrogen(H2).Herein,the development of nickel(Ni) supported on ceria-modified mesoporous γ-alumina(γ-Al2 O3) catalysts and their applications in catalytic SRG(at550-750℃ atmospheric pressure and weight hourly space velocity,WHSV,of 44,122 ml·g^-1·h^-1(STP)) is presented.Properties of the developed catalysts were characterised using many technique s.The findings show that ceria modification improved Ni dispersion on γ-Al2 O3 catalyst support with highly active small Ni particles,which led to a remarkable catalytic performance with the total glycerol conversion(ca.99%),glycerol conversion into gaseous products(ca.77%) and H2 yield(ca.62%).The formation rate for H2 production(14.4 ×10^(-5)mol·s^-1·g^-1, TOF(H2)=3412 s^-1) was significantly improved with the Ni@12 Ce-Al2 O3 catalyst,representing nearly a 2-fold increase compared with that of the conventional Ni@AI2 O3 catalyst.In addition,the developed catalyst also exhibited comparatively high stability(for 12 h) and coke resistance ability.展开更多
Ce0.6Zr0.3RE0.1O2(RE=Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite structur...Ce0.6Zr0.3RE0.1O2(RE=Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite structure. The different dopant ion radii bring different effect on the cell parameter of Ce0.6Zr0.3RE0.1O2. The X-ray photoelectron spectroscopy (XPS) results show that the binding energy of Ce3d, Zr3d and O1s for Ce0.6Zr0.3RE0.1O2 rises compared with that for Ce0.6Zr0.4O2, indicating that dopant elements change chemistry environment of solid solutions which is available to improve redox performance. Compared with Pd/Ce0.6Zr0.4O2, doping Y and La does not change air/fuel (A/F) characteristic of TWCs, but doping Pr and Tb widens A/F operating window and makes HC, CO and NO have higher conversion. The light-off temperature of Pd/Ce0.6Zr0.3La0.1O2 is corresponding to that of Pd/Ce0.6Zr0.4O2. However, the light-off temperatures of Pd/Ce0.6Zr0.3M0.1O2 (M=Y, Pr, Tb) are lower than that of Pd/Ce0.6Zr0.4O2, which keep much lower after high temperature treatments. Among Pd/Ce0.6Zr0.3RE0.1O2, Pd/Ce0.6Zr0.3Tb0.1O2 represents wider A/F operating window, higher conversion, lower light-off temperature and better high-temperature resistance.展开更多
The granule shape and crystal structure of the the ceria-based rare earth oxide which were roasted at 600～1050 ℃ for 2～6 h and then cooled in furnace, cooled out of furnace or cooled in water were studied by means ...The granule shape and crystal structure of the the ceria-based rare earth oxide which were roasted at 600～1050 ℃ for 2～6 h and then cooled in furnace, cooled out of furnace or cooled in water were studied by means of XRD and SEM. The results revealed that the rich cerium rare earth carbonate could be changed into the rare earth oxide which was a kind of sandwich made of globose granule whose diameter was between 0.5～3.0 μm after being roasted in 900 ℃ for 2 h. This kind of crystal lattice in rare earth oxide belonged to face-centered cubic lattice and its space between crystal surface {111} and {200} (viz. L111 and L200) would enlarge as the roasting temperature increasing. With increasing roasting temperature, L111 would rise straightly upward, and L200 would rise straightly upward when roasting time was 2～4 h but changed little when roasting time was 4～6 h. The glass-polishing experiments found that the polishing ability of the ceria-based rare earth oxide was the best as L111 was 43～53 nm and the L200 was 43～56 nm.展开更多
Zirconia-ceria mixed oxide powders were prepared by high temperature aging method.The effects of the temperature and the time of aging, cerium content and calcination on powder performance were studied.The result show...Zirconia-ceria mixed oxide powders were prepared by high temperature aging method.The effects of the temperature and the time of aging, cerium content and calcination on powder performance were studied.The result shows that high temperature aging is an efficient way of preparation of ZrO2-CeO2 mixed oxide powders with high specific surface area and good thermal stability, and that addition of a small amount of cerium to hydrous zirconia can promote the preparation of high specific surface area powders.展开更多
Martensitic transformation behavior was studied for zirconia containing 4%～10% CeO2 (in mole fraction) by using a dilatometric method. The Ms (Martensite start temperature) decreased near linearly with increasing CeO...Martensitic transformation behavior was studied for zirconia containing 4%～10% CeO2 (in mole fraction) by using a dilatometric method. The Ms (Martensite start temperature) decreased near linearly with increasing CeO2. Different transformation modes were observed depending on the composition and cooling rate. ZrO2 containing 6% CeO2 showed isothermal transformation behavior, whereas ZrO2 containing 9% and 10% CeO2 showed athermal transformation behavior. However, ZrO2 containing 8% CeO2 showed either isothermal or athermal transformations behavior depending on the cooling rate. A TTT (Time-Temperature-Transformation) diagram was proposed for ZrO2 containing 8% CeO2.展开更多
Nanocrystalline solid solution CeO2-Nd2O3 powders were prepared by low temperature combustion process.Special attention was paid to the influence of the glycine/metal ratio and calcination temperature on the powders p...Nanocrystalline solid solution CeO2-Nd2O3 powders were prepared by low temperature combustion process.Special attention was paid to the influence of the glycine/metal ratio and calcination temperature on the powders phase structure, morphology and particle size.TG-DSC curves and XRD peaks of different glycine/metal ratio show that smaller particle size can be obtained with a slightly fuel-deficient ratio.XRD results indicate that the as-prepared powders are crystallized in a single fluorite structure.The crystalline size ranges from 9 to 24 nm, which increases with the increase of calcination temperature.The lower SEM images were characterized by the spongy and form-like microstructure of the powders.Organic agent may be gradually eliminated by high temperature calcination process.展开更多
CeO_(2)-based catalysts are emerging as novel candidates for catalyzing nitrogen reduction reaction(NRR).However, despite the increasing amount of experimental and theoretical research, the design of more efficient ce...CeO_(2)-based catalysts are emerging as novel candidates for catalyzing nitrogen reduction reaction(NRR).However, despite the increasing amount of experimental and theoretical research, the design of more efficient ceria catalysts for NRR remains a challenge due to the poor knowledge of the catalytic mechanism, particularly the nature of the active sites and how they catalyze NRR. Here, using first-principle calculations, we investigated the NRR catalysis process involving adjacent Ce Lewis acid clusters formed on(111),(110), and(100) facets of CeO_(2) as active sites. Our results revealed that the assembled structures of the Ce Lewis acid as active centers after the oxygen vacancies(Ovs) were opened. The exposed Ce sites on CeO_(2)(111), CeO_(2)(110), and CeO_(2)(100) can cause N_(2) to be adsorbed in a ‘‘lying-down" manner, which facilitates the N2 activation and thus leads to much higher NRR activity. Furthermore, from the perspective of electronic structure, we establish two useful descriptors for assessing the NRR activity on ceria with Ovs:The N–N bond strength of the adsorbed N_(2) and the adsorption energy of the *N_(2)H intermediate. This work thus provides direct guidance for the design of more-effective oxide catalysts without the use of scarce metals.展开更多
Ceria(CeO_(2))nanoparticles were successfully synthesized via a simple complex-precipitation route that employs cerium chloride as cerium source and citric acid as precipitant.The elemental analysis results of carbon,...Ceria(CeO_(2))nanoparticles were successfully synthesized via a simple complex-precipitation route that employs cerium chloride as cerium source and citric acid as precipitant.The elemental analysis results of carbon,hydrogen,oxygen,and cerium in the precursors were calculated,and the results revealed that the precursors were composed of Ce(OH)_(3),Ce(H_(2)Cit)_(3),or CeCit.X-ray diffraction analysis showed that all ceria nanoparticles had a face-centered cubic structure.With the molar ratio of citric acid to Ce^(3)+(n)of 0.25 and pH of 5.5,the specific surface area of the sample reached the maximum value of 83.17 m^(2)/g.Ceria nanoparticles were observed by scanning electron microscopy.Selected area electron diffraction patterns of several samples were obtained by transmission electron microscopy,and the crystal plane spacing of each low-exponent crystal plane was calculated.The ultraviolet(UV)–visible transmittance curve showed that ceria can absorb UV light and pass through visible light.Among all samples,the minimum average transmittance of ultraviolet radiation a(UVA)was 4.42%,and that of ultraviolet radiation b(UVB)was 1.56%.展开更多
Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were ...Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce^(3+) ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.展开更多
The solid structures and thermostabilities of Cu Fe O and Cu Fe Ce O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe 2CuO 4, CuO and α Fe 2O 3 phase...The solid structures and thermostabilities of Cu Fe O and Cu Fe Ce O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe 2CuO 4, CuO and α Fe 2O 3 phases in Cu Fe O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe 2CuO 4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu 2+ concentration, inhibits the crystal growth of CuO and Fe 2CuO 4 in the catalyst except that of Fe 2O 3, and eliminates the difference for reductive reaction of oxygen in Fe O and Cu O. At 800 ℃, the crystal growth of Fe 2O 3 in Cu Fe Ce O is slower than that in Cu Fe O, i.e., CeO 2 in Cu Fe Ce O inhibits the growth of Fe 2O 3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO 2 promotes the reducibility of catalysts at lower temperature.展开更多
Europium doped CeO_2 was synthesized via combustion synthesis method. The powders were found to be in a single phase. The average crystallite size was found to be about 30nm. It was revealed from photoluminescence spe...Europium doped CeO_2 was synthesized via combustion synthesis method. The powders were found to be in a single phase. The average crystallite size was found to be about 30nm. It was revealed from photoluminescence spectra that there was an excitation band around 368 nm and a narrow excitation peak at 468nm. The emission spectrum showed four peaks at 589, 608, 629 and 650nm.展开更多
Ceria- and alumina-pillared interlayered clays were synthesized in the presence of PEO surfactant by using laponite clay as raw material.And the synthesized pillared clays were used as supports to load palladium catal...Ceria- and alumina-pillared interlayered clays were synthesized in the presence of PEO surfactant by using laponite clay as raw material.And the synthesized pillared clays were used as supports to load palladium catalysts for complete oxidation of benzene.Nitrogen adsorption/desorption experiments reveal that the pillared clays have higher tests show that ceria pillar exhibited promoting effect on the activity of the palladium catalysts, and ceria-pillared clay supported palladium catalyst catalyzed the complete oxidation of benzene at less than 250 ℃.The calcination temperature affects the activity of the catalysts significantly, and it is found that the optimal calcination temperature are 600 and 400 ℃ for ceria- and alumina-pillared clay supported palladium catalysts, respectively.展开更多
Mixed ionic electronic conductors(MIECs)have attracted increasing attention as anode materials for solid oxide fuel cells(SOFCs)and they hold great promise for lowering the operation temperature of SOFCs.However,there...Mixed ionic electronic conductors(MIECs)have attracted increasing attention as anode materials for solid oxide fuel cells(SOFCs)and they hold great promise for lowering the operation temperature of SOFCs.However,there has been a lack of understanding of the performance-limiting factors and guidelines for rational design of composite metal-MIEC electrodes.Using a newly-developed approach based on 3 D-tomography and electrochemical impedance spectroscopy,here for the first time we quantify the contribution of the dual-phase boundary(DPB)relative to the three-phase boundary(TPB)reaction pathway on real MIEC electrodes.A new design strategy is developed for Ni/gadolinium doped ceria(CGO)electrodes(a typical MIEC electrode)based on the quantitative analyses and a novel Ni/CGO fiber-matrix structure is proposed and fabricated by combining electrospinning and tape-casting methods using commercial powders.With only 11.5 vol%nickel,the designer Ni/CGO fiber-matrix electrode shows 32%and 67%lower polarization resistance than a nano-Ni impregnated CGO scaffold electrode and conventional cermet electrode respectively.The results in this paper demonstrate quantitatively using real electrode structures that enhancing DPB and hydrogen kinetics are more efficient strategies to enhance electrode performance than simply increasing TPB.展开更多
A series of CeO2-Al2O3, CeO2-TiO2, CeO2-ZrO2, and CeO2-SiO2 mixed-oxide supported copper catalysts were prepared by a modified deposition-precipitation method from ultra dilute aqueous solutions and were investigated ...A series of CeO2-Al2O3, CeO2-TiO2, CeO2-ZrO2, and CeO2-SiO2 mixed-oxide supported copper catalysts were prepared by a modified deposition-precipitation method from ultra dilute aqueous solutions and were investigated for hydrogenolysis of cellulose in aqueous medium, in the presence of hydrogen to produce sorbitol as major product. Among all the catalysts tested in the present work, CuO/CeO2ZrO2?catalyst proved to be the most promising with high conversion (92%) and excellent selectivity (sorbitol 99.1%), at an intermediate reaction temperature of 245°C in a neutral aqueous solution without an aid of liquid phase acid. The catalyst was recyclable in repeated runs and no deactivation was observed even after five reaction cycles. CuO/CeO2-ZrO2 has been characterized by XRD, SEM, TPR and BET surface area techniques.展开更多
Copper-based composites strengthened by ceria nanoparticles were processed by conventional powder metallurgy: mixing (30 min and 46 rpm), compaction (cold, uniaxial, 1080 MPa for 10 s) and sintering (800°C for 6 ...Copper-based composites strengthened by ceria nanoparticles were processed by conventional powder metallurgy: mixing (30 min and 46 rpm), compaction (cold, uniaxial, 1080 MPa for 10 s) and sintering (800°C for 6 h in vacuum atmosphere of 10−5 torr). It was studied the microstructure (optical microscopy, scanning electron microscopy), X-ray diffraction with Rietveld refinement and some properties (electrical conductivity, Vickers hardness and fracture analysis) of the compositions 92 wt% Cu - 8 wt% CeO2 and 80 wt% Cu - 20 wt% CeO2. The results showed uniform phase distribution, low porosity and ceria disperse inside copper grain. In despite of properties, the composites had electrical conductivity of 38% IACS and 15% IACS and hardness of 69 and 88 HV5, respectively. The results of 92 wt% Cu - 8 wt% CeO2 composites were promising, and they are in according with actual literature.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.
文摘Ceria-based heterostructure composite(CHC)has become a new stream to develop advanced low-temperature(300–600°C)solid oxide fuel cells(LTSOFCs)with excellent power outputs at 1000 mW cm−2 level.The state-ofthe-art ceria–carbonate or ceria–semiconductor heterostructure composites have made the CHC systems significantly contribute to both fundamental and applied science researches of LTSOFCs;however,a deep scientific understanding to achieve excellent fuel cell performance and high superionic conduction is still missing,which may hinder its wide application and commercialization.This review aims to establish a new fundamental strategy for superionic conduction of the CHC materials and relevant LTSOFCs.This involves energy band and built-in-field assisting superionic conduction,highlighting coupling effect among the ionic transfer,band structure and alignment impact.Furthermore,theories of ceria–carbonate,e.g.,space charge and multi-ion conduction,as well as new scientific understanding are discussed and presented for functional CHC materials.
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 impedance spectra,and the SDC impregnation significantly reduced the polarization resistance.After performance test the cells were characterized with scanning electron microscopy(SEM),and the cathode morphology showed the impregnated SDC particles were nanosized and were deposited on the surface of the PCM framework.The possible mechanism for the performance improvement was discussed.
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funding from European Union's Horizon 2020 research and innovation programme under grant agreement No.872102financial support by the Petroleum Technology Development Fund(PTDF),Nigeria(PTDF/ED/OSS/PHD/IA/1209/17)+2 种基金financial support from the European Commission Marie Sklodowska-Curie Individual Fellowship(H2020-MSCAIF-NTPleasure-748196)the Chinese Scholarship Council(CSC)for her academic visiting fellowship at the University of Manchester(No.201708440477)the Foundation of Department of Education of Guangdong Province(Nos.2017KZDXM085,2018KZDXM070)。
文摘Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals.In this context,catalytic steam reforming of glycerol(SRG) was proposed as a promising and sustainable alternative for producing renewable hydrogen(H2).Herein,the development of nickel(Ni) supported on ceria-modified mesoporous γ-alumina(γ-Al2 O3) catalysts and their applications in catalytic SRG(at550-750℃ atmospheric pressure and weight hourly space velocity,WHSV,of 44,122 ml·g^-1·h^-1(STP)) is presented.Properties of the developed catalysts were characterised using many technique s.The findings show that ceria modification improved Ni dispersion on γ-Al2 O3 catalyst support with highly active small Ni particles,which led to a remarkable catalytic performance with the total glycerol conversion(ca.99%),glycerol conversion into gaseous products(ca.77%) and H2 yield(ca.62%).The formation rate for H2 production(14.4 ×10^(-5)mol·s^-1·g^-1, TOF(H2)=3412 s^-1) was significantly improved with the Ni@12 Ce-Al2 O3 catalyst,representing nearly a 2-fold increase compared with that of the conventional Ni@AI2 O3 catalyst.In addition,the developed catalyst also exhibited comparatively high stability(for 12 h) and coke resistance ability.
基金Project supported by the Doctoral Foundation of Shandong Province (2004BS08001 ) Science Foundation of Ludong University (042901)
文摘Ce0.6Zr0.3RE0.1O2(RE=Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite structure. The different dopant ion radii bring different effect on the cell parameter of Ce0.6Zr0.3RE0.1O2. The X-ray photoelectron spectroscopy (XPS) results show that the binding energy of Ce3d, Zr3d and O1s for Ce0.6Zr0.3RE0.1O2 rises compared with that for Ce0.6Zr0.4O2, indicating that dopant elements change chemistry environment of solid solutions which is available to improve redox performance. Compared with Pd/Ce0.6Zr0.4O2, doping Y and La does not change air/fuel (A/F) characteristic of TWCs, but doping Pr and Tb widens A/F operating window and makes HC, CO and NO have higher conversion. The light-off temperature of Pd/Ce0.6Zr0.3La0.1O2 is corresponding to that of Pd/Ce0.6Zr0.4O2. However, the light-off temperatures of Pd/Ce0.6Zr0.3M0.1O2 (M=Y, Pr, Tb) are lower than that of Pd/Ce0.6Zr0.4O2, which keep much lower after high temperature treatments. Among Pd/Ce0.6Zr0.3RE0.1O2, Pd/Ce0.6Zr0.3Tb0.1O2 represents wider A/F operating window, higher conversion, lower light-off temperature and better high-temperature resistance.
文摘The granule shape and crystal structure of the the ceria-based rare earth oxide which were roasted at 600～1050 ℃ for 2～6 h and then cooled in furnace, cooled out of furnace or cooled in water were studied by means of XRD and SEM. The results revealed that the rich cerium rare earth carbonate could be changed into the rare earth oxide which was a kind of sandwich made of globose granule whose diameter was between 0.5～3.0 μm after being roasted in 900 ℃ for 2 h. This kind of crystal lattice in rare earth oxide belonged to face-centered cubic lattice and its space between crystal surface {111} and {200} (viz. L111 and L200) would enlarge as the roasting temperature increasing. With increasing roasting temperature, L111 would rise straightly upward, and L200 would rise straightly upward when roasting time was 2～4 h but changed little when roasting time was 4～6 h. The glass-polishing experiments found that the polishing ability of the ceria-based rare earth oxide was the best as L111 was 43～53 nm and the L200 was 43～56 nm.
文摘Zirconia-ceria mixed oxide powders were prepared by high temperature aging method.The effects of the temperature and the time of aging, cerium content and calcination on powder performance were studied.The result shows that high temperature aging is an efficient way of preparation of ZrO2-CeO2 mixed oxide powders with high specific surface area and good thermal stability, and that addition of a small amount of cerium to hydrous zirconia can promote the preparation of high specific surface area powders.
文摘Martensitic transformation behavior was studied for zirconia containing 4%～10% CeO2 (in mole fraction) by using a dilatometric method. The Ms (Martensite start temperature) decreased near linearly with increasing CeO2. Different transformation modes were observed depending on the composition and cooling rate. ZrO2 containing 6% CeO2 showed isothermal transformation behavior, whereas ZrO2 containing 9% and 10% CeO2 showed athermal transformation behavior. However, ZrO2 containing 8% CeO2 showed either isothermal or athermal transformations behavior depending on the cooling rate. A TTT (Time-Temperature-Transformation) diagram was proposed for ZrO2 containing 8% CeO2.
文摘Nanocrystalline solid solution CeO2-Nd2O3 powders were prepared by low temperature combustion process.Special attention was paid to the influence of the glycine/metal ratio and calcination temperature on the powders phase structure, morphology and particle size.TG-DSC curves and XRD peaks of different glycine/metal ratio show that smaller particle size can be obtained with a slightly fuel-deficient ratio.XRD results indicate that the as-prepared powders are crystallized in a single fluorite structure.The crystalline size ranges from 9 to 24 nm, which increases with the increase of calcination temperature.The lower SEM images were characterized by the spongy and form-like microstructure of the powders.Organic agent may be gradually eliminated by high temperature calcination process.
基金supported by the National Natural Science Foundation of China (21973013 and 21673040 to S.L, and 21962007 to S.Z)the Natural Science Foundation of Fujian Province of China (2020J02025 to S.L)+2 种基金the Natural Science Foundation of Jiangxi Province (2020BABL203009 to S.Z)the Foundation of Jiangxi Educational Committee (GJJ190697 to S.Z)the Qishan Scholarship Program of Fuzhou University (XRC-17055 to S.L)。
文摘CeO_(2)-based catalysts are emerging as novel candidates for catalyzing nitrogen reduction reaction(NRR).However, despite the increasing amount of experimental and theoretical research, the design of more efficient ceria catalysts for NRR remains a challenge due to the poor knowledge of the catalytic mechanism, particularly the nature of the active sites and how they catalyze NRR. Here, using first-principle calculations, we investigated the NRR catalysis process involving adjacent Ce Lewis acid clusters formed on(111),(110), and(100) facets of CeO_(2) as active sites. Our results revealed that the assembled structures of the Ce Lewis acid as active centers after the oxygen vacancies(Ovs) were opened. The exposed Ce sites on CeO_(2)(111), CeO_(2)(110), and CeO_(2)(100) can cause N_(2) to be adsorbed in a ‘‘lying-down" manner, which facilitates the N2 activation and thus leads to much higher NRR activity. Furthermore, from the perspective of electronic structure, we establish two useful descriptors for assessing the NRR activity on ceria with Ovs:The N–N bond strength of the adsorbed N_(2) and the adsorption energy of the *N_(2)H intermediate. This work thus provides direct guidance for the design of more-effective oxide catalysts without the use of scarce metals.
基金financially supported by the Major State Basic Research Development Program of China(No.2012CBA01205)the National Natural Science Foundation of China(No.51274060)。
文摘Ceria(CeO_(2))nanoparticles were successfully synthesized via a simple complex-precipitation route that employs cerium chloride as cerium source and citric acid as precipitant.The elemental analysis results of carbon,hydrogen,oxygen,and cerium in the precursors were calculated,and the results revealed that the precursors were composed of Ce(OH)_(3),Ce(H_(2)Cit)_(3),or CeCit.X-ray diffraction analysis showed that all ceria nanoparticles had a face-centered cubic structure.With the molar ratio of citric acid to Ce^(3)+(n)of 0.25 and pH of 5.5,the specific surface area of the sample reached the maximum value of 83.17 m^(2)/g.Ceria nanoparticles were observed by scanning electron microscopy.Selected area electron diffraction patterns of several samples were obtained by transmission electron microscopy,and the crystal plane spacing of each low-exponent crystal plane was calculated.The ultraviolet(UV)–visible transmittance curve showed that ceria can absorb UV light and pass through visible light.Among all samples,the minimum average transmittance of ultraviolet radiation a(UVA)was 4.42%,and that of ultraviolet radiation b(UVB)was 1.56%.
基金financially supported by the National Natural Science Foundation of China (21872065, 21763013, and 21503100)the Natural Science Foundation of Jiangxi Province (20192ACBL21027 and 20192BAB203007)the Project of Education Department of Jiangxi Province (GJJ170227)。
文摘Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce^(3+) ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.
文摘The solid structures and thermostabilities of Cu Fe O and Cu Fe Ce O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe 2CuO 4, CuO and α Fe 2O 3 phases in Cu Fe O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe 2CuO 4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu 2+ concentration, inhibits the crystal growth of CuO and Fe 2CuO 4 in the catalyst except that of Fe 2O 3, and eliminates the difference for reductive reaction of oxygen in Fe O and Cu O. At 800 ℃, the crystal growth of Fe 2O 3 in Cu Fe Ce O is slower than that in Cu Fe O, i.e., CeO 2 in Cu Fe Ce O inhibits the growth of Fe 2O 3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO 2 promotes the reducibility of catalysts at lower temperature.
文摘Europium doped CeO_2 was synthesized via combustion synthesis method. The powders were found to be in a single phase. The average crystallite size was found to be about 30nm. It was revealed from photoluminescence spectra that there was an excitation band around 368 nm and a narrow excitation peak at 468nm. The emission spectrum showed four peaks at 589, 608, 629 and 650nm.
文摘Ceria- and alumina-pillared interlayered clays were synthesized in the presence of PEO surfactant by using laponite clay as raw material.And the synthesized pillared clays were used as supports to load palladium catalysts for complete oxidation of benzene.Nitrogen adsorption/desorption experiments reveal that the pillared clays have higher tests show that ceria pillar exhibited promoting effect on the activity of the palladium catalysts, and ceria-pillared clay supported palladium catalyst catalyzed the complete oxidation of benzene at less than 250 ℃.The calcination temperature affects the activity of the catalysts significantly, and it is found that the optimal calcination temperature are 600 and 400 ℃ for ceria- and alumina-pillared clay supported palladium catalysts, respectively.
基金the financial support from EPSRC(EP/P024807/1,EP/M014045/1,EP/S000933/1 and EP/N009924/1)by the EPSRC energy storage for low carbon grids project(EP/K002252/1)+3 种基金the EPSRC Joint UK-India Clean Energy center(JUICE)(EP/P003605/1)the Integrated Development of Low-Carbon Energy Systems(IDLES)project(EP/R045518/1)the Innovate UK BAFTA project,the Innovate UK for Advanced Battery Lifetime Extension(ABLE)project for funding underthe China Scholarship Council。
文摘Mixed ionic electronic conductors(MIECs)have attracted increasing attention as anode materials for solid oxide fuel cells(SOFCs)and they hold great promise for lowering the operation temperature of SOFCs.However,there has been a lack of understanding of the performance-limiting factors and guidelines for rational design of composite metal-MIEC electrodes.Using a newly-developed approach based on 3 D-tomography and electrochemical impedance spectroscopy,here for the first time we quantify the contribution of the dual-phase boundary(DPB)relative to the three-phase boundary(TPB)reaction pathway on real MIEC electrodes.A new design strategy is developed for Ni/gadolinium doped ceria(CGO)electrodes(a typical MIEC electrode)based on the quantitative analyses and a novel Ni/CGO fiber-matrix structure is proposed and fabricated by combining electrospinning and tape-casting methods using commercial powders.With only 11.5 vol%nickel,the designer Ni/CGO fiber-matrix electrode shows 32%and 67%lower polarization resistance than a nano-Ni impregnated CGO scaffold electrode and conventional cermet electrode respectively.The results in this paper demonstrate quantitatively using real electrode structures that enhancing DPB and hydrogen kinetics are more efficient strategies to enhance electrode performance than simply increasing TPB.
文摘A series of CeO2-Al2O3, CeO2-TiO2, CeO2-ZrO2, and CeO2-SiO2 mixed-oxide supported copper catalysts were prepared by a modified deposition-precipitation method from ultra dilute aqueous solutions and were investigated for hydrogenolysis of cellulose in aqueous medium, in the presence of hydrogen to produce sorbitol as major product. Among all the catalysts tested in the present work, CuO/CeO2ZrO2?catalyst proved to be the most promising with high conversion (92%) and excellent selectivity (sorbitol 99.1%), at an intermediate reaction temperature of 245°C in a neutral aqueous solution without an aid of liquid phase acid. The catalyst was recyclable in repeated runs and no deactivation was observed even after five reaction cycles. CuO/CeO2-ZrO2 has been characterized by XRD, SEM, TPR and BET surface area techniques.
文摘Copper-based composites strengthened by ceria nanoparticles were processed by conventional powder metallurgy: mixing (30 min and 46 rpm), compaction (cold, uniaxial, 1080 MPa for 10 s) and sintering (800°C for 6 h in vacuum atmosphere of 10−5 torr). It was studied the microstructure (optical microscopy, scanning electron microscopy), X-ray diffraction with Rietveld refinement and some properties (electrical conductivity, Vickers hardness and fracture analysis) of the compositions 92 wt% Cu - 8 wt% CeO2 and 80 wt% Cu - 20 wt% CeO2. The results showed uniform phase distribution, low porosity and ceria disperse inside copper grain. In despite of properties, the composites had electrical conductivity of 38% IACS and 15% IACS and hardness of 69 and 88 HV5, respectively. The results of 92 wt% Cu - 8 wt% CeO2 composites were promising, and they are in according with actual literature.
