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1.
The design and optimization of nanostructures with unique morphologies and properties are at the forefront of biomedical nanotechnology. Cerium oxides are widely used to investigate the effect of morphology on performance. However, elucidating the morphology–activity relationship of cerium oxide nanocrystals in biomedical applications remains challenging. Herein, the therapeutic effects of cerium oxide nanoparticles with different morphologies: cerium oxide nanorods with two different aspect ratios (CeOx NRs_A and CeOx NRs_B), cerium oxide nanopolyhedra (CeOx NPs), and cerium oxide nanocubes (CeOx NCs) are investigated in in vivo and in vitro mild traumatic brain injury (TBI) models. Cerium oxide nanoparticles inhibit oxidative stress and inflammation after mild TBI, alleviating cognitive impairment; furthermore, the therapeutic effect is significantly affected by their morphology. Owing to the higher Ce3+/Ce4+ ratio, exposure of more active crystal surfaces, and greater number of exposed oxygen vacancies, CeOx NRs show better activity than CeOx NPs and CeOx NCs for mild TBI. Among the two investigated types of cerium oxide nanorods, CeOx NRs_A, with a higher Ce3+/Ce4+ ratio on the surface, appear to spread better than CeOx NRs_B in the injured lesions. The factors causing morphology-controlled biomedical performance, such as Ce3+/Ce4+ molar ratio, surface area, and aspect ratio, are discussed.  相似文献   

2.
《Ceramics International》2022,48(18):25714-25722
Nano-crystalline Ce0.9Zr0.1-xSmxO2-δ (0 ≤ x ≤ 0.10) mixed oxides were synthesized for the first time by a urea-hydrothermal method without the use of template or structure directing agents. The use of a high molar ratio of urea to metal cations and temperature reaction ensures the formation of a single-phase homogeneous ternary solid solution. The (NH4)2Ce(NO3)6 precursor, in a greater proportion, together with urea acts as a structure directing agent towards the completion of a self-assembly shuttle to dumbbells to sphere sequence. The analysis of the obtained morphologies has demonstrated that the physicochemical nature of the doping precursor in solution has a strong influence on the final morphology without losing morphological control. Thus, the ZrO(NO3)2 precursor favors the formation of cauliflower-type particles whereas Sm(NO3)3 favors the formation of spheres. As a result, the morphology of the samples evolves from cauliflowers to spheres as Sm content increases in the mixed oxides, with a great effect on the high specific surface area (80–115 m2.g?1) and total pore volume (0.109–0.315 cm3.g?1) obtained in all cases. Solids reduce in three stages reaching high reduction percentages (≈50%).  相似文献   

3.
《Ceramics International》2019,45(12):15199-15204
{100} planes of CeO2 are unstable polar surfaces and important to enhance the oxygen storage capacity. However, a convenient method is still needed for the synthesis of ceria nanocubes which expose six {100} facets. Here, a new and facile synthesis strategy has been developed to synthesize single-crystalline nanocubes of CeO2. According to transmission electron microscopy, these nanocubes are enclosed by six {100} facets. It is proved that in the synthesis process, the acetate radical ions would adsorb on the positive charged Ce(OH)3 formed from the reaction of Ce3+ and ammonia, then partially inhibit the redox between Ce(OH)3 and NO3 and protect the {100} facets during crystal growth. Meanwhile, the Ce4+ ions would act as crystal seeds to facilitate the formation of single crystals. Both of the addition of Ce4+ ions and CH3COO ions are necessary for the synthesis of monocrystal ceria nanocubes. Throughout the synthesis process, it is moderate reaction conditions that the pressure is atmospheric pressure and temperature is no higher than 80 °C.  相似文献   

4.
The influence of lanthanide metal cations doped into the CeO2 crystal structure (to form Ce0.9Ln0.1O2; Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, or Er) on thermochemical reduction and the CO2 splitting ability of Ce0.9Ln0.1O2 is scrutinized using thermogravimetric analysis. Ce0.9Ln0.1O2 redox materials are effectively synthesized by co-precipitation of hydroxides. As-synthesized Ce0.9Ln0.1O2 redox materials are further characterized based on their phase composition, crystallite size, surface area, and morphology using powder X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, and scanning electron microscopy. The thermal reduction and CO2 splitting aptitude of Ce0.9Ln0.1O2 redox materials are examined by performing 10 consecutive thermochemical cycles. The results imply that insertion of Sm3+, Er3+, Tb3+, Dy3+, and La+3 in place of Ce4+ in the fluorite crystal structure of CeO2 (forming Ce0.9Ln0.1O2) enhances the O2 liberation by 22.5, 14.6, 12.6, 5.85, and 2.96 μmol O2/g·cycle, respectively. Besides, CeLa is observed to be more active towards the CO2 splitting reaction than CeO2 and the other Ce0.9Ln0.1O2 redox materials investigated in this study.  相似文献   

5.
《Ceramics International》2016,42(10):11724-11731
Cobalt-doped cerium dioxide thin films exhibit room temperature ferromagnetism due to high oxygen mobility in doped CeO2 lattice. CeO2 is an excellent doping matrix as there is a possibility of it losing oxygen while retaining its structure. This leads to increased oxygen mobility within the fluorite CeO2 lattice, leading to formation of Ce3+ and Ce4+ species. Magnetic ceria materials are important in several applications from magnetic data storage devices to magnetically recoverable catalysts. In this paper, the room temperature ferromagnetism of rf sputtered Co doped CeO2 thin films is reported whereas undoped CeO2 thin films exhibit paramagnetic behavior. The ferromagnetic properties of the Co doped films were explained based on oxygen vacancies created by Co ions in Ce sites. This is further supported by X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman. Change in surface morphology due to Co doping of the samples were analyzed using atomic force microscopy (AFM).  相似文献   

6.
《Ceramics International》2020,46(5):5976-5982
CeO2 was successfully prepared by electrotransformation of CeCl3 solution in previous work. In this work, the oxidation mechanism of Ce3+ was determined by cyclic voltammetry and a potential-pH diagram, which indicated that Ce3+ was oxidized by oxygen during the electrotransformation, and the important role of the oxygen content in solution was confirmed. Thus, the influence of atmosphere (air/argon/oxygen) on CeO2 preparation was investigated by adjusting the gas type and flow rate. XRD patterns demonstrated the cubic fluorite structure and grain size of CeO2. With an increase in the gas flow rate, the grain size decreased, but the particle size increased. This result indicated that the smaller grains contained more lattice defects and higher surface energy, so the grains preferred to agglomerate together, forming larger particles. XPS spectra proved that Ce3+ and Ce4+ both existed in the CeO2 samples. Raman scattering revealed that more oxygen vacancies could be produced with an argon atmosphere and high gas flow.  相似文献   

7.
Uniform orange‐to‐red spherical phosphors of Sr2P2O7:Ce3+, Mn2+ have been synthesized by the co‐precipitation method and characterized by X‐ray powder diffraction, scanning electron microscopy, and photoluminescence spectroscopy. The results indicate that the morphology, size, and photoluminescence properties of Sr2P2O7:Ce3+, Mn2+ phosphors can be effectively controlled by the reaction and the sintering temperatures. Energy transfer from Ce3+ to Mn2+ in Sr2P2O7 phosphor was observed from photoluminescence spectra of Sr2P2O7:Ce3+, Sr2P2O7:Mn2+, and Sr2P2O7:Ce3+, Mn2+. Moreover, based on a self‐assembly process, a possible formation mechanism for the spherical phosphors is proposed. The uniform phosphor spheres obtained in this work exhibit great potential for high‐resolution display devices such as light emitting diodes.  相似文献   

8.
A series of Fe2O3–CeO2 composite catalysts were synthesized by coprecipitation and characterized by X-ray diffraction (XRD), BET surface area measurement, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Their catalytic activities in CO oxidation were also tested. The Fe2O3–CeO2 composites with an Fe molar percentage below 0.3 form solid solutions with the CeO2 cubic fluorite structure, in which the doped Fe3+ initially substitutes Ce4+ in fluorite cubic CeO2, but then mostly locate in the interstitial sites after a critical concentration of doped Fe3+. With an Fe molar percentage between 0.3 and 0.95, the Fe2O3–CeO2 composites are mixed oxides of the cubic fluorite CeO2 solid solution and the hematite Fe2O3. XPS results indicate that CeO2 is enriched in the surface region of Fe2O3–CeO2 composites. The Fe2O3–CeO2 composites have much higher catalytic activities in CO oxidation than the individual pure CeO2 and Fe2O3, and the Fe0.1Ce0.9 composite shows the best catalytic performance. The structure-activity relation of the Fe2O3–CeO2 composites in CO oxidation is discussed in terms of the formation of solid solution and surface oxygen vacancies. Our results demonstrate a proportional relation between the catalytic activity of cubic CeO2-like solid solutions and their density of oxygen vacancies, which directly proves the formation of oxygen vacancies as the key step in CO oxidation over oxide catalysts.  相似文献   

9.
The synthesis and characterization of some bioglasses based on Hench’s Bioglass® 45S5 with additions of CeO2 (1.0, 2.0, or 3.0%) have been carried out. Two objectives have been focused upon; first, the effect of successive ionizing gamma irradiation on the undoped and CeO2-doped bioglass samples has been evaluated with the aim of justifying the role of the rare earth oxide CeO2 on gamma irradiation. The second objective was directed to test the bioactivity of such prepared CeO2-doped samples after soaking for 1 month in a simulated body fluid at 37 °C. The results indicate that the additions of CeO2 suppress, to a marked extent, the generation of radiation induced defects especially in the visible region. The bioactivity results show that the studied CeO2-doped bioglass samples gave rise to a calcium phosphate surface layer upon immersion in a simulated body fluid for 1 month at 37 °C and the bioactivity extent was almost identical in the CeO2 doping interval limit (1?→?3% CeO2) to that of the undoped base Hench’s Bioglass. The presence of both Ce3+ and Ce4+ ions were confirmed by optical absorption spectra. Electron spin resonance (ESR) studies of gamma irradiated CeO2-doped glasses indicate and confirm the dominance of Ce4+ in the bioglass compositions and its transformation to Ce3+ by high gamma irradiation.  相似文献   

10.
Transparent and colorless CeO2‐activated borogermanate glasses, with the nominal molar composition of 25B2O3–40GeO2–14Gd2O3–1CeO2–(20?x) BaO–xBaF2 (x = 0, 2.5, 5, 10, 15 and 20), were synthesized by a melt‐quenching method in air. Their optical investigation on the transmittance, photoluminescence (excitation and emission spectra), the luminescence decay curves, as well as the temperature‐dependent Ce3+ emission are studied systematically with the gradual substitution of BaF2 for BaO. The room‐temperature photoluminescence results reveal that the emission intensity can be improved by about 2.5 times with the full substitution of BaF2 for BaO. The blue shift of the cut‐off edge, excitation and emission spectra of Ce3+‐activated borogermanate glass, and the emission intensity of Ce3+ ions as a function of temperature range in 80–500 K are also discussed.  相似文献   

11.
《Ceramics International》2020,46(11):18791-18799
Morphology features of cerium oxide nanoparticles, such as size and agglomeration, are important as a coating that improves corrosion resistance and as reinforcement in mechanical applications. In this work, the influence of two heat treatments (160° and 190 °C) in combination with three different chelating agents in the preparation of CeO2 and CeO2 decorated on graphite (CeO2_Gr) nanoparticles is studied. The novelty of this work is that CeO2_Gr was successfully prepared using the hydrothermal method. All the samples evaluated by X-ray diffraction exhibit a single fluorite-type structure in the cubic phase and Fm3m space group. The spherical harmonics method using the Fullprof Suite program was used to determine the average crystallite sizes, which were 9 nm for CeO2 and 7 nm for CeO2_Gr. Transmission electron micrographs for the prepared samples with citric acid showed non-agglomerate particles with homogeneous particle sizes and a quasi-spherical shape distribution. Raman spectra show a band centre at 600 cm-1 associated with the presence of Frenkel-type oxygen vacancies that induced the reduction of Ce4+ to Ce3+. The analysis of X-ray photoelectron spectra corroborates the coexistence of Ce3+ and Ce4+ species for CeO2 and CeO2_Gr nanoparticles. This work forms new perspectives in the development of CeO2 decorated on graphite prepared by the hydrothermal method to obtain composites not only for sensing applications and wastewater treatment but also for corrosion resistance and reinforcement materials.  相似文献   

12.
Surface quality of fused silica, particularly surface defect and surface roughness, is a key factor affecting the performance of high-power laser and short-wave optical instrument, and so on. Herein, the super smooth surface of fused silica with roughness of sub-angstrom level and exceedingly few submicron defects was achieved by using ultrafine nano-CeO2 with primary particle size less than 4 nm, low secondary particle agglomeration strength, and high Ce3+ concentration. Furthermore, CeO2 involve in polishing process in the form of primary particle was certified by experiment. Moreover, the cause for the generation of submicron defects on fused silica surface was investigated for the first time from the perspective of secondary particle agglomeration strength of CeO2. The concentration of Ce3+ in CeO2 was characterized by the redshift of the band-gap energy, and the analysis of material removal rate (MRR) and contact angle of polished fused silica shows that Ce3+ enhances MRR through increasing the silanol group on fused silica.  相似文献   

13.
A series of cerium oxide based materials for hydrogen production from water was studied by temperature-programmed reduction, X-ray diffraction and X-ray photoelectron spectroscopy (XPS) in addition to thermal reactions with water vapour. The addition of uranium ions into CeO2, making mixed oxides Ce x U1?x O2, resulted in noticeable modification of the reduction properties of CeO2; with the main observations being the decrease in reduction temperature and the increase of hydrogen consumption when compared to CeO2 alone. XPS U4f of the as prepared Ce0.5U0.5O2 showed the presence of large amounts of U6+ cations at 380.9 eV in addition to the U4+ cations at 379.9 eV; the ratio U4+ to U6+ cations was found equal to 0.35. XPS Ce3d showed, on the contrary, considerable amount of Ce3+ cations with an estimated ratio of Ce3+ to Ce4+ = ca. 0.5. Ar-ions sputtering results in decreasing the U6+ contribution and a dramatic increase of the Ce3+ contribution. The decrease of U6+ cations was, however, not mirrored by the increase in Ce3+ cations. After five minutes of Ar ions sputtering (1 kV, 10 mA) the surface and near surface Ce3d line shapes looked closer to those of Ce2O3 with prominent Ce3d5/2 and Ce3d3/2 lines at 885.6 and 904.0 eV attributed to v′ and u′, respectively. The Ce x U1?x O2 series was tested for hydrogen production from water (where x = 0, 0.25, 0.5, 0.75 and 1). All uranium containing oxides had higher activity than CeO2 or UO2 alone. Ce0.75U0.25O2 was found to have the highest activity in the studied series; about one order of magnitude higher than that of CeO2 alone at the same temperature. The reason for the enhanced activity is linked to the ease by which oxygen ions are removed from the oxide materials.  相似文献   

14.
A chemical treatment to remove residual CeO2 phase on CeO2–ZrO2 (CZ) solid solution was carried out. A CZ was treated by H2O2 for the reduction of Ce4+ to Ce3+ and then HNO3 for the dissolution of Ce3+ compounds (H–CZ). H2-TPR, TEM-EDX and XPS analyses revealed the removal of CeO2 phase and the homogeneous distribution of Ce species. About 20% improvement in oxygen storage capacity (OSC) of H–CZ was confirmed at 773 K by the weight measurements under H2/N2 and air atmospheres, indicating that the HNO3/H2O2 treatment was effective to avoid the deterioration of the OSC by segregated CeO2 on the CZ binary oxides.  相似文献   

15.
《Applied Catalysis A: General》2001,205(1-2):117-128
We report here the results from a study on the photocatalytic decomposition of water to oxygen over pure WO3, CeO2, and TiO2. It has been demonstrated that Feaq3+ and Ceaq4+ species are efficient electron acceptors during the photoproduction of O2 over a variety of oxides, even at very low concentrations. The O2 yield was found to depend on the type and surface activity of the cation used as an electron acceptor, and the salt counter anion. While Ceaq4+ gives slightly higher initial O2 rates, Feaq3+ tends to give higher long-term O2 yields. The O2 yield was found to be mainly sensitive to the intrinsic properties of a given material, such as the type of the oxide used and its physicochemical characteristics, e.g. crystal structure and level of crystallinity. For the powders tested, O2 production was independent of the BET surface area and the activity does not correlate directly with the onset of light absorption of the powders. With a light having λ≥330 nm, O2 production activity decreased in the order TiO2-rutile>TiO2-anatase>WO3>CeO2⪢amorphous TiO2, whereas with a light having λ≥420 nm, it decreased in the order WO3>TiO2>CeO2. Small amounts of Sn on TiO2-rutile markedly improved its activity. In addition, the O2 yield strongly depended on the concentration of the electron acceptor and the pH of the suspension. During the reaction, small amounts of hydrogen were also produced. The reaction pathways for electron scavenging by Ceaq4+ and Feaq3+, and the process leading to O2 evolution will be discussed.  相似文献   

16.
The catalytic oxidation of soot particulates has been investigated over CeO2, CeO2–ZrO2 and CeO2–HfO2 nanocomposite oxides. These oxides were synthesized by a modified precipitation method employing dilute aqueous ammonia solution. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and BET surface area methods. The soot oxidation has been evaluated by a thermogravimetric method under ‘tight contact’ conditions. The XRD results revealed formation of cubic CeO2, Ce0.75Zr0.25O2 and Ce0.8Hf0.2O2 phases in case of CeO2, CeO2–ZrO2 and CeO2–HfO2 samples, respectively. TEM studies confirm the nanosized nature of the catalysts. Raman measurements suggest the presence of oxygen vacancies, lattice defects and oxide ion displacement from normal ceria lattice positions. UV-Vis DRS studies show presence of charge transfer transitions Ce3+←O2? and Ce4+←O2? respectively. The catalytic activity studies suggest that the oxidation of soot could be enhanced by incorporation of Zr4+ and Hf4+ into the CeO2 lattice. The CeO2–HfO2 combination catalyst exhibited better activity than the CeO2–ZrO2. The observed high activity has been related to the nanosized nature of the composite oxides and the oxygen vacancy created in the crystal lattice.  相似文献   

17.
X-ray photoelectron spectroscopy measurements indicate that the Ce3+ fraction in Al2O3-supported CeO2 can be decreased by the incorporation of La3+. If La3+ is incorporated into the Al2O3 before CeO2 is added, a higher CeO2 dispersion and a greater range of reversible reducibility of the CeO2 may also be obtained. These changes offer potential for improvement in the oxygen storage capacity provided by CeO2 in three-way catalysts.  相似文献   

18.
The Ce x Ti1?x O2 mixed oxides at different mole ratios (x=0.1–1.0) were prepared by co-precipitation of TiCl4 and Ce(NO3)3. The structural and reductive properties of the Ce x Ti1? x O2 were affected by calcination temperature. At x=0.1–0.3, CeTi2O6 phase was formed and mainly as amorphous after calcination at 650°C. At x=0.3, only CeTi2O6 was formed after calcination at 750°C and CeTi2O6 crystallized completely after calcination at 800°C. TPR analyses showed that the amount of H2 consumption by Ce x Ti1?xO2 (650°C) (except x=0.1) was greater than that by single CeO2, and the valence of CeO2was the lowest (+3.18) at x=0.3. CuO/Ce0.3Ti0.7O2 was prepared by the impregnation method and catalytic properties were examined by means of a GC micro-reactor NO+CO reaction system, BET, TPR, XRD, XPS and NO-TPD. It was found that CuO/Ce0.3Ti0.7O2 calcined at 650°C had the highest activity in NO+CO reaction with 100% NO conversion at reaction temperature of 300°C, and at 650°C Ce0.3Ti0.7O2just began to crystallize. The catalytic activities were largely affected by the pre-treatment conditions. At low reduction temperature (100°C), CuO species was difficult to reduce. When high degree of reductions took place, both CuO species and Ce0.3Ti0.7O2 reduced and thus a part of CuO species on the support surface would be covered. The XPS and NO-TPD analyses showed that CuO/Ce0.3Ti0.7O2 had four NO absorption centers (Cu+, Cu2+(I), Cu2+(II) and Ce3+). The CuO species involving in NO+CO reaction included Cu2+(I) and Cu+, and CeO2 species (Ce3+ and Ce4+).  相似文献   

19.
Cu/CeO2, Pd/CeO2, and CuPd/CeO2 catalysts were prepared and their reduction followed by in-situ XPS in order to explore promoter and support interactions in a bimetallic CuPd/CeO2 catalyst effective for the oxygen-assisted water-gas-shift (OWGS) reaction. Mutual interactions between Cu, Pd, and CeO2 components all affect the reduction process. Addition of only 1 wt% Pd to 30 wt% Cu/CeO2 greatly enhances the reducibility of both dispersed CuO and ceria support. In-vacuo reduction (inside XPS chamber) up to 400 °C results in a continuous growth of metallic copper and Ce3+ surface species, although higher temperatures results in support reoxidation. Supported copper in turn destabilizes metallic palladium metal with respect to PdO, this mutual perturbation indicating a strong intimate interaction between the Cu–Pd components. Despite its lower intrinsic reactivity towards OWGS, palladium addition at only 1 wt% loading significantly improved CO conversion in OWGS reaction over a monometallic 30 wt% Cu/CeO2 catalysts, possibly by helping to maintain Cu in a reduced state during reaction.  相似文献   

20.
Quaternary Ni1-xCuxFe2-yCeyO4 complex nano-ferrites system with different cerium content ratio and copper substitution degree were synthesized via co-precipitation wet chemical technique. The newly obtained nanoparticles, with general formula Ni1-xCuxFe2-yCeyO4 (where x = 0.0, 0.3, 0.6 and y = 0.00, 0.03, 0.05, 0.08 and 0.10) were heated up to 600 °C to stabilize the specific crystalline spinel structure. The limit of cerium content was quantitively determined to be around 0.08 and up to 0.10. Furthermore, the powders were pelletized in a 13 mm wide pellets and thermally treated at 950 °C. The thermal treatment affected even more the phases segregation process, as CeO2 was identified in the sample with lowest degree of cerium insertion – 0.03. Also, a difference in color and size of pelletized samples was noticed after the 950 °C thermal treatment. The Rietveld refinement, crystal structure confirmation, morphology magnetic and electrical properties of samples have been deeply studied. The cation distribution carried out from Rietveld refinement confirms the occupancy of (Fe3+) on tetrahedral sites and [Ni2+], [Cu2+], [Fe3+] and [Ce2+] on octahedral sites in the crystal lattice. Preliminary information regarding the cation distribution in spinel structures were suggested by FTIR spectral results, precisely in the 650-520 cm?1 region, as a consequence of peak shape and lack of shiftiness of MTd – O bond. Spherical-shaped quaternary nano-ferrites of 17–28 nm were determined from FE-SEM analysis and the samples composition was confirmed by EDX analysis. Hysteresis loops shows modifications in coercivity, magnetization and magnetic remanence with Ni2+ and Cu2+ ions doping in Ni1-xCuxFe2-yCeyO4 complex systems with typical ferrimagnetic behavior. Dielectric measurements were employed in order to determine the electrical permittivity, dielectric losses and conductivity values in a 10 Hz – 1 MHz frequency range.  相似文献   

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