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1.
This work reports the analysis of the distribution of Gd atoms and the quantification of O vacancies applied to individual CeO2 and Gd‐doped CeO2 nanocrystals by electron energy‐loss spectroscopy. The concentration of O vacancies measured on the undoped system (6.3±2.6 %) matches the expected value given the typical Ce3+ content previously reported for CeO2 nanoparticles. The doped nanoparticles have an uneven distribution of dopant atoms and an atypical amount of O vacant sites (37.7±4.1 %). The measured decrease of the O content induced by Gd doping cannot be explained solely by the charge balance including Ce3+ and Gd3+ ions.  相似文献   

2.
Cerium oxide (CeO(2) ) nanoparticles display excellent antioxidant properties by scavenging free radicals. However, some studies have indicated that they can cause an adverse response by generating reactive oxygen species (ROS). Hence, it is important to clarify the factors that affect the oxidant/antioxidant activities of CeO(2) nanoparticles. In this work, we report the effects of different buffer anions on the antioxidant activity of CeO(2) nanoparticles. Considering the main anions present in the body, Tris-HCl, sulfate, and phosphate buffer solutions have been used to evaluate the antioxidant activity of CeO(2) nanoparticles by studying their DNA protective effect. The results show that CeO(2) nanoparticles can protect DNA from damage in Tris-HCl and sulfate systems, but not in phosphate buffer solution (PBS) systems. The mechanism of action has been explored: cerium phosphate is formed on the surface of the nanoparticles, which interferes with the redox cycling between Ce(3+) and Ce(4+) . As a result, the antioxidant activity of CeO(2) nanoparticles is greatly affected by the external environment, especially the anions. These results may provide guidance for the further practical application of CeO(2) nanoparticles.  相似文献   

3.
采用不同方法制备了铈锆复合氧化物催化剂用于催化HCl氧化反应。自发沉积策略制备的CeO2@ZrO2催化剂中,超细CeO2纳米粒子均匀的镶嵌于非晶态ZrO2中。CeO2粒子显著的“尺寸效应”使得该催化剂具有更高的Ce3+和氧空位浓度,而较高的Ce3+和氧空位浓度使得催化剂具有优异的低温氧化还原性能和储释氧能力。催化性能测试表明,CeO2@ZrO2催化剂展现出最好的催化活性(1.90 gCl2·gcat-1·h-1),同时CeO2粒子周围非晶态的ZrO2阻碍CeO2的高温烧结,提高了该催化剂的稳定性。  相似文献   

4.
Highly dispersed Pt‐CeO2 hybrids arched on reduced graphene oxide (Pt‐CeO2/rGO) were facilely synthesized by a combination of the reverse micelle technique and a redox reaction without any additional reductant or surfactant. Under a N2 atmosphere, the redox reaction between Ce3+ and Pt2+ occurs automatically in alkaline solution, which results in the formation of Pt‐CeO2/rGO nanocomposites (NCs). The as‐synthesized Pt‐CeO2/rGO NCs exhibit superior catalytic performance relative to that shown by the free Pt nanoparticles, Pt/rGO, Pt‐CeO2 hybrid, and the physical mixture of Pt‐CeO2 and rGO; furthermore, the nanocomposites show significantly better activity than the commercial Pt/C catalyst toward the hydrolysis of ammonia borane (NH3BH3) at room temperature. Moreover, the Pt‐CeO2/rGO NCs have remarkable stability, and 92 % of their initial catalytic activity is preserved even after 10 runs. The excellent activity of the Pt‐CeO2/rGO NCs can be attributed not only to the synergistic structure but also to the electronic effects of the Pt‐CeO2/rGO NCs among Pt, CeO2, and rGO.  相似文献   

5.
《Electroanalysis》2017,29(6):1586-1595
In this work, we report the development of a highly sensitive capacitance chemical sensor based on a copper C,C,C,C‐ tetra‐carboxylic phthalocyanine‐acrylate polymer adduct (Cu(II)TCPc‐PAA) for phosphate ions detection. A capacitance silicon nitride substrate based Al−Cu/Si‐p/SiO2/Si3N4 structure was used as transducer. These materials have provided good stability of electrochemical measurements. The functionalized silicon‐based transducers with a Cu(II)Pc‐PAA membrane were characterized by using Mott‐Schottky technique measurements at different frequency ranges and for different phosphate concentrations. The morphological surface of the Cu(II)Pc‐PAA modified silicon‐nitride based transducer was characterized by contact angle measurements and atomic force microscopy. The pH effect was also investigated by the Mott‐Schottcky technique for different Tris‐HCl buffer solutions. The sensitivity of silicon nitride was studied at different pH of Tris‐HCl buffer solutions. This pH test has provided a sensitivity value of 51 mV/decade. The developed chemical sensor showed a good performance for phosphate ions detection within the range of 10−10 to 10−5 M with a Nernstian sensitivity of 27.7 mV/decade. The limit of detection of phosphate ions was determined at 1 nM. This chemical sensor was highly specific for phosphate ions when compared to other interfering ions as chloride, sulfate, carbonate and perchlorate. The present capacitive chemical sensor is thus very promising for sensitive and rapid detection of phosphate in environmental applications.  相似文献   

6.
采用不同方法制备了铈锆复合氧化物催化剂用于催化HCl氧化反应。自发沉积策略制备的CeO_2@ZrO_2催化剂中,超细CeO_2纳米粒子均匀的镶嵌于非晶态ZrO_2中。CeO_2粒子显著的"尺寸效应"使得该催化剂具有更高的Ce~(3+)和氧空位浓度,而较高的Ce~(3+)和氧空位浓度使得催化剂具有优异的低温氧化还原性能和储释氧能力。催化性能测试表明,CeO_2@ZrO_2催化剂展现出最好的催化活性(1.90 gCl2·gcat~(-1)·h~(-1)),同时CeO_2粒子周围非晶态的ZrO_2阻碍CeO_2的高温烧结,提高了该催化剂的稳定性。  相似文献   

7.
Ag nanoparticles grown on reduced CeO2-x thin films have been studied by X-ray photoelec-tron spectroscopy and resonant photoelectron spectroscopy of the valence band to understand the effect of oxygen vacancies in the CeO2-x thin films on the growth and interfacial elec-tronic properties of Ag. Ag grows as three-dimensional particles on the CeO2-x(111) surface at 300 K. Compared to the fully oxidized ceria substrate surface, Ag favors the growth of smaller particles with a larger particle density on the reduced ceria substrate surface, which can be attributed to the nucleation of Ag on oxygen vacancies. The binding energy of Ag3d increases when the Ag particle size decreases, which is mainly attributed to the final-state screening. The interfacial interaction between Ag and CeO2-x(111) is weak. The resonant enhancement of the 4f level of Ce3+ species in RPES indicates a partial Ce4+→Ce3+ re-duction after Ag deposited on reduced ceria surface. The sintering temperature of Ag on CeO1.85(111) surface during annealing is a little higher than that of Ag on CeO2(111) surface, indicating that Ag nanoparticles are more stable on the reduced ceria surface.  相似文献   

8.
Perylene diimide‐modified magnetic γ‐Fe2O3/CeO2 nanoparticles (γ‐Fe2O3/CeO2‐PDI) were prepared and exhibited excellent peroxidase‐like activity. The samples were characterized by HR‐TEM, XRD, Raman, N2 adsorption, magnetic strength and XPS. The obtained γ‐Fe2O3/CeO2‐PDI had size of 10~20 nm with high specific surface area of 77 m2/g, and could be easily separated from the aqueous solution by using a magnet, which are in favor of its practical application. Due to the decoration of PDI, the γ‐Fe2O3/CeO2‐PDI possessed more surface defects (Ce3+) and active oxygen species than that of γ‐Fe2O3/CeO2, resulting in the outstanding catalytic performance. And the composite catalyst also showed highly sensitive and selectivity toward VC with a limit of detection of 0.45 μM. Based on the fluorescent results, a possible hydroxyl radical (?OH) catalytic mechanism was proposed. It is believed that the as‐prepared γ‐Fe2O3/CeO2‐PDI nanoparticles are promising biosensors applied for biomedical and food analysis.  相似文献   

9.
A series of precipitants and commercial surfactants (soft templates) were employed to synthesize mesoporous/nano CeO2 by a hydrothermal method. As-prepared CeO2 was impregnated with palladium and employed for low-temperature catalytic oxidation of CO. It was found that both soft templates and precipitants had significant effects on the morphology, particle size, crystallinity, and porous structure of the CeO2, having a significant effect on the surface palladium abundance, molar ratios of surface species, and catalytic activity of the final impregnated Pd/CeO2. Using ammonia as precipitant could facilitate increased surface palladium abundance and surface molar ratios of PdO/Pd SMSI , Ce3+/(Ce3+ + Ce4+), and Osurface/Olattice. The catalytic activity of the final Pd/CeO2 catalysts could be enhanced as well. The optimal P123-assisted ammonia-precipitated Pd/CeO2 catalyst exhibited over 99% catalytic conversion of CO at 50 °C.  相似文献   

10.
It is demonstrated by ESR measurements that O 2 (CO + O2) radical anions result from CO + O2 adsorption on the oxidized surface of CeO2. These radical anions are stabilized in the coordination sphere of Ce4+ cations located in isolated and associated anionic vacancies. This reaction shows an activation behavior determined by CO adsorption. The variation of O 2 (CO + O2) concentration with CO adsorption temperature suggests that surface carbonates and carboxylates participate in this reaction. In the (0.5– 10.0)%CeO2/ZrO2 system, O 2 forms on supported CeO2 and is stabilized on Ce4+ and Zr4+ cations. The stability of O 2 -Ce4+ complexes is lower on supported CeO2 than on unsupported CeO2, indicating a strong interaction between the cerium cations and the support.__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 423–429.Original Russian Text Copyright © 2005 by Il’ichev, Kuli-zade, Korchak.  相似文献   

11.
We report the structural, thermal, optical, and redox properties of Fe‐doped cerium oxide (CeO2) nanoparticles, obtained using the polyol‐co‐precipitation process. X‐ray diffraction data reveal the formation of single‐phase structurally isomorphous CeO2. The presence of Fe3+ may act as electron acceptor and/or hole donor, facilitating longer lived charge carrier separation in Fe‐doped CeO2 nanoparticles as confirmed by optical band gap energy. The increased content of localized defect states in the ceria gap and corresponding shift of the optical absorption edge towards visible range in Fe‐doped samples can significantly improve the optical activity of nanocrystalline ceria. The better‐quality redox performances of the Fe‐doped CeO2 nanoparticles, compared with undoped CeO2 nanoparticles, were ascribed mainly to a decrease in band gap energy and an increase in specific surface area of the material. As observed from TPR studies all Fe ‐doped CeO2 nanoparticles, particularly the 10 mol % Fe doped CeO2 nanoproduct, exhibit excellent reduction performance.  相似文献   

12.
It was established by X-ray diffraction, TPR, and EPR that microemulsion (m.e.) synthesis yields the binary oxides ZrO2(m.e.) and CeO2(m.e.) and the mixed oxide Zr0.5Ce0.5O2(m.e.) in the form of a tetragonal, cubic, and pseudocubic phase, respectively, having crystallite sizes of 5–6 nm. The bond energy of surface oxygen in the (m.e.) samples is lower than in their analogues prepared by pyrolysis. Hydrogen oxidation on the oxides under study occurs at higher temperatures than CO oxidation. ZrO2(m.e.) and CeO2(m.e.) are active in O2 formation during NO + O2 adsorption, while CeO2 is active during CO + O2 adsorption, too. However, its amount here is one-half to one-third its amount in the pyrolysis-prepared samples, signifying a reduced number of active sites, which are Zr4+ and Ce4+ coordinatively unsaturated cations and Me4+-O2− pairs. O2 radical anions are stabilized in the coordination sphere of Zr4+ coordinatively unsaturated cations via ionic bonding, and in the sphere of Ce4+ cations, via covalent bonding. Ionic bonds are stronger than ionic-covalent bonds and do not depend on the ZrO2 phase composition. Zr0.5Ce0.5O2 is inactive in these reactions because of the strong interaction of Zr and Ce cations. It is suggested that Ce(4 + β)+ coordinatively unsaturated cations exist on its surface, and their acid strength is lower than that of Zr4+ and Ce4+ cations in ZrO2 and CeO2, according to the order ZrO2 > CeO2 ≥ Zr0.5Ce0.5O2. Neither TPR nor adsorption of probe molecules revealed Zr cations on the surface of the mixed oxide.  相似文献   

13.
研究了低于300 ℃时两种氧化铈对稀燃阶段NOx存储性能的影响,催化剂由2%(w)Pt/Al2O3(PA)与CeO2-X(X=S,I)机械混合制备. X射线衍射(XRD),BET表面积和扫描电子显微镜(SEM)用于表征材料的物理结构. X射线光电子能谱(XPS)和H2程序升温还原(H2-TPR)用于表面Ce3+和活性氧定量. 原位漫反射傅里叶变换红外光谱(in-situ DRIFTS)用于分析表面NOx吸附物种. 相比于CeO2-I,CeO2-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce3+浓度. 因而,Pt/Al2O3+CeO2-S 表现出优异的NOx存储能力. 此外,PA+CeO2-X(X=S,I)上存在Pt 与CeO2之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NOx存储. PA+CeO2-S上的这种相互作用要强于PA+CeO2-I. 研究表明,表面Ce3+浓度和活性氧含量对NOx存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈(ACS,ACI)之间的相互作用降低,并且两种氧化铈NOx存储性能显著下降. 另外,与PA+ACS(ACI)相比,PA+PACS(PACI)样品NOx存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成.  相似文献   

14.
Organophosphorus‐based nerve agents, such as paraoxon, parathion, and malathion, inhibit acetylcholinesterase, which results in paralysis, respiratory failure, and death. Bacteria are known to use the enzyme phosphotriesterase (PTE) to break down these compounds. In this work, we designed vacancy‐engineered nanoceria (VE CeO2 NPs) as PTE mimetic hotspots for the rapid degradation of nerve agents. We observed that the hydrolytic effect of the nanomaterial is due to the synergistic activity between both Ce3+ and Ce4+ ions located in the active site‐like hotspots. Furthermore, the catalysis by nanoceria overcomes the product inhibition generally observed for PTE and small molecule‐based PTE mimetics.  相似文献   

15.
Antibacterial photodynamic therapy had attracted considerable attention in implant-associated infections treatment due to its high selectivity and no resistance. Actually, bacteria readily formed protective biofilm to cover themselves and impede the permeation of photosensitizers, severely impairing the therapeutic effect. Herein, a collaborative nanosystem was constructed by in-situ growing cerium oxide (CeO2) nanoparticles on porphyrinic metal-organic framework PCN-224, and then mixed with poly-l-lactic acid (PLLA) powder to fabricate CeO2@PCN-224/PLLA scaffold. In the nanosystem, CeO2 was expected to disrupt the biofilm integrity by releasing Ce4+, exposing bacteria. Subsequently, PCN-224 could grab this opportunity to kill the bacteria by generating reactive oxygen species (ROS) under light irradiation, thereby achieving the desired antibacterial effect. Crystal violet staining and agarose gel electrophoresis results demonstrated that the bacterial biofilm was effectively eliminated by cleaving the extracellular DNA chains. Coomassie brilliant blue and acridine orange staining revealed that the generated ROS effectively killed bacteria by destroying their cell membrane, causing DNA hydrolysis and protein leakage. Furthermore, ROS could also weaken the antioxidant capacity of bacteria by consuming their glutathione, further accelerating bacterial death. As a consequence, the scaffolds presented a robust antibacterial rate of 97% against S. aureus. Collectively, this work provides a promising strategy for efficient implant-related infection treatment.  相似文献   

16.
The necessity to drastically act against mercury pollution has been emphatically addressed by the United Nations. Coal‐fired power plants contribute a great deal to the anthropogenic emissions; therefore, numerous sorbents/catalysts have been developed to remove elemental mercury (Hg0) from flue gases. Among them, ceria (CeO2) has attracted significant interest, due to its reversible Ce3+/Ce4+ redox pair, surface‐bound defects and acid‐base properties. The removal efficiency of Hg0 vapor depends among others, on the flue gas composition and temperature. CeO2 can be incorporated into known materials in such a way that the abatement process can be effective at different operating conditions. Hence, the scope of this account is to discuss the role of CeO2 as a promoter, active phase and support in the design of composite Hg0 sorbents/catalysts. The elucidation of each of these roles would allow the integration of CeO2 advantageous characteristics to such degree, that tailor‐made environmental solution to complex issues can be provided within a broader application scope. Besides, it would offer invaluable input to theoretical calculations that could enable the materials screening and engineering at a low cost and with high accuracy.  相似文献   

17.
The two oxidation states of ceria nanoparticles, Ce3+ and Ce4+, play a pivotal role in scavenging reactive oxygen species (ROS). In particular, Ce3+ is largely responsible for removing O2 and .OH that are associated with inflammatory response and cell death. The synthesis is reported of 2 nm ceria–zirconia nanoparticles (CZ NPs) that possess a higher Ce3+/Ce4+ ratio and faster conversion from Ce4+ to Ce3+ than those exhibited by ceria nanoparticles. The obtained Ce0.7Zr0.3O2 (7CZ) NPs greatly improve ROS scavenging performance, thus regulating inflammatory cells in a very low dose. Moreover, 7CZ NPs are demonstrated to be effective in reducing mortality and systemic inflammation in two representative sepsis models. These findings suggest that 7CZ NPs have the potential as a therapeutic nanomedicine for treating ROS‐related inflammatory diseases.  相似文献   

18.
Single Crystals of the Cerium(III) Borosilicate Ce3[BSiO6][SiO4] Colorless, lath‐shaped single crystals of Ce3[BSiO6]‐ [SiO4] (orthorhombic, Pbca; a = 990.07(6), b = 720.36(4), c = 2329.2(2) pm, Z = 8) were obtained in attempts to synthesize fluoride borates with trivalent cerium in evacuated silica tubes by reaction of educt mixtures of elemental cerium, cerium dioxide, cerium trifluoride, and boron sesquioxide (Ce, CeO2, CeF3, B2O3; molar ratio 3 : 1 : 3 : 3) in fluxing CsCl (700 °C, 7 d) with the glass wall. The crystal structure contains eight‐ (Ce1) and ninefold coordinated Ce3+ cations (Ce2 and Ce3) surrounded by oxygen atoms. Charge balance is achieved by both discrete borosilicate ([BSiO6]5– ≡ [O2BOSiO3]5–) and ortho‐silicate anions ([SiO4]4–). The former consists of a [BO3] triangle linked to a [SiO4] tetrahedron by a single vertex. The anions form layers in [001] direction alternatingly built up from [BSiO6]5– and [SiO4]4– groups while Ce3+ cations are located in between.  相似文献   

19.
Ce3Cl5[SiO4] and Ce3Cl6[PO4]: A Chloride‐Rich Chloride Silicate of Cerium as Compared to the Phosphate By reacting CeCl3 with CeO2, cerium and SiO2, or P2O5, respectively, in molar ratios of 5 : 3 : 1 : 3 or 8 : 3 : 1 : 2, respectively, in sealed evacuated silica tubes (7 d, 850 °C) colorless, rod‐shaped single crystals of Ce3Cl5[SiO4] (orthorhombic, Pnma; a = 1619.7(2), b = 415.26(4), 1423.6(1) pm; Z = 4) and Ce3Cl6[PO4] (hexagonal, P63/m; a = 1246.36(9), c = 406.93(4) pm; Z = 2) are obtained as products insensitive to air and water. Excess cerium trichloride as flux promotes crystal growth and can be rinsed off again with water after the reaction. The crystal structures are determined by discrete [SiO4]4– or [PO4]3– tetrahedra as isolated units. Both, the chloride silicate Ce3Cl5[SiO4] and the chloride phosphate Ce3Cl6[PO4], exhibit structural similarities to CeCl3 (UCl3 type), when four or three Cl anions are each substituted formally by one [SiO4]4– or [PO4]3– unit, respectively, in the tripled formula (Ce3Cl9). The coordination number for Ce3+ is thus raised from nine in CeCl3 to ten in Ce3Cl5[SiO4] and Ce3Cl6[PO4], along with a drastic reduction of the molar volume with the transition from Ce3Cl9 (Vm = 186.17 cm3/mol) to Ce3Cl5[SiO4] (Vm = 144.15 cm3/mol) and Ce3Cl6[PO4] (Vm = 164.84 cm3/mol). The polyhedra of coordination around Ce3+ can be described as quadruple‐capped trigonal prisms, which in addition to seven Cl anions each also show another three oxygen atoms of two ortho‐silicate or ortho‐phosphate tetrahedra, respectively.  相似文献   

20.
As an exceptional Fenton-like reagent, cerium oxide (CeO2) finds applications in biomedical science and organic pollutants treatment. The Fenton-like reaction catalyzed by CeO2 typically encompasses two distinct processes: one resembling the classical Fenton reaction, wherein cerium (Ce3+) triggers the decomposition of hydrogen peroxide (H2O2) to yield reactive oxygen species (ROS), and the other involves the complexation of H2O2 on the Ce3+ surface, leading to the formation of peroxides. However, the influence of diverse CeO2 morphologies on these two reaction pathways has not been comprehensively explored. In this study, CeO2 exhibiting three typical morphologies, rods, cubes, and spheres, were prepared. The generation of ROS and peroxides was evaluated using the 3,3,5,5-tetramethylbenzidine (TMB) oxidation reaction and the reduction current of H2O2, respectively. Moreover, the impacts of pH variations and CeO2/H2O2 concentrations on the production and conversion of these two reaction products were investigated. To corroborate the distinctions between the resultant products and their applicability, apoptosis assays and acid orange 7 (AO7) degradation analyses were performed. Notably, CeO2 rods exhibited the highest proportion of Ce3+, predominantly engaging in complexation with H2O2 to foster peroxide formation, thereby facilitating the robust degradation of AO7. However, the generated peroxides appeared to occupy Ce3+ sites, thereby impeding the H2O2 decomposition process. Conversely, Ce3+ species on the surface of CeO2 cubes were primarily involved in H2O2 decomposition, leading to heightened ROS production, and thus showcasing substantial potential for damaging A549 tumor cells. It is worth noting that the ability of these Ce3+ species to form peroxides through complexation with H2O2 was comparatively reduced. In summation, this study sheds light on the intricate interplay between distinct CeO2 morphologies and their divergent impacts on Fenton-like reactions. These findings expand our comprehension of the influences on its reactivity of CeO2 morphologies and open new insights for applications in diverse domains, from organic dye degradation to tumor therapy.  相似文献   

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