TSL and EPR studies of SrBPO5 doped with CeO2 and co-doped with CeO2 and Sm2O3

Thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) investigations were carried out on gamma irradiated SrBPO₅ samples doped with CeO₂ and co-doped with CeO₂ and Sm₂O₃. On gamma-irradiation at room temperature, BO₃ ^2–, O₂ ^– and O^– radicals were produced. It was seen that the O^– radical ion disappeared in the sample annealed at 500 K. It is proposed that the recombination between trapped electrons and O^– radical ions results in transfer of recombination energy to the impurity centre Ce³⁺ resulting in TSL glow peak at 485 K. In the case of co-doped samples energy transfer occurs between Ce³⁺ to Sm³⁺ resulting in increase in the intensity of glow peak at 485 K.The authors are grateful to Dr. V. K. Manchanda, Head, Radiochemistry Division, BARC for his keen interest and encouragement during the course of this work.     

Mechanism of the Formation of O2? Radical Anions on CeO2 and (0.5–10)%CeO2/ZrO2 during the Adsorption of an NO-O2 Mixture

It is established by ESR that the adsorption of an NO + O₂ mixture at 20°C on oxidized CeO₂ (O₂, T = 400–700°C) produces radical anions O ₂ ⁻ located both on isolated Ce⁴⁺ cations (O ₂ ⁻ (1)) and in associated anionic vacancies (O ₂ ⁻ (2)). These species differ in thermal stability. For example, O ₂ ⁻ (2) decomposes at 20°C, while O ₂ ⁻ (1) decomposes at 50°C. Only O ₂ ⁻ (1) species are observed at −196°C in ZrO₂-supported CeO₂. In the case of NO + O₂ adsorption at 20°C, O ₂ ⁻ is stabilized on Zr⁴⁺ cations and decomposes at 270°C. Increasing the cerium oxide content of the ZrO₂ surface from 0.5 to 10% only partially inhibits the formation of O ₂ ⁻ -Zr⁴⁺. The Zr⁴⁺ cation is shown to possess a higher Lewis acidity than the Ce⁴⁺ cation, and the ionic bond in O ₂ ⁻ -Zr⁴⁺ complexes is stronger than that in O ₂ ⁻ -Ce⁴⁺ complexes. ESR, temperature-programmed desorption, and IR spectroscopic data for various adsorption complexes of NO on CeO₂ suggest that, in the key step of O ₂ ⁻ formation, free electrons appear on the surface owing to the conversion of adsorbed NO molecules into nitrito chelates on coordinately unsaturated ion pairs Ce⁴⁺-O ₂ ⁻ .__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 414–422.Original Russian Text Copyright © 2005 by Il’ichev, Shibanova, Ukharskii, Kuli-zade, Korchak.     

Nanosized CeO2–SiO2, CeO2–TiO2, and CeO2–ZrO2 Mixed Oxides: Influence of Supporting Oxide on Thermal Stability and Oxygen Storage Properties of Ceria

The influence of SiO₂, TiO₂, and ZrO₂ on the structural and redox properties of CeO₂ were systematically investigated by various techniques namely, X-ray diffraction (XRD), Raman spectroscopy (RS), UV–Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HREM), BET surface area, and thermogravimetry methods. The effect of supporting oxides on the crystal modification of ceria was also mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahigh dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO₂–SiO₂ sample primarily consists of nanocrystalline CeO₂ on the amorphous SiO₂ surface. Both crystalline CeO₂ and TiO₂-anatase phases were noted in the case of CeO₂–TiO₂ sample. Formation of cubic Ce_0.75Zr_0.25O₂ and Ce_0.6Zr_0.4O₂ (at 1073 K) were observed in the case of CeO₂–ZrO₂ sample. The cell ‘a’ parameter estimations revealed an expansion of the ceria lattice in the case of CeO₂–TiO₂, while a contraction is noted in the case of CeO₂–ZrO₂. The DRS studies suggest that the supporting oxides significantly influence the band gap energy of CeO₂. Raman measurements disclose the presence of oxygen vacancies, lattice defects, and displacement of oxide ions from their normal lattice positions in the case of CeO₂–TiO₂ and CeO₂–ZrO₂ samples. The XPS studies revealed the presence of silica, titania, and zirconia in their highest oxidation states, Si(IV), Ti(IV), and Zr(IV) at the surface of the materials. Cerium is present in both Ce⁴⁺ and Ce³⁺ oxidation states. The HREM results reveal well-dispersed CeO₂ nanocrystals over the amorphous SiO₂ matrix in the case of CeO₂–SiO₂, isolated CeO₂ and TiO₂ (A) nanocrystals and some overlapping regions in the case of CeO₂–TiO₂, and nanosized CeO₂ and Ce–Zr oxides in the case of CeO₂–ZrO₂ sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO₂ is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of mixed oxides is more than that of pure CeO₂ and the CeO₂–ZrO₂ exhibits highest OSC.     

Synthesis and luminescent properties of rare-earth-doped CeO2–CaF2 solid solutions via chemical solution routes

CeO₂–CaF₂ solid solutions were synthesized by a chemical solution method starting from metal acetates, trifluoroacetic acid as a fluorine source, and anhydrous ethanol as a solvent. Precursor gels, which were obtained by drying the resultant ethanolic solution at 110 °C, were heat-treated at a temperature in the range 400–1000 °C in air to obtain powdery products. Elemental analysis by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that heating products actually contained cerium, calcium, oxygen, and fluorine. According to X-ray diffraction analysis, possible reaction pathways under high-temperature treatments were considered as initial formation of fluorides (CeF₃ and CaF₂), subsequent oxidation of Ce³⁺ to Ce⁴⁺ in air, and final conversion to fluorite-type Ce–Ca–O–F solid solutions. Doping of Eu³⁺ or Sm³⁺ ions in the solid solutions led to occurrence of their characteristic photoluminescence due to intra-configurational f–f electronic transitions. Photo-excitation was achieved by irradiation with near ultraviolet light mainly through charge transfer from O²⁻ to Ce⁴⁺ in the solid solutions and subsequent energy transfer to the doped ions. Spectral structures of photoluminescence suggested the occupation of Eu³⁺ or Sm³⁺ in Ce⁴⁺ sites with inversion symmetry in the solid solutions.     

Subsolidus phase relations in the systems CeO2RE2O3 (RE2O3 = C-type rare earth sesquioxide)

The systems CeO₂RE₂O₃ (RE₂O₃ = C-type rare earth sesquioxide) were studied to: (1) investigate the claims of several workers for the existence of a complete solid solution series between CeO₂ and RE₂O₃ and (2) to characterize the weak C-type X-ray diffraction peaks reported by others from samples in the single-phase fluorite solid solution region. It is shown that a complete solid solution series does not exist, and an explanation for the observations of others reporting such is tendered. It is also shown that the observation of C-type reflections in the supposed single-phase fluorite field can be attributed to the partial reduction of Ce⁴⁺ to Ce³⁺ at the firing temperature, resulting in the movement of the bulk composition into a two-phase field of the CeO₂RE₂O₃Ce₂O₃ phase diagram, rather than the formation of a domain structure due to ordering.     

离子交换-双氧水氧化法制备纳米CeO2晶体

以99.995% Ce(NO₃)₃和强碱性阴离子交换树脂为原料，采用离子交换-双氧水氧化法合成制备出纳米CeO₂晶体。并就离子交换反应中的Ce³⁺浓度、树脂加入速度和离子交换温度及H₂O₂加入速度等条件对CeO₂粒径的影响进行了探讨，得出了离子交换-双氧水氧化法制备纳米CeO₂晶体的最佳工艺条件。FTIR、TEM分析表明，离子交换法无需对合成的Ce(OH)₃溶胶进行洗涤即可去除NO₃^-、CO₃^2-等阴离子杂质，并用H₂O₂将该溶胶氧化，经真空干燥可制得粒径分布均匀，平均晶粒尺寸约3 nm，高纯度的CeO₂粉体。     

Raman, XRD and microscopic investigations on CeO2-Lu2O3 and CeO2-Sc2O3 systems: A sub-solidus phase evolution study

A sub-solidus phase evolution study was done in CeO₂-Sc₂O₃ and CeO₂-Lu₂O₃ systems under slow-cooled conditions from 1400 °C. Long-range order probing of X-ray diffraction technique is utilized in conjunction with the ability of Raman spectroscopy to detect the changes in local co-ordination. Lu₂O₃ showed solubility of 30 mol% in CeO₂, thus forming an anion deficient fluorite-type (F-type) solid solution, whereas Sc₂O₃ did not show any discernible solubility. A biphasic region (F+C) was unequivocally detected by Raman spectroscopy in Ce_1−xLu_xO_2−x/2 (0.4?x?0.9) and in Ce_1−xSc_xO_2−x/2 (0.1?x?0.9) systems. Raman spectroscopy was valuable in studying these systems since oxygen vacancies are created on doping RE₂O₃ into ceria and Raman spectroscopy is very much sensitive to oxygen polarizability and local coordination. Back scattered images collected on representative compositions support the above-mentioned results.     

共沉淀法和模板法制备均匀负载CeO2/ SiO2的研究

CeO2是三效催化剂(简称TWC)中被广泛应用的涂层材料[1],其优良的储放氧能力(OSC)可以扩大TWC的工作窗口,并可以在与γ-Al2O3的相互作用中提高Al2O3的高温稳定性[2]。在高温下,CeO2会因晶粒迅速长大而失去储放氧能力。为了提高CeO2的高温抗烧结能力,以及进一步提高其氧化还原能力,大部分研究者选择了在CeO2晶格中掺入其他离子的方法,如:Zr4 、Pr3 、La3 等[3￣5],这些离子在CeO2晶格中引入了晶格缺陷,不但稳定了结构,而且提高了氧传输能力。SiO2具有很高的化学稳定性、高比表面及高热稳定性,是载体的理想选择。研究表明,CeO2负载…     

Electron spin resonance of diluted solid solutions of Gd2O3 in CeO2

Electron spin resonance spectra of Gd³⁺ in diluted solid solutions of Gd₂O₃ in CeO₂ have been studied at room temperature for Gd concentrations between 0.01 and 1.00 mol%. While in the case of Mn²⁺:CeO₂ samples, both the linewidth and the line intensity go through a maximum between 0.2 and 0.4% Mn and then start to decrease, in the case of Gd³⁺:CeO₂ samples the linewidth and the line intensity increase monotonically with the dopant concentration. This as taken as evidence that in Gd₂O₃-CeO₂ diluted solid solutions there are no clustering effects similar to the ones observed in Mn:CeO₂ solid solutions. It is not clear why clustering effects are present in Mn:CeO₂ solid solutions and not in Gd:CeO₂ solid solutions; however, it seems reasonable to assume that this is due to the fact that the ionic radius of Mn²⁺ (81 pm) is about 25% smaller that that of Gd³⁺ (107.8 pm). In any case, the fact that Gd:CeO₂ solid solutions do not exhibit clustering effects means that ESR linewidth data can be used to estimate the concentration of Gd in CeO₂ samples, as it is possible to do in several solid solutions of paramagnetic ions in ceramic materials. The results also suggest that the range of the exchange interaction between Gd³⁺ ions in CeO₂ is about 0.89 nm.     

非晶态ZrO2镶嵌的超细CeO2催化HCl氧化

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 g_Cl2·g_cat^-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。     

费托合成CeO2助Co/SiO2催化剂的失活

在固定床反应器上考察了原粒度(1～3mm)CeO2助Co/SiO2催化剂的费托反应性能,提出了催化剂失活的机理,并采用程序升温还原、X射线衍射和X射线光电子能谱对催化剂进行了表征.结果表明,在1.5MPa,488K和400h-1条件下进行的300h稳定性实验中,原粒度CeO2助Co/SiO2催化剂上的CO平均转化率达到41%,液态烃选择性达到85%,液态烃中C10 烃的质量含量占88%以上.反应器出口的催化剂中有少量的CoO和Co2SiO4生成.催化剂的失活过程受动力学控制而非热力学控制,催化剂的失活机理为:高分散的纳米Co离子在反应器出口高水蒸气压力的作用下,以CoO为中间物种,与水合SiO2作用生成Co2SiO4,即Co H2O→CoO H2,SiO2 H2O→OSi(OH)2,2CoO OSi(OH)2→Co2SiO4 H2O.     

ESR Study of the Formation of O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> Radical Anions on Oxidized CeO<Subscript>2</Subscript> and CeO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript> Adsorbing a CO + O<Subscript>2</Subscript> Mixture

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.     

Role of radical ions in the thermally stimulated luminescence of uranium doped BaCO3 system

Electron paramagnetic resonance (EPR) studies of -irradiated uranium doped BaCO₃ have shown the formation of CO₃ ^–, CO₂ ^–, O₃ ^– and O₂ ^– ions. Thermally stimulated luminescence (TSL) glow curves of the -irradiated samples in the 300–600 K range have exhibited an intense peak around 360 K and a weak one around 440 K. The trap parameters for these peaks have been determined from TSL data. Spectral studies of the glow have revealed emission around 566, 583 and 590 nm characteristic of the uranate ion. From studies on the thermal stabilities of the radical ions, it has been inferred that the glow peak around 360 K is associated with the thermal destruction of O₂ ^– ion and the peak around 440 K is associated with the thermal destruction of CO₃ ^– ion.     

合成方法对Rh/CeO2-ZrO2-La2O3催化剂的结构、表面性能及DeNOx活性的影响

用沉积沉淀法合成两种不同系列的CeO2-ZrO2-La2O3混合氧化物(ZrO2和La2O3沉积CeO2粒子(标记为A-x)以及CeO2和La2O3沉积ZrO2粒子(标记为B-x)),并用作Rh催化剂的载体。XRD、拉曼、TPR、XPS和O2脉冲等表征结果显示出不同的沉积顺序将导致不同的结构和氧化还原性能,且B-x具有更高的氧迁移性、储氧能力和表面Ce浓度。当其负载Rh后,Rh/B-x催化剂具有更高的NO和CO转化率及N2选择性,且Ce的最佳含量为50at%。这可能归因于Rh负载于富铈表面形成更多有利于NO分解的表面Ce3+活性位。     

非晶态ZrO_2镶嵌的超细CeO_2催化HCl氧化

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。     

Growth and Electronic Properties of Ag Nanoparticles on Reduced CeO2-x(111) Films

Ag nanoparticles grown on reduced CeO_2-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 CeO_2-x thin films on the growth and interfacial elec-tronic properties of Ag. Ag grows as three-dimensional particles on the CeO_2-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 CeO_2-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 CeO_1.85(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.     

XRD and UV-Vis diffuse reflectance analysis of CeO2-ZrO2 solid solutions synthesized by combustion method

A series of ceria-incorporated zirconia (Ce_1−xZr_xO₂,x = 0 to 1) solid solutions were prepared by employing the solution combustion synthesis route. The products were characterized by XRD and UV-Vis-NIR diffuse reflectance spectroscopy. The materials are crystalline in nature and the lattice parameters of the solid solution series follow Vegard’s law. Diffuse reflectance spectra of the solid solutions in the UV region show two intense bands at 250 and 297 nm which are assigned respectively to Ce³⁺ ← O²⁻and Ce⁴⁺ ← O²⁻ charge transfer transitions. The two vibrational bands in 6960 cm⁻¹ and 5168 cm⁻¹ in the NIR region indicate the presence of surface hydroxyl groups on these materials.     

纳米CexFe1-xO2固溶体的模板法制备及其乙醇水蒸气重整催化性能

以超高比表面炭材料为模板,硝酸盐为氧化物前体,通过改进的模板路线制备了具有较高比表面积的纳米CexFe1-xO2固溶体.采用X射线衍射、拉曼光谱、物理吸附和透射电镜对制备的样品进行了表征.结果表明,α-Fe2O3,CexFe1-xO2固溶体和CeO2的粒子尺寸为5~15nm,CeO2中部分Ce4 离子被Fe3 离子取代,从而形成了CexFe1-xO2固溶体.乙醇水蒸气重整反应结果显示,CexFe1-xO2固溶体比相应的α-Fe2O3和CeO2具有更高的催化活性和对氢气的选择性.     

Effect of Copper on Solid Electrolytes (Ce0.8Sm0.2)1 ? xCuxO2 ? δ and Composite Cathodes Based on La0.8Sr0.2MnO3

The phase composition and electroconduction in air of solid electrolytes (Ce_0.8Sm_0.2)_{1 − x} Cu_xO_{2 − δ} (CSCu), where x = 0, 2, 5, 10, and 20 mol % and which are synthesized using the ceramic technology, are studied. Adding an additive of CuO lowers the CSCu sintering temperature by 100– 200°C and leads to the formation of single-phase solid solutions of a fluorite type up to x = 10 mol %. The electroconductivity of the CSCu electrolytes remains practically invariant upon adding up to 5 mol % Cu and equals 0.089–0.095 and 0.017–0.021 S cm⁻¹ at 800 and 600°C. The sintering, adhesion, and electroconductance of composite cathodes based on La_0.8Sr_0.2MnO₃ with 40% CSCu and their electrochemical behavior in air in the temperature interval 900–1000°C on carrying electrolyte Zr^0.9Y_0.1O_1.95 with a CSCu sublayer containing 2 mol % Cu are studied.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 656–661.Original Russian Text Copyright © 2005 by Bogdanovich, Gorelov, Balakireva, Dem’yanenko.     

Study on Gd3+ and Sm3+ co-doped ceria-based electrolytes

Doped ceria electrolytes of Ce_1-aGd_a-ySm_yO_2–0.5a, wherein a=0.15 or 0.2, and 0ya, were prepared with the citrate method, and characterized by inductively coupled plasma–atomic emission spectrometry, energy dispersive spectrometry, scanning electron microscopy, powder X-ray diffraction, and AC impedance spectroscopy. The effect of composition on the structure and conductivity was studied. All the samples were fluorite-type ceria-based solid solutions. For the singly doped samples, the optimal composition was Ce_0.85Gd_0.15O_1.925 for Gd³⁺-doped ceria (CGO), which showed higher ionic conductivity than the best Sm³⁺-doped ceria (CSO) at 773–973 K. For the co-doped samples, the ionic conductivities were higher than those of the singly doped ones in the temperature range 673–973 K when a=0.15, but only better in 673–773 K when a=0.2. For the samples of Ce_0.85Gd_0.15-ySm_yO_1.925, wherein 0.05y0.1, much higher ionic conductivity was observed than those of the singly doped ceria at 773K~973 K. Therefore, these co-doped samples would be better than CGO and CSO to be the electrolytes of intermediate-temperature solid oxide fuel cells.