氧化共沉淀法制备纳米级铈锆固溶体

采用改进的氧化共沉淀法制备了Ce0.5Zr0.5O2固溶体, 利用XRD和BET测定了其结构和比表面积. 采用H2的程序升温还原(TPR)研究铈锆固溶体的还原特性, 以考察它的低温还原特性. 改进的氧化共沉淀法制备的铈锆固溶体在550 ℃可形成立方相固溶体, 具有较大的比表面积和较小的晶粒度, 同时还具有良好的低温还原特性和较高的热稳定性, 经900 ℃焙烧6 h后比表面积达到34.37 m2*g-1.     

不同铝源与铈锆复合的性能及机制

制备了CZ及CZ/AL,CZ/AS与CZ/AM(铈锆固溶体与氧化铝的复合氧化物),通过X射线衍射(XRD)、比表面(BET)、储放氧(OSC)和透射电镜(TEM)等手段对样品的晶相结构、比表面、储氧性能及微观结构等进行表征。结果表明:CZ/AL及CZ/AS都可形成单一稳定的立方晶型结构,氧化铝的掺杂可提高铈锆固溶体的比表面及耐高温稳定性,其中CZ/AS的比表面最高,CZ/AL储氧性能最大。此外,其复合机理表明,Al2O3与铈锆固溶体在纳米级别上的化学复合与纯粹的机械混合相比,前者具有更加稳定的晶型结构、更大的比表面和更好的储氧性能。     

铈锆固溶体制备、表征及其催化分解甲硫醇(CH_3SH)研究

采用微波辅助柠檬酸络合法制备一系列不同铈锆比的铈锆固溶体,考察不同含量锆的掺杂对制备固溶体结构特性以及催化分解甲硫醇性能的影响。通过XRD,BET,Raman,XPS,H_2-TPR,CH_3SH-TPD等手段对其结构物化性能进行表征。表征结果显示:该制备方法成功合成铈锆固溶体且均保留立方萤石结构;锆的引入会导致合成固溶体的晶粒变小、晶格收缩,且晶格参数a随着锆引入量的增加而降低;同时,锆的添加仅仅导致物种缺陷的形成而不会产生更多的氧空位。此外,不同铈锆比固溶体催化分解甲硫醇活性实验结果表明:Ce_(0.75)Zr_(0.25)O_2氧复合物表现出最好的催化活性,之后随着锆的添加其催化性能呈现下降趋势。根据BET,XPS及H_2-TPR表征结果:在表面晶格氧相对含量相近的情况下,Ce_(0.75)Zr_(0.25)O_2因具有最大比表面积、最好的还原性能而表现出最佳的甲硫醇催化活性。最后,考察了Ce_(0.75)Zr_(0.25)O_2催化分解甲硫醇的产物分布情况,结合CH_3SH-TPD表征结果表明:铈锆固溶体催化分解甲硫醇的反应中,二甲基硫醚为中间产物且仅在低温区产生。     

不同沉淀剂对Ce0.65Zr0.35O2复合氧化物性能的影响

本文选用不同沉淀剂,用共沉淀法制备了稀土储氧材料Ce0.65Zr0.35O2复合氧化物,对用不同沉淀剂制备出的氧化物样品进行了XRD,BET,OSC和H2-TPR的测试和分析。结果表明,用不同沉淀剂制备出的氧化物,均为立方相的铈锆固溶体,经1000℃5小时老化后也无相的分离;以(NH4)2CO3和NH3.H2O的混合物为沉淀剂制备出的氧化物有最大的比表面积,经600℃焙烧后高达120m2/g以上;并且样品具有良好的储氧性能及低温还原能力。     

高热稳定性、 高比表面积低铈型铈锆钇储氧材料的制备及其性能研究

采用氨水 碳酸铵混合沉淀剂制备了低铈型铈锆钇三组分储氧材料. 采用X射线衍射、 BET、 氧脉冲吸附和H2程序升温还原(H2-TPR)等技术对材料的晶体结构、 比表面积、 孔结构、 储氧性能和还原性能进行了研究. 结果表明， 该材料经873 K焙烧4 h后比表面积达到116.8 m2/g, 孔容达到0.30 cm3/g, 经1 273 K老化10 h后, 比表面积和孔容仍然保持在68.1 m2/g和 0.22 cm3/g. 由XRD结果可知, 材料的物相组成为四方相的Zr0.84 Ce0.16 O2, 在热处理过程中物相结构稳定. 氧脉冲吸附和程序升温还原的结果表明, 材料储氧性能保持较好.     

铈锆固溶体制备方法的研究进展

铈锆固溶体具有优良的储释氧性能,在三效汽车尾气净化催化剂中起着重要作用,而铈锫固溶体的制备方法与其物化性质又有着密切联系.综述了近几年来国内外铈锆固溶体的制备方法(包括共沉淀法、模板剂法、溶胶-凝胶法、微乳液法等).讨论了晶相结构、比表面积、热稳定性等对固溶体储释氧性能的影响,通过分析固溶体的程序升温还原(TPR)谱图,解释了不同制备方法对所得铈锆固溶体氧化-还原能力的差异.结合文献结果,可以认为寻找工艺简单、性能稳定、重复性好的可控制备方法将是此类材料得到大规模应用的努力方向.     

一锅法合成Ce_xZr_(1-x)O_2固溶体催化剂用于热化学循环分解CO_2制CO

采用一锅蒸发诱导自组装法(EISA)制备了一系列不同铈锆物质的量比的铈锆固溶体催化剂,用TGA研究了其热化学循环分解CO_2制CO的催化性能,并采用XRD、Raman光谱、H2-TPR、XPS、SEM和N_2吸附-脱附等手段对催化剂的物相结构、还原性能和表面化学性质进行了表征分析,用热重分析(TGA)研究了铈锆固溶体对热化学循环分解CO_2制CO的催化性能。结果表明,随着Ce/Zr物质的量比增加,铈锆固溶体催化剂的CO_2高温分解活性先增大后减小。Ce/Zr物质的量比为1的Ce_(0.5)Zr_(0.5)O_2催化剂由于具有较多的晶格缺陷和氧空穴,氧迁移能力强,催化活性高,而Ce/Zr物质的量比为3的Ce_(0.75)Zr_(0.25)O_2催化剂具有相对稳定的氧空穴数,循环稳定性好。循环反应后,所有的催化剂均出现了一定程度的烧结,且富锆固溶体发生了相分离,这可能会影响催化剂的性能。     

CexZr1-xO2/Co/C-N催化CO2加氢性能研究

将不同比例的铈锆前驱体负载到ZIF-67,氮气气氛焙烧制备CexZr1-xO2/Co/C-N催化剂,对催化剂进行了XRD,H2-TPR、XPS表征,并在固定床反应器评价其CO2加氢制甲醇性能。XRD结果表明,在铈中加入适量锆形成铈锆固溶体,铈锆固溶体与钴物种较强的相互作用力可以阻止表明金属Co的氧化。但过量加入的锆又会削弱这一作用力,部分金属Co被氧化为Co3O4。H2-TPR结果表明适量的锆的加入改善催化剂的还原性能,催化剂还原温度降低。XPS证实了25%Ce0.67Zr0.33O2/Co/C-N催化剂中含有更多的氧空穴及氮含量,氧空穴和碱性氮都有利于CO2的解离吸附。优化后的25%Ce0.67Zr0.33O2/Co/C-N 催化剂在225 oC,2 MPa,GHSV = 6 L/gcat/h反应条件下取得最高甲醇时空收率,为3.0 mmol/gcat/h。     

钾元素掺杂对铈锆固溶体中氧物种的影响

采用溶胶-凝胶法制备了一系列不同摩尔比K+掺杂的铈锆固溶体xK-Ce0.7Zr0.3O2(x=0.05,0.10,0.15,0.20,0.25,0.30,0.35,0.40),对其催化碳烟颗粒物(PM)燃烧的活性进行了评价,并采用XRD,H2-TPR,O2-TPD,XPS测试方法对催化剂样品进行了表征。结果表明:K+掺杂后均形成了具有立方面心萤石结构的K-Ce-Zr-O固溶体催化剂。K+掺杂量的改变导致铈锆固溶体产生不同程度的晶格畸变及表面活性氧的含量改变;掺杂K+有利于晶格氧的流动性和铈锆固溶体的释放氧能力的增强,促进催化活性的提高。当0.10≤x≤0.40时,催化剂具有较好的催化性能。     

CexTh1-xO2固溶体的制备和表征

采用柠檬酸法制备了CexTh1-xO2固溶体, 并对固溶体的结构和还原性能进行了表征. 结果表明, 在焙烧过程ThO2和CeO2很容易相互形成立方相的CexTh1-xO2固溶体. 随着Th含量的增加, CexTh1-xO2固溶体的晶胞参数变大. 当形成固溶体时, 经过高温焙烧后固溶体的晶粒明显小于单组分的CeO2和ThO2, 其中Ce0.5Th0.5O2的晶粒最小, 表明CexTh1-xO2固溶体的形成提高了催化剂的抗烧结. Raman光谱表明复合氧化物能促进氧缺位的形成. CexTh1-xO2固溶体的程序升温还原结果表明, 样品有2个还原峰 (α和β), α峰归属为表面Ce4 的还原; β峰归属为体相CeO2的还原. 固溶体的形成使得还原温度降低, 促进CeO2的还原.     

Magnetoresistance in La0.5Sr0.5MnO2.5

Resistance measurements indicate the presence of magnetoresistance in the La_0.5Sr_0.5MnO_2.5 brownmillerite related compound. An 80 % of magnetoresistance is found at 75 K. In spite of the partial break‐up occurring at the 3D network of octahedra sharing corners, characteristic of the full oxygen content perovskite phase, the oxygen deficient compound exhibits complex magnetic and electric properties. Such behavior can be explained on the basis of ferromagnetic and metallic clusters randomly distributed at the octahedral layers separated from each other by an insulating antiferromagnetic matrix. AC susceptibility measurements suggest spin glass behavior at low temperature as a consequence of the competition between different magnetic interactions.     

Amorphous Mo-doped NiS0.5Se0.5 Nanosheets@Crystalline NiS0.5Se0.5 Nanorods for High Current-density Electrocatalytic Water Splitting in Neutral Media

It is vitally important to develop highly active, robust and low-cost transition metal-based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo-doped NiS_0.5Se_0.5 nanosheets@crystalline NiS_0.5Se_0.5 nanorods (Am−Mo−NiS_0.5Se_0.5) was synthesized using a facil one-step strategy. In phosphate buffer saline solution, the Am−Mo−NiS_0.5Se_0.5 shows tiny overpotentials of 48 and 209 mV for hydrogen evolution reaction (HER), 238 and 514 mV for oxygen evolution reaction (OER) at 10 and 1000 mA cm⁻², respectively. Moreover, Am−Mo−NiS_0.5Se_0.5 delivers excellent stability for at least 300 h without obvious degradation. Theoretical calculations revealed that the Ni sites in the defect-rich amorphous structure of Am−Mo−NiS_0.5Se_0.5 owns higher electron state density and strengthened the binding energy of H₂O, which will optimize H adsorption/desorption energy barriers and reduce the adsorption energy of OER determining step.     

SrAu0.5Pt0.5 and CaAu0.5Pt0.5, analogues to the respective Ba compound,but featuring purely intermetallic behaviour

Both, SrAu_0.5Pt_0.5 and CaAu_0.5Pt_0.5, have been synthesized by reaction of corresponding mixtures of the pure elements at 1223 K in an argon atmosphere, and characterized by single-crystal X-ray analysis as well as by magnetic susceptibility and electric resistivity measurements. The new compounds crystallize in the CrB type of structure and thus are isostructural to BaAu_0.5Pt_0.5 (SrAu_0.5Pt_0.5: Cmcm; a = 4.262(1) Å; b = 11.435(3) Å; c = 4.632(1) Å; Z = 4; CaAu_0.5Pt_0.5: Cmcm; a = 3.9858(4) Å; b = 10.920(1) Å; c = 4.5249(5) Å; Z = 4). SrAu_0.5Pt_0.5 as well as CaAu_0.5Pt_0.5 are poor metallic conductors with ρ_300K = 0.95 mΩ.cm and ρ_300K = 3.93 mΩ.cm, respectively, and featuring diamagnetic behaviour.According to ESCA measurements SrAu_0.5Pt_0.5 and CaAu_0.5Pt_0.5 both can be formulated as having intermetallic character, showing a negligible electron transfer from alkaline earth metals to the noble metals.     

Magnetoelectric perovskite (Bi0.5Pb0.5)(Fe0.5Zr0.5)O3: Preparation,structural and magnetic properties

The perovskite (Bi_0.5Pb_0.5)(Fe_0.5Zr_0.5)O₃ was synthesized by solid-state reaction in an attempt to find magnetoelectric materials, in which ferroelectricity and ferromagnetism coexist. This complex perovskite has been studied by X-ray and neutron powder diffraction in combination with magnetic measurements. The compound crystallizes in the orthorhombic space group Pbam with a ～ √2a_p, b ～ 2√2a_p and c ～ 2a_p (with a_p ～ 4.057 Å). The field and temperature dependence of the magnetization combined with neutron diffraction data showed antiferromagnetic behavior with the Neel temperature, T_N ～ 450 K. Rietveld refinements of neutron powder diffraction data collected at different temperatures, between 10 and 700 K, have been carried out in order to extract information about the thermal evolution of the nuclear and magnetic structures. A distorted orthorhombic perovskite structure was found within the whole temperature interval. The Bi/Pb and Fe/Zr ions were found to be partially ordered over the perovskite A-site and disordered over the B-site. The neutron diffraction patterns of the (Bi_0.5Pb_0.5)(Fe_0.5Zr_0.5)O₃ sample showed evidence of a long-range magnetic ordering below T_N with a propagation vector k = (0,0,0) and an antiferromagnetic arrangement of the magnetic moments of the Fe³⁺ cations in the B-site. This is consistent with an A_y-type magnetic structure. The factors governing the structural and magnetic properties of (1 ? x)BiFeO₃–xPbZrO₃ solid solutions are discussed and compared with those of pure BiFeO₃ and PbZrO₃. A solid solution strategy for developing magnetoelectric properties in BiFeO₃-based compounds is described, with the aim of realizing both a spontaneous polarization and magnetization at room temperature.     

Ultra-incompressible Ternary Diborides Re_（0.5）Ir_（0.5）B_2,Re_（0.5）Tc_（0.5）B_2,Os_（0.5）W_（0.5）B_2 and Os_（0.5）Ru_（0.5）B_2：Density Functional Calculation

In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal (P63/mmc) and orthorhombic (Pmmn) structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B (Ru-B) than those of Re-B (Os-B). All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.     

稀土取代的复合氧化物Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．

利用固相反应合成了稀土取代的复合氧化物Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ）．测量了这些化合物的ＸＲＤ和ＸＰＳ谱。在ＸＰＳ研究中发现，稀土取代而使稀土元素本身的结合能相对于其倍半氧化物中的有所降低；在取代的复合氧化物中，随着ＲＥ离子半径的减小，Ｆｅ、Ｍｎ的结合能随之增加。     

Synthesis and structure of CsLi0.5Al0.5PO4

A new phosphate CsLi_0.5Al_0.5PO₄ with a structure related to the β-tridymite structure has been synthesized by a precipitation method. X-ray powder diffraction, electron probe microanalysis, second harmonic generation of laser radiation, and IR spectroscopy have been used for studying the compound. Differential scanning calorimetry shows that the synthesized phosphate undergoes phase transitions at T _tr = 68 and 130°C. The crystal structure of CsLi_0.5Al_0.5PO₄ was refined on the basis of X-ray powder diffraction data by the Rietveld method in space group P2₁/a (Z = 8) with the unit cell parameters a = 17.8323(3) Å, b = 5.4250(1) Å, c = 9.3666(2) Å, β = 89.984(8)°, V = 906.10(9) ų.     

Effect of ZnO on sintering and microwave dielectric properties of 0.5CaTiO3-0.5 (Li0.5La0.5) TiO3 ceramics

The novel calcium titanate-lithium lanthanum titanate doped with zinc oxide (0.10, 0.30, and 0.50 mol. %) ceramic samples were prepared by solid-state reaction route. The phase formation, microstructure, densification, and microwave dielectric properties were investigated. It was found that the doping with zinc oxide led to a decrease in sintering temperature by 25 ^oC as compared with pure calcium titanate lithium lanthanum titanate due to the liquid phase effect. Also, the calcium titanate lithium lanthanum titanate (10ZCTLLT&30ZCTLLT)) doped with lower zinc oxide (0.10 and 0.30 mol. %) led to higher densification parameter. This was followed by increasing the zinc oxide doping up to (0.50 mol. %) which resulted in a decrease in densification and microwave dielectric properties which may be attributed to increase in porosity and grain growth upon the evaporation of zinc and oxygen vacancy. This led to the increase in dielectric loss (≈10 × 10^?4) value with 50ZCTLLT. Hence, the best result of microwave dielectric characteristics was obtained for 0.5CaTiO₃–0.5(Li_0.5La_0.5)TiO₃ with (0.10 and 0.30 mol. % ZnO) 10ZCTLLT and 30ZCTLLT ceramic samples sintered at 1175 ^oC/2h, with low dielectric constant (ε_r) = 4.4–10.5, very low dielectric loss = 1.07-2.23 × 10^?4 and high quality factor (Q x ?) ≈59-55 × 10⁴ at 8 GHz. Consequently, they can be used not only in wireless satellite communications technology but also can be used in the fifth-generation telecommunication 5G technology construction.