铈对混合型贵金属尾气净化催化剂性能的影响

系统地研究了CeO2对负载型混合贯金属催化剂性能的影响，考察了模拟尾气排放条件下铈对催化剂CO氯化性能的影响，并应用XRD、TPD等手段对CeO2在催化剂中的作用机理进行了研究。结果表明，添加助剂后催化剂活性明显提高．铈的添加改变了催化剂的吸附性能．有利于降低催化反应的活化能。     

钴铈复合氧化物在催化氧化中吸附氧的EPR研究

以溶胶-凝胶法制备了钴、铈及其复合氧化物,考察了其对对甲酚催化氧化的性能,复合氧化物表现出优良的活性和选择性.用EPR方法对3个催化剂样品表面吸附氧及其在可控气氛下与对甲酚的作用进行了研究,实验表明,O₂^-可能为活性氧物种,其吸附量及配位环境可与催化活性和选择性相关联。     

邻苯二酚衍生物与希土元素的配位反应Ⅱ．铈(Ⅳ)配合物显现颜色机理的探讨

用实验与量化计算对邻苯二酚类衍生物与铈（Ⅵ）生成的配合笺显现颜色的机理进行了探讨，认为是由配体上大π键电子向中心金属离子跃迁所 产生的Ｌ→Ｍ荷移所致。     

Isomorphous rare‐earth tris[bis(2,6‐diisopropylphenyl) phosphate] complexes and their catalytic properties in 1,3‐diene polymerization and in the inhibited oxidation of polydimethylsiloxane

Crystals of mononuclear tris[bis(2,6‐diisopropylphenyl) phosphato‐κO]pentakis(methanol‐κO)lanthanide methanol monosolvates of lanthanum, [La(C₂₄H₃₄O₄P)₃(CH₃OH)₅]·CH₃OH, ( 1 ), cerium, [Ce(C₂₄H₃₄O₄P)₃(CH₃OH)₅]·CH₃OH, ( 2 ), and neodymium, [Nd(C₂₄H₃₄O₄P)₃(CH₃OH)₅]·CH₃OH, ( 3 ), have been obtained by reactions between LnCl₃(H₂O)_n (n = 6 or 7) and lithium bis(2,6‐diisopropylphenyl) phosphate in a 1:3 molar ratio in methanol media. Compounds ( 1 )–( 3 ) crystallize in the monoclinic P2₁/c space group and have isomorphous crystal structures. All three bis(2,6‐diisopropylphenyl) phosphate ligands display a κO‐monodentate coordination mode. The coordination number of the metal atom is 8. Each [Ln{O₂P(O‐2,6‐ⁱPr₂C₆H₃)₂}₃(CH₃OH)₅] molecular unit exhibits four intramolecular O—H…O hydrogen bonds, forming six‐membered rings. The unit forms two intermolecular O—H…O hydrogen bonds with one noncoordinating methanol molecule. All six hydroxy H atoms are involved in hydrogen bonding within the [Ln{O₂P(O‐2,6‐ⁱPr₂C₆H₃)₂}₃(CH₃OH)₅]·CH₃OH unit. This, along with the high steric hindrance induced by the three bulky diaryl phosphate ligands, prevents the formation of a hydrogen‐bond network. Complexes ( 1 )–( 3 ) exhibit disorder of two of the isopropyl groups of the phosphate ligands. The cerium compound ( 2 ) demonstrates an essential catalytic inhibition in the thermal decomposition of polydimethylsiloxane in air at 573 K. Catalytic systems based on the neodymium complex tris[bis(2,6‐diisopropylphenyl) phosphato‐κO]neodymium, ( 3′ ), which was obtained as a dry powder of ( 3 ) upon removal of methanol, display a high catalytic activity in isoprene and butadiene polymerization.     

纳米KZnF_3∶Ce~(3+)的制备及其光谱特性

采用微乳液法合成了KZnF3∶Ce3 纳米颗粒.分析了样品的结构与形态,结果表明:所合成的样品为单相,颗粒粒度分布均匀.讨论了光谱特性,并与高温固相法合成的产物作了对比.研究发现KZnF3∶Ce3 纳米晶的发射光谱与体相多晶相比,最强谱峰位置红移约35 nm,谱带半高宽加宽约12 nm.     

Synthesis and Structure of One Novel Polyoxometalate Compound Connected via Cerium(Ⅲ) Cation with Three-dimensional Framework H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O

One novel polyoxometalate compound connected via trivalent cerium cation as bridge H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O 1 was designed and synthesized in aqueous solution. X-ray diffraction analysis reveals that the structure of 1 is a three-dimensional framework assembled from the arrangement of H2Mo1.16W10.84O42 (named paradodecmetalate-B) and Ce(H2O)53 containing two planes, which are constructed through the unification of H2Mo1.16W10.84O4210- and Ce(H2O)53 along the [100] and [001] directions. Crystal data: H96Ce4K4Mo2.32O128W21.68, Mr = 7074.89, monoclinic, P21/n, a = 12.5037(17), b = 17.002(2), c = 12.7473(17) (A), β = 105.966(2)°, V = 2605.4(6) (A)3, Z = 1, Dc = 4.509 g/cm3, F(000) = 3132, μ = 26.098 mm(1, R = 0.0377 and wR = 0.0789 (I ＞ 2σ(I)).     

高性能Ce0.35Zr0.55Y0.1O1.95稀土储氧材料的研究

The oxygen storage material (OSM) Ce_0.35Zr_0.55Y_0.1O_1.95 was prepared by co-precipitation routine and studied by means of TEM, XRD, XPS, BET, H₂-TPR and oxygen storage capacity (OSC) measurements. The results indicated that this material possessed plenty of Ce³⁺ and lattice oxygen vacancy (percentage of Ce³⁺ was 59.6%) and high cerium atom utilization ratio (80.04%). The porous material was with an average BET surface area of 97 m²·g^-1 and pore volume of 0.26 mL·g^-1. After aged at 1 000 ℃ in air for 5 h, the sample still possessed plenty of Ce³⁺ and lattice oxygen vacancy (percentage of Ce³⁺ was 57.1%), and showed high cerium atom utilization ratio (78.25%), and high thermal stability.     

Ce和Mg改性的γ-Al2O3负载Pt催化剂催化乙二醇水相重整制氢

 采用浸渍法制备了Ce和Mg改性的 γ-Al2O3 负载Pt乙二醇水相重整制氢催化剂. 采用催化活性评价、N2物理吸附、CO化学吸附、X射线衍射(XRD)和程序升温还原(TPR)等手段系统研究了催化剂的活性、选择性及物化性质. 实验结果表明, Ce和Mg改性的 γ-Al2O3 负载Pt催化剂的活性明显高于Pt/γ-Al2O3 催化剂. 在498 K和2.58 MPa条件下,乙二醇的转化率由72.3%提高到100%, 氢的选择性接近100%. 在Pt/(Ce)γ-Al2O3 和Pt/(Mg)γ-Al2O3 催化剂的XRD谱中,除了 γ-Al2O3 特征峰外,还分别出现了CeO2和Mg-Al层状化合物及微弱的Mg-Al尖晶石结构化合物的特征峰. Ce的存在促进了Pt对乙二醇的吸附-裂解作用和CO水煤气变换反应; Mg的存在中和了 γ-Al2O3 表面的酸性,增加了载体的碱性中心,影响了PtCl2-6的分散,抑制了乙二醇的脱水反应.     

Syntheses and Crystal Structures of Hydrated Ternary Cerium Sulfates: Mixed‐valence K5Ce2(SO4)6·H2O and K2Ce(SO4)3·H2O

A new chemical and structural interpretation of K₅Ce₂(SO₄)₆·H₂O ( I ) and a redetermination of the structure of K₂Ce(SO₄)₃·H₂O ( II ) is presented. The mixed‐valent compound I crystallizes in the space group C2/c with a = 17.7321(3), b = 7.0599(1), c = 19.4628(4) Å, β = 112.373(1)° and Z = 4. Compound I has been discussed earlier with space group Cc. In the structure of I , there are pairs of edge sharing cerium polyhedra connected by sulfate oxygen atoms in the μ₃ bonding mode. These cerium dimers are linked through edge and corner sharing sulfate bridges, forming layers. The layers are joined by potassium ions which together with the water molecules are placed between the layers. No irregularity in the distribution of the Ce^III and Ce^IV to cause the lost of a crystallographic center of symmetry was detected. We suggest that the charge exerted by the extra f¹ electron for every cerium dimer is delocalized over the Ce1–O₂–Ce2 moiety in a non‐bonding mode. As a result, the oxidations state of each cerium ion is a mean value between III and IV at each atomic position. Compound II crystallizes in the space group C2 with a = 20.6149(2), b = 7.0742(1), c = 17.8570(1) Å, β = 122.720(1)° and Z = 8. The hydrogen atoms have been located and the absolute structure has been established. Neither hydrogen atom positions nor anisotropic displacement parameters were given in the previous reports. In compound II , the cerium polyhedra are connected by edge and corner sharing sulfate groups forming a three‐dimensional network. This network contains Z‐shaped channels hosting the charge compensating potassium ions.