RESEARCH ON CATALYSTS OF ANTI-CARBON DEPOSITION FOR CH_4 REFORMING WITH CO_2

IntroductionMethaneandcarbondioxidearetWomaincompositionsforthegreenhouseeffectandtheworldglobewanningll].ItisbeneficialtoourlivingenviroIUnenttocontrolthereleaseofthesetwogases.Theconversionofmethanetothecommonfeedstocksynthesisgas(carbonmonoxideandhydro…     

α-异丙基、β-异丁基丙烯酸希土配合物的合成和配位性质研究

本文制备了α-异丙基、β-异丁基丙烯酸的15种希土配合物RE(C₉H₁₇COO)₃,用X射线多晶粉末衍射、电子光谱、红外光谱和热重差热分析方法研究了配合物中RE-O键的成键性能以及羧基的配位性质.配合物中存在两种不同的羧基配位形式,轻中希土配合物(La,Ce,Pr,Nd,Sm,Eu)中羧基具有不对称桥式双齿配位形式,而重希土配合物(Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y)中羧基具有对称螯合双齿配位形式,配位形式的不同使得希土配合物呈现两种不同的多晶衍射图和热分解过程.     

Anderson结构铁钼杂多酸稀土盐的合成与结构表征

制备了具有Anderson结构的铁钼杂多酸稀土盐，经元素组成分析、TG和ICP确定其通式为Ln[FeMo6O24H6](Ln^3 =La，Ce，Pr，Nd，Sm，Gd，Dy，Yb)．采用IR，UV,^95Mo-NMR，XRD等方法进行了结构表征，发现在IR光谱图上呈现出羟基和H2O的两个振动谱带，并进行了归属，表明此类杂多酸稀土盐属Anderson结构B型．借鉴TG-DTA、不同温度下的IR和XRD及水溶性实验对Ln[FeMo6O24H6]和(NH4)3[FeMo6O24H6]的热解性质研究表明，此类杂多酸稀土盐的分解温度为350～400℃．比母体酸盐的热稳定性提高了10℃．     

RING-OPENING POLYMERIZATION OF TRIMETHYLENE CARBONATE CATALYZED BY NOVEL SINGLE COMPONENT RARE EARTH CALIXARENE COMPLEXES

In this paper, ring-opening polymerization of trimethylene carbonate (TMC) with rare earth (Nd, Y, La) p-tert-butylcalix[n]arene (n=4, 6, and 8) complexes as catalysts has been studied. Poly(trimethylene carbonate) (PTMC) with Mv of 21,400 was produced by bulk polymerization under the conditions as follows: [TMC]0/[Nd] (molar ratio)=1000,80℃,8h. Mechanism study reveals that the polymerization proceeds via a coordination mechanism.     

稀土配位催化马来酸酐-苯乙烯-N-苯基马来酰亚胺三元共聚合

采用稀土配位催化剂研究了马来酸酐、苯乙烯和N 苯基马来酰亚胺的三元共聚合反应 .考察了Al La物质的量的比、不同稀土元素、催化剂浓度、聚合反应时间、单体配比等因素对共聚合反应的影响 .利用核磁、红外、热分析等方法对共聚物进行了初步的表征     

Prospects of Sol-Gel Process for Spectral Hole-Burning Glasses

Persistent spectral hole burning was studied in Eu³⁺ ions-doped Al₂O₃-SiO₂ glass prepared by a sol-gel method. The gel synthesized by the hydrolysis of Si- and Al-alkoxides and EuCl₃·6H₂O was heated in air and hydrogen gas atmospheres. For the glass heated in air to contain OH bonds, the hole was formed by the photoinduced rearrangement of the OH bonds surrounding the Eu³⁺ ions, and was thermally refilled and erased above 200 K. On the other hand, the glass heated in hydrogen gas showed the hole spectrum above 200 K. It was found that the hole depth was independent of the temperature and was 7% of the total intensity at room temperature. The proposed mechanism was the electron transfer between the Eu³⁺ ions and the defect centers formed in glass matrix.     

稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究

合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr₂(L-α-Glu)₂(ClO₄)(H₂O)₇](ClO₄)₃•4H₂O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78～370 K温区, 用精密绝热量热仪测量其低温热容, 在285～306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度T_tr、相变焓Δ_trH_m和相变熵Δ_trS_m分别为(297.158±0.280) K, (12.338±0.016) kJ•mol^－1和(41.520±0.156) J•K^－1•mol^－1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm^－3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: Δ_fH_m⁰＝－(7223.1±2.4) kJ•mol^－1.     

交联聚异丁烯酸甲酯型负载树脂的孔结构与分离稀土性能的关系

本文报导异丁烯酸甲酯型负载树脂的交联度、致孔剂组成和含量对负载树脂孔结构的影响.结果指出,良溶剂和劣溶剂按一定比例混合作为致孔剂,可制备不同孔结构的树脂.致孔剂量增加,树脂表观比重减小,而比表面积、孔体积与平均孔径均增加.交联度从10％增加到35%,表观比重和比表面积增加,而孔体积与平均孔径减小.增加致孔剂所含良溶剂的比例,树脂的表观比重、比表面积增加,而孔体积与平均孔径减小.已制备一系列不同孔结构的2-乙己基膦酸单2-乙己基酯(P507)负载树脂,比较了它们分离La、Ce、Pr、Nd的性能.结果表明,适当孔结构的负载树脂用于萃取色层分离稀土元素具有优良的分离性能.     

Synthesis and structural characterization of ferrocene-based bis(pyrazol-1-yl)borate ligands: FcB(Me)pz2K, Fc2Bpz2K, and 1,1′-fc[B(Me)pz2]2K2 (Fc: ferrocenyl, fc: ferrocenylene, pz: pyrazolyl)

Reaction of the ferrocenyl(dimethylamino)boranes FcB(Me)NMe₂, Fc₂BNMe₂, and 1,1′-fc[B(Me)NMe₂]₂ with 1:1 mixtures of pyrazole and potassium pyrazolide in refluxing THF gave the potassium salts of the ferrocene-based bis(pyrazol-1-yl)borate ligands FcB(Me)pz₂K, Fc₂Bpz₂K, and 1,1′-fc[B(Me)pz₂]₂K₂ in good yield (Fc: ferrocenyl, fc: ferrocenylene, pz: pyrazolyl). In the solid state, FcB(Me)pz₂K and Fc₂Bpz₂K form centrosymmetric dimers with short K?Cp contacts suggesting an η⁵ coordination mode of the potassium ion. The crystal lattice of the ditopic ligand 1,1′-fc[B(Me)pz₂]₂K₂ consists of coordination polymer strands featuring essentially the same structural motif that has been observed for the monotopic derivatives. All three scorpionate ligands are thus promising building blocks for the preparation of ferrocene-containing multiple-decker sandwich complexes.     

Synthesis and Characterization of Poly（butylene adipate-co-terephthalate） Catalyzed by Rare Earth Stearates

Rare earth （Nd, Y, La, Dy） stearates have been synthesized and used as single component catalysts for the polycondensation of dimethyl terephthalate, adipic acid and 1,4-butanediol for the first time preparing biodegradable poly（butylene adipate-co-terephthalate） （PBAT） with high molecular weight, The microstructures of PBAT were characterized by ^1H NMR spectra. The PBAT exhibits good mechanical properties such as high tensile strength （ca. 20 MPa） and long break elongation （〉700%）.