还原温度对超细K－Co－Mo催化剂合成低碳醇性能的影响

 用溶胶－凝胶法合成了K－Co－Mo催化剂．样品经不同温度还原后，用于低碳醇的合成．XRD和HRTEM结果表明，样品是超细粒子，粒子尺寸为2～5nm．考察了催化剂的还原温度和反应条件对催化剂性能的影响．实验结果表明，还原温度对催化剂的活性有较大的影响，最佳还原温度为500℃．最佳反应温度范围为310～330℃．升高压力和空速可以提高醇的收率和选择性．在空速14400h－1，压力6．0MPa和温度310℃的条件下，醇的选择性为55．8％，收率为520．0g／（kg·h），MeOH／C2＋OH为0．27．催化剂稳定性良好，在200h的寿命实验中，活性基本不变．与文献中催化剂相比，超细K－Co－Mo催化剂对合成醇具有较高的活性和选择性，尤其是对C2＋OH的合成明显高于其他合成醇催化剂体系．     

α碘-α-甲氧羰亚甲基三苯胂的合成及其与芳醛的反应

胂叶立德分子中砷原子是以4 d 轨道稳定α-碳负离子,比相应的膦叶立德具有更强的亲核性,甲氧羰亚甲基三苯胂能与醛、酮顺利反应。因此,研究稳定的胂叶立德更具有合成     

苯与丙烯烷基化失活沸石催化剂氢再生机理

对工业中试用于苯与丙烯烷基化失活β－沸石改性催化剂进行了H2再生研究。通过对失活、新鲜和再生后催化剂的TPO、TPD、孔结构测定和活性评价以及失活和再生催化剂样品上炭组成的GC－MS分析，讨论了H2再生后催化剂催化性能的恢复状况。解释了虽然仍有部分炭未被除去，但酸性和活性恢复良好的原因。提出了本文体系失活催化剂H2再生过程的作用机理。     

Water/Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous highsurface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

3-N-丙酰基-2-芳基-5-(2-碘苯基)-1,3,4-噁唑啉类化合物的合成

2-碘苯甲酰肼与芳醛反应得到相应的酰腙(1),1再与丙酸酐脱水环化合成了3-N-丙酰基-2-芳基-5-(2-碘苯基)-1,3,4-噁唑啉类化合物,其结构经1H NMR,IR,MS和元素分析表征。     

La2O3-Mo5Si3/MoSi2复合材料的高温氧化行为

研究了0．8％La2O3-MosSi3／MoSi2复合材料在1200℃空气中的高温氧化行为。结果表明：0．8％稀土和MoSi3的加入，使材料的抗氧化性能降低。MosSi3含量越高，材料的抗氧化性能越差。当MosSi3含量低于30％时，在氧化初始阶段，质量变化呈直线下降，随着氧化的进行，氧化逐渐增重，材料表面形成较致密的SiO2阻止了材料的进一步氧化，使得氧化增重较小。而0．8％La2O3-40％Mo5Si3／MoSi2复合材料却出现了“粉化”现象。0．8％La2O3．MosSi3／MoSi2复合材料抗氧化性能的降低，归因于Mo5Si3差的抗氧化性和材料致密度的降低；另外，稀土和Mo5Si3的加入，细化了材料的晶粒，使晶界面积增加，加速了氧在晶界中的扩散，促进了材料的氧化。     

Synthesis and Structure of a Dinuclear Copper（Ⅱ）- ditetrazolate Involving in situ Ligand Synthesis

The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuCl2, 2,2′-bipyridine and H2O affords a novel dinuclear copper(II)-ditetrazolate, [Cu(bpy)- (pdtz)]2 (Hpdtz = 5,5′-1,2-phenylene-ditetrazole, bpy = 2,2′-bipyridine). The pdtz ligand is generated in situ through Sharpless 2 3 cycloaddition reaction. Its crystal structure was deter- mined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P21/n with a = 8.2096(16), b = 18.580(4), c = 11.838(2) , β = 103.12(3)o, V = 1758.5(6) 3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm3, F(000) = 876 and μ = 1.272 mm-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.     

机械球磨与反应烧结合成Sr2CeO4发光体的研究

Sr₂CeO₄ phosphor was synthesized by mechanical milling and reactive sintering in this work. The solid state reaction of SrCO₃and CeO₂ (2∶1) started at about 850 ℃ and completed at 1 000 ℃ for about 4 h. Two types of formation mechanism of Sr₂CeO₄ were proposed. When the starting powder mixture was fired above 1 000 ℃, the unstable intermediate phase SrCeO₃was developed, which then reacted with SrCO₃to form the final product Sr₂CeO₄, however, SrCO₃and CeO₂ converted directly to Sr₂CeO₄ at a lower temperature. The XRD results showed the crystal structure of Sr₂CeO₄ was orthorhombic. The emission spectra displayed a broad band with maximum at about 465 nm. The mechanical milling of starting power mixture and the sintering temperature had no effect on this emission spectra.     

稀土对MoSi2力学性能和抗氧化性能的影响

采用自蔓延和真空烧结方法制备了掺杂0．9％La2O3的MoSi2基复合材料，利用热重分析法，SEM和X射线考察了La2O3颗粒对MoSi2力学性能、抗氧化特性以及循环氧化后力学性能的影响。结果表明，与纯MoSi2相比，RE／MoSi2材料的弯曲强度和断裂韧性分别提高了46％和78％；稀土对MoSi2材料的强韧化机制主要是细晶强化、弥散强化和细晶韧化。RE／MoSi2的氧化增重是纯MoSi2的2．5倍，稀土使MoSiz材料的抗氧化性能降低。由于纯MoSi2材料氧化后的晶粒长大，其抗弯强度比氧化前降低了17％。稀土对MoSi2氧化时的晶粒长大倾向有抑制作用，使得RE／MoSi2材料的抗弯强度基本不变。     

Studies of a new series of ion-pair complexes [Mo(dtc)_4][Ln(dtc)_4] (Ln=La-Er,exp.Pm)

A new series of ion-pair complexes [Mo(dtc)4][Ln(dtc)4] (Ln=La-Er, exp. Pm) were synthesized from MoCl5, LnCl3 and Nadtc in anhydrous methanol. The crystal structures of the four complexes, [Mo(dtc)4][Ln(dtc)4] (Ln=Nd, Sm, Ho and Er) have been determined by X-ray diffraction. Spectroscopic properties of all these complexes are also discussed here.