高效组合型 Pd/C 催化剂用于 Suzuki 偶联反应

 采用有机金属 Pd2(dba)3 (dba 为二亚苄基丙酮) 还原分解法制得均匀分布的 Pd 纳米颗粒 (粒径为 3~6 nm) 混合液, 并用活性炭直接吸附得到了组合型 Pd/C 纳米催化剂. 采用透射电子显微镜、X 射线光电子能谱和 X 射线衍射等手段测定了催化剂表面 Pd 颗粒大小分布、晶型和化学态等. 将该催化剂用于 Suzuki 碳-碳偶联反应, 其催化活性比浸渍法制备的 Pd/C 催化剂高 2 倍以上. 以溴代芳烃为底物时, 在 80 oC 下 0.5 h 后偶联产物收率可达 98% 以上. 以邻氯硝基苯为底物时, 在 110 oC 下 1 h 后偶联产物收率可达 64%; 延长反应时间, 产物收率可达 90% 以上.     

Zr基载体负载Pd催化剂用于贫燃天然气汽车尾气净化

 采用共沉淀法制备了 ZrO2, Y0.1Zr0.9Ox, Ce0.1Zr0.9Ox 和 Al0.1Zr0.9Ox 系列 Zr 基载体, 并用 N2 吸附-脱附和 X 射线衍射对其进行了表征. 再以此为载体, 采用浸渍法制备了整体式负载 Pd 催化剂, 催化剂涂层的涂覆量为 180 g/L 左右, Pd 含量为 1.25%. 测定了催化剂上 Pd 的分散度. 在模拟的贫燃天然气汽车尾气中考察了催化剂的活性, 并在尾气中有或无 SO2 存在的条件下比较了催化剂活性的差异. 结果表明, Y3+, Ce4+ 或 Al3+ 改性载体负载的 Pd 催化剂的耐硫性能明显改善; 无论尾气中是否存在 SO2, 以 Y3+ 或 Al3+ 改性载体负载的 Pd 催化剂的活性均明显高于 ZrO2 负载体的 Pd 催化剂.     

助剂对镍基催化剂催化裂解生物质气化焦油性能的影响

 采用等体积浸渍法制备了不同助剂 (Fe, Mg, Mn 和 Ce) 修饰的镍-凹凸棒石粘土基催化剂 (Ni/PG), 并用于催化裂解生物质气化焦油反应. 采用 X 射线衍射和透射电子显微镜对 Ni/PG 催化剂进行了表征, 并用总碳分析仪测定了催化剂上的积炭. 结果表明, 助剂的种类及其含量对催化剂性能的影响显著, 在所选用的助剂中, Fe 助剂入最有利于提高 Ni/PG 催化剂上焦油的去除率和 H2 的收率, 且随助剂 Fe 含量的增加, 催化剂活性逐渐提高.     

铈酸钡和钇掺杂的铈酸钡复合氧化物的制备及其在钌基氨合成催化剂中的应用

 采用柠檬酸法合成了 BaCeO3 和掺杂 Y3+的 BaCe0.9Y0.1O3-δ 复合氧化物, 以 Ru3(CO)12 为前体, 利用浸渍法制备了 Ru/BaCeO3 和 Ru/BaCe0.9Y0.1O3-δ 催化剂. 通过 X 射线衍射、扫描电镜和透射电镜技术对样品进行了表征, 并在固定床反应器中考察了催化剂的氨合成反应活性. 结果表明, 载体 BaCeO3 的稳定性优于 BaCe0.9Y0.1O3-δ, 但 Ru/BaCe0.9Y0.1O3-δ 催化剂的氨合成活性明显高于 Ru/BaCeO3, 在 3.0 MPa, 15 000 h1, 425 oC 反应时, Ru/BaCe0.9Y0.1O3-δ 催化剂上氨合成反应速率达到 432.5 ml/(g•h), 是 Ru/BaCeO3 催化剂的 1.6 倍. 这种活性和稳定性的显著差异来自载体中 Ce4+ 与 Ru 纳米粒子间的电子作用.     

Synthesis and Crystal Structure of a New Zn(Ⅱ) Complex Exhibiting Strong Luminescence

The title complex,[Zn(ip)2(H2O)2][ZnCl4]·H2O·2DMF 1(ip=imidazo[4,5-f][1,10] phenanthroline),has been synthesized via the slow evaporation of concentrated reaction solution at room temperature.It was characterized by single-crystal X-ray diffraction.Crystal data for C32H36Cl4N10O5Zn2:white prism,0.17mm×0.15mm×0.10mm,monoclinic,space group P2/c,a=11.928(8),b=9.868(6),c=16.520(11),β=104.879(12)°,V=1879(2)3,Z=2,Mr=913.25,Dc=1.614 g/cm3,F(000)=932,μ=1.616 mm-1,λ(MoKα)=0.71073,GOOF=1.045,R=0.0710 and wR=0.1755 for 3055 observed reflections with Ⅰ2σ(Ⅰ).X-ray diffraction study reveals that the title complex has an interesting 3D architecture via hydrogen bonding interactions and π-π interactions.The IR,TGA,XRD and luminescent properties of complex 1 were also studied.     

Hydrothermal Syntheses and Crystal Structures of Zn(Ⅱ) and Co(Ⅱ) Complexes Constructed from 5-Methoxyisophthalic Acid and 1,10-Phenanthroline Ligands

Two new one-dimensional coordination polymers,[Zn(L)(phen)]n 1 and {[Co2(L)2(phen)2]·2H2O}n 2(H2L=5-methoxyisophthalic acid,phen=1,10-phenanthroline),have been obtained by hydrothermal conditions.According to their single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P2/c with a=8.9195(11),b=12.3620(15),c=17.0211(18),β=106.690(5)o,V=1797.7(4)3,the final R=0.0298 and wR=0.0715 for 3351 independent reflections with Rint=0.0353.Complex 2 crystallizes in the monoclinic system,space group C2/c with a=24.981(4),b=11.1204(19),c=18.125(3),β=132.5620(10)o,V=3708.5(11)3,the final R=0.0349 and wR=0.0914 for 3424 independent reflections with Rint=0.0214.Both 1 and 2 show L-bridged one-dimensional chain.1 and 2 are further assembled by π-π and hydrogen bonding interactions into 2-D layer structures,and they also display 3-D supramolecular frameworks through their other hydrogen bonds.Zn(Ⅱ) ion is five-coordinated with a distorted trigonal bipyramidal coordination geometry,while Co(Ⅱ) ion is six-coordinated and resides in a distorted octahedral coordination geometry.Additionally,complex 1 shows fluorescence in the solid state at room temperature.     

A New Supramolecular Compound Based on Cd（II）-Schiff-base and Keggin-type [PMo_（12）O_（40）]~3

A new supramolecular compound, {[Cd(L)2]2[PMo12O40NO3]·CH3CN·2H2O}n 1 (L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), based on Cd(II)-Schiff-base and Keggin- type [PMo12O40]3- was synthesized via self-assembly and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a = 12.0128(11), b = 13.6196(13), c = 13.9995(13) , α = 103.868(2), β = 95.225(2), γ = 101.024(2)°, V = 2160.0(3) 3, Z = 1, C34H39N26O45Cd2Mo12P, Mr = 2938.96, Dc = 2.259 g/cm3, μ = 2.276 mm-1, F(000) = 1400, the final R = 0.0565 and wR = 0.1613 for 4973 observed reflections with I 2σ(I). The crystal structure can be described by the packing of Keggin anionic and Metal-Schiff-base cationic layers.     

Synthesis and Crystal Structure of a Di-μ_2-phenolic Bridged Binuclear Manganese(Ⅲ) Schiff Base Complex

A new complex [Mn(L)(NCS)]2·0.5CH3CN (H2L = N,N'-bis(chlorosalicylidene)-1,2-diaminoethane) has been synthesized,and its structure (C70H51Cl8Mn4N13O8S4,Mr = 1833.84) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system,space group C2/c with a = 25.883(2),b = 12.3320(13),c = 13.5951(16) ,β = 112.906(2),V = 3997.2(7) 3,Z = 2,Dc = 1.524 g/cm3,μ(MoKα) = 1.050mm-1,F(000) = 1852,S = 1.098,the final R = 0.0630 and wR = 0.1847 for 2542 reflections with Ⅰ 2σ(Ⅰ). The centrosymmetric title complex contains a dimer in which two distorted octahedral Mn(Ⅲ) centers are bridged equatorially by phenolic oxygen of the Schiff base ligand. The units of the complex are linked via weak C-H···N hydrogen bonds,leading to the formation of 1D chains along the b axis. The weak π-π packing interactions and weak intermolecular C(3)-H(3)···N(3) hydrogen bonds stabilize the crystal structure.