Titanium-Containing Mesoporous Materials：Synthesis and Application in Selective Catalytic Oxidation

Titanium-containing mesoporous molecular sieves are of great significance in selective catalytic oxidation processes with bulky molecules. Recent researches and developments on the designing and synthesis of Ti-containing mesoporous materials have been reviewed. Various strategies for the preparation of Ti-containing rnesoporous materials, such as direct synthesis and post-synthesis, are described. Modifications of Ti-containing mesoporous materials by surface-grafting and atom-planting are also discussed. All approaches aimed mainly at the improving of the stability, the hydrophobicity, and mostly the catalytic activity. Structural and mechanistic features of various synthetic systems are discussed. Ti-containing mesoporous materials in liquid phase catalytic oxidation of organic compounds with H2O2 as an oxidant is briefly summarized, showing their broad utilities for green synthesis of fine chemicals by catalytic oxidative reactions.     

Cu-Mn-Ce/γ-Al2O3汽车尾气净化催化材料的合成及性能的研究

采用固定床反应装置，模拟汽车尾气的组成成分，以CO氧化和NH3选择还原NO为探针反应，研究了焙烧温度和焙烧时间等因素对复合金属氧化物催化材料Cu-Mn-Ce-O／γ-Al2O3的催化活性的影响，并考察了该催化剂的抗硫化中毒性能。在本研究条件下，焙烧温度在700℃左右，焙烧时间为2．5h时，催化剂对NO-CO体系中CO的氧化率在76％，以上，对NH3-NO体系中的NO的最佳催化还原率在80％以上。催化剂在3．O％S02／空气气氛中强制中毒后，其在NH3-NO气氛中的最佳反应温度．450℃，同样条件下未中毒催化剂的最佳反应温度为350℃左右，并且催化剂中毒后对NO—NH3的最大转化率没有下降，但是对NO-CO体系的反应活性明显下降，说明该催化剂具有良好的高温活性和抗硫中毒性能。     

可膨胀石墨催化合成乙酸苄酯

可膨胀石墨作为一种重要的非金属材料已广泛应用于各工业领域 ,将其作为有机质反应催化剂的研究尚不多见[1～ 3] 。工业上 ,乙酸苄酯常是以浓Ｈ2 ＳＯ4、对甲苯磺酸等质子酸作催化剂由乙酸和苄醇制得[4] ,但此法腐蚀设备 ,污染环境 ,且副反应多。近年来 ,为了寻找对设备腐蚀性小的酯化反应催化剂进行了一些研究 ,如曾报道的酯化反应催化剂有 :四氯化锡复合物[5] 、复合固体超强酸[6] 、稀土硫酸盐[7]等。本文报道可膨胀石墨催化乙酸苄酯的合成 ,与其它催化剂相比 ,具有催化活性高 ,反应温度低 ,反应时间短 ,收率高 ,易分离及再生处理简单等…     

镧掺杂硫酸钛的酸性及催化缩酮活性

以La2O3为镧源,硫酸钛掺杂镧后经高温焙烧制得一类稀土改性固体酸.用DTA,XRD表征催化剂结构,用吸附吡啶的FT-IR表征其表面酸性,由Hammett指示剂来测定酸强度,以正丁胺定量分析催化剂表面Bronsted酸和Lewis酸酸量;用环己酮与乙二醇缩酮化反应表征其酸催化性能.结果表明:催化剂表面同时存在B酸和L酸中心,且B/L酸量比与焙烧温度、镧的含量呈现较好的线性关系;在缩酮化反应中具有良好的催化活性,在300～600℃的实验范围内,催化活性随灼烧温度的升高而降低,随镧含量的增加而升高,兼有B酸和L酸的催化剂具有更好的催化活性.催化剂易回收和再生,反应后处理简单,无废酸排放,可重复使用多次,该固体酸是一种环境友好催化剂.     

稀土A-Ce-O催化剂的合成及性能研究

采用改进的溶胶-凝胶法合成出了几种含铈稀土复合氧化物催化剂,运用XRD,IR等不同测试手段对复合氧化物催化剂进行了表征,测试了甲烷催化燃烧活性.XRD分析结果表明:经1200 ℃焙烧3 h后4种催化剂中Ba-Ce-O,Sr-Ce-O主要以单一相钙钛矿结构BaCeO3和SrCeO3的形式存在,La-Ce-O体系催化剂呈现面心立方晶体结构特征衍射峰,与立方结构CeO2的衍射峰相似,只是峰的位置偏向低角度;Mg-Ce-O主要以简单氧化物CeO2的相存在,在甲烷催化燃烧反应中La-Ce-O显示出了良好的催化活性,T10为510 ℃,T90为670 ℃;主相为SrCeO3的Sr-Ce-O体系催化剂的甲烷催化活性最差,T10为570 ℃,T90为743 ℃.     

片层纺锤形纳米CuO的制备及性能研究

室温下,以高纯铜片为阳极,石墨棒为阴极,聚乙二醇为分散剂,电解液为pH=10的缓冲溶液,设定初始电压12V.电解后,微波分解,制备了由片层组成的纺锤形纳米CuO(简称片层纺锤形纳米CuO).扫描电子显微镜(SEM)、X-射线衍射仪(XRD)等表征样品的形貌、微观结构及其成分,循环伏安法和计时电流法研究了该纳米CuO对H2O2氧化的催化作用.结果表明：所得产物是纯的单斜片层纺锤形CuO纳米晶,对H2O2的电化学检测具有较高的灵敏度,线性范围为1.0 μmol?L-1~1.0 mmol?L-1,检出限为0.5 μmol.L-1.     

Synthesis and Catalytic Activity of Magnetic Cryptomelane-Type Manganese Oxide Nanotubes

Magnetic cryptomelane-type manganese oxide (OMS-2) nanotubes were successfully prepared by grafting Fe₃O₄ nanoparticles onto the OMS-2 nanotubes. SEM and HRTEM images show that the prepared magnetic OMS-2 nanotubes exhibited diameters of 100?nm, lengths less than 3.0???m, and the diameters of the Fe₃O₄ nanoparticles are less than 10?nm. The synthesized material exhibits excellent magnetic separation and catalytic properties for the degradation of methylene blue (MB) by a Fenton-like reaction.     

氧化二辛基锡催化合成邻苯二甲酸二辛酯

用氧化二辛基锡催化合成邻苯二甲酸二辛酯。探讨了影响其产率的各种因素，邻苯二甲酸酐用量为l00mmol时，n(邻苯二甲酸酐)：n(异辛醇)：n(氧化二辛基锡)=1：3：0．0028，反应温度184℃-220℃，反应时间3．5h，产率在98％以上。     

Cobalt Carbonyls Stabilized by N,P-Ligands: Synthesis,Structure, and Catalytic Property for Ethylene Oxide Hydroalkoxycarbonylation

Reactions of N,P-Ligands as Ph₂P(o-NMe₂C₆H₄) (¹L), 2,6-iPr₂C₆H₃NHC(Ph)=NC₆H₄(o-PPh₂) (²L), and Ph₂PN(R)PPh₂ (R=iPr (³L), cyclo-C₆H₁₁ (⁴L), tBu (⁵L), CH₂C₄H₇O (⁶L)) each with dicobalt octacarbonyl produced complexes [¹LCo(CO)₃]₂ ( 1 ), [²LCo(CO)(μ-CO)₂Co(CO)₃] ( 2 ), [³LCo(CO)₃]⁺[Co(CO)₄]⁻ ( 3 ), [³LCo(CO)₂]₂ ( 4 ), [⁴LCo(CO)₂]₂ ( 5 ), [⁵LCo(CO)₂]⁺[Co(CO)₄]⁻ ( 6 ), and [⁶LCo(CO)₂]⁺[Co(CO)₄]⁻ ( 7 ). Complexes 1–7 have all been structurally characterized by X-ray crystallography, IR and NMR spectroscopies, and elemental analysis. Catalytic tests on transformation of ethylene oxide (EO), CO and MeOH into methyl 3-hydroxypropionate (3-HMP) indicate that complexes 1 – 7 are active, where ion-pair complexes 3 and 6 – 7 behave more excellently (by achieving 88.4–93.6% 3-HMP yields) than the neutral species 1 – 2 and 4 – 5 (35.0–46.5% 3-HMP yields) when the reactions are all operated at 2 MPa CO pressure and 50 °C in MeOH solvent. Density functional theory (DFT) study by selecting 3 as a model suggests a cooperative catalytic reaction mechanism by [Co(CO)₄]⁻ and its counter cation [³LCo(CO)₃]⁺. The cobalt-homonuclear ion-pair catalyzed hydroalkoxycarbonylation of EO is present herein.     

钴铬复合氧化物超细微粒的制备,结构及其催化性能

钴铬复合氧化物超细微粒的制备、结构及其催化性能刘常坤，申永存，奚强（武汉化工学院精细化工系武汉４３００７３）关键词钴铬复合氧化物，超细微粒，催化剂，制备，结构，催化氧化，三甲苯酚，三甲苯醌２，３，６－三甲苯酚（ＴＭＰ）的氧化产物之一２，３，６－三甲苯...     

受限几何型金属化合物的合成和催化性能

通过筛选合成路线和方法制备了3种桥联芴基-芳胺基化合物Me₂Si[（Flu）H]NH-2,6-ⁱPr₂C₆H₃（L¹）、Me₂Si[2,7-^tBu₂Flu（H）]NH-2,6-ⁱPr₂C₆H₃（L²）和Me₂Si[2,7-^tBu₂Flu（H）]NH-2,4,6-Me₃C₆H₂）（L³）,分别与第四族金属氯化物MCl₄反应制备了4种受限几何结构的茂金属化合物[Me₂Si（Flu）（N-2,6-ⁱPr₂C₆H₃）]ZrCl₂（THF）₂（1）、[Me₂Si（2,7-^tBu₂Flu）（N-2,6-ⁱPr₂C₆H₃）]TiMe₂（2）、[Me₂Si（2,7-^tBu₂Flu）（N-2,4,6-Me₃C₆H₂）]TiMe₂（3）和[Me₂Si（2,7-^tBu₂Flu）（N-2,6-ⁱPr₂C₆H₃）]HfMe₂（4）。化合物L¹~L³和1~4都经过谱学和元素分析表征,其中1~3还经过X射线衍射单晶结构确认。在AlⁱBu₃和（Ph₃C）⁺[B（C₆F₅）₄]-双助剂作用下研究了1~4分别催化乙烯/1-辛烯聚合性能,结果显示茂金属单活性中心作用特点以及1-辛烯的共聚效果。考察和比较了其它3种受限几何钛化合物[Me₂Si（C₅Me₄）（N^tBu）]TiCl₂、[Me₂Si（Ind）（N^tBu）]TiCl₂和[Me₂Si（Flu）（N^tBu）]TiMe₂的催化性能;讨论了1~4的结构和催化作用的关联性。     

Catalytic Property of Perovskite-Type Oxide Prepared by Thermal Decomposition of Heteronuclear Complex

It is well-known that the perovskite-type oxides exhibit high catalytic activity for oxidation reaction. The present paper concentrates on catalytic activity and surface composition of the perovskite-type oxide prepared by thermal decomposition of heteronuclear complex.     

新型膦胺配体羰基钌化合物的合成及其催化性能研究

以十二羰基三钌和o-PPh2C6H4NR2(R=H,Me)配体为原料,成功制备了三种新型羰基钌化合物(μ-o-PPh2-C6H4NH)Ru3(μ-H)(CO)9(2)、(o-PPh2C6H4NH)2Ru(CO)2(3)和(μ-o-PPh2C6H4NMe2)2Ru(CO)3(4).对这三个化合物进行了核磁共振和红外谱学、元素分析和X射线单晶衍射分析表征,并对这三个化合物进行了催化性能研究.化合物2和4可催化苯甲醛加氢反应生成苯甲醇,但是3没有催化活性.从实验角度阐述了膦胺配体钌催化剂的结构与性能关联,进一步探讨了加氢催化反应失活的可能原因.     

氧化石墨的谱学表征及分析

采用改进的Hummers法,通过改变氧化剂用量获得不同氧化程度的氧化石墨,用X射线衍射(XRD)、红外光谱(FTIR)和拉曼光谱(Raman)对产物进行结构和谱学特性的表征,并结合数学分析软件对部分红外和拉曼数据进行分峰拟合。结果表明,石墨经氧化后形成了含有C-OH、-COOH和C-O-C等官能团的石墨层间化合物;氧化剂用量较少时,石墨片层插层氧化不完全,产物的结构中仍存在未被氧化的原石墨周期性结构;随着氧化剂用量的增加,氧化石墨产物的XRD图中原石墨(002)衍射峰逐渐消失,结构中含氧官能团的量逐渐增加,产物的亲水性也逐渐增强;通过对红外光谱的拟合发现,氧化石墨样品在3 198 cm^-1附近有一个红外吸收峰,应归属于C-OH中OH的伸缩振动;随着氧化剂用量的增加,所得氧化石墨产物的拉曼光谱中D峰与G峰的强度积分比R(I_D/I_G)逐渐增大,产物结构中sp²平面域的平均尺寸逐渐减小。     

二苯基膦功能化氧化石墨固载铂催化剂的制备及其催化烯烃硅氢加成性能

以氧化石墨为载体,采用二苯基膦配体对其进行改性,再利用膦配体对Pt的螯合配位作用合成了氧化石墨固载膦铂配合物催化剂(GO-P-Pt),并采用元素分析、FT-IR、XRD等方法对催化剂进行了表征,考察了催化剂催化不同烯烃与三乙氧基硅烷的硅氢加成反应性能。结果表明,该催化剂对烯烃与三乙氧基硅烷的硅氢加成反应具有良好的催化活性,在100℃,反应180min后,1-辛烯的转化率为94.6%,β-加成产物的选择性高达99.4%;当底物为芳香烯烃时,β-加成产物的选择性比脂肪烯烃低。此外,催化剂在重复使用4次之后,活性基本保持不变。     

二苯基膦功能化氧化石墨固载铂催化剂的制备及其催化烯烃硅氢加成性能

以氧化石墨为载体,采用二苯基膦配体对其进行改性,再利用膦配体对Pt的螯合配位作用合成了氧化石墨固载膦铂配合物催化剂(GO-P-Pt),并采用元素分析、FT-IR、XRD等方法对催化剂进行了表征,考察了催化剂催化不同烯烃与三乙氧基硅烷的硅氢加成反应性能。结果表明,该催化剂对烯烃与三乙氧基硅烷的硅氢加成反应具有良好的催化活性,在100℃,反应180 min后,1-辛烯的转化率为94.6%,β-加成产物的选择性高达99.4%;当底物为芳香烯烃时,β-加成产物的选择性比脂肪烯烃低。此外,催化剂在重复使用4次之后,活性基本保持不变。     

介稳态氧化钨超微粉体的水热合成与光致变色性质研究

Under hydrothermal conditions, the superfine powders of cubic pyrochlore-type of tungsten oxide and hexagonal tungsten bronze were obtained by using Na₂WO₄·2H₂O as the starting material. The products were characterized by XRD, TG, IR, UV and EPMA, respectively. The effects of the pH value, the acid concentration, reaction temperature and time on the structure and particle size of products were investigated in detail. The conditions for the preparation of superfine powders of tungsten oxide were optimized. The pH 2.5～4.5 of the reaction system led to the formation of a pyrochlore phase and pH 0.5～2.0 gave the hexagonal tungsten bronze structure. The photochromism property of the hexagonal tungsten bronze was studied. The results show that pyrochlore and bronze phases are decomposed at 300 ℃ and 450 ℃, respectively. With the increasing of temperature, the structure of the two oxides changes. The pyrochlore-type powder changes completely into triclinic Na₂W₄O₁₃ around 500 ℃, while the bronze phase into a mixture of Na₂W₆O₁₉ and triclinic WO₃ at 550 ℃. The powder of the hexagonal tungsten bronze showed better photochromism property.     

Catalytic Performance of Graphite Oxide Supported Au Nanoparticles in Aerobic Oxidation of Benzyl Alcohol: Support Effect

Various Au/GO catalysts were prepared by depositing Au nanoparticles on thermally- and chemically-treated graphite oxide (GO) supports using a sol-immobilization method. The surface chemistry and structure of GO supports were characterized by a series of analytical techniques including X-ray photoelectron spectroscopy, temperature-programmed desorption and Raman spectroscopy. The results show that thermal and chemical treatments have large influence on the presence of surface oxygenated groups and the crystalline structure of GO supports. A strong support effect was observed on the catalytic activity of Au/GO catalysts in the liquid phase aerobic oxidation of benzyl alcohol. Compared to the amount and the type of surface oxygen functional groups, the ordered structure of GO supports may play a more important role in determining the catalytic performance of Au/GO catalysts.     

双(烷基二茂铁基)丙烷的合成及其燃速催化性质

双(烷基二茂铁基)丙烷的合成及其燃速催化性质;二茂铁衍生物;燃速催化剂     

Birnessite和Cryptomelane型氧化锰的可控合成及其催化性能

以葡萄糖和高锰酸钾为原料,采用溶胶-凝胶法合成了birnessite(K_(1.35)MnO_2,简写为Bir)和cryptomelane(K_(0.27)MnO_2,简写为Cry)型氧化锰;采用X射线衍射、原子吸收光谱等考察了凝胶处理方法、反应物浓度比、焙烧温度和反应时间等对氧化锰晶型的影响.结果表明,采用不同方法处理凝胶可实现对Bir和Cry型氧化锰的可控合成.以不同的处理方法,葡萄糖和高锰酸钾的浓度比为O.74,反应20s制成凝胶,并在400℃焙烧2h,可分别制取高结晶度和高纯度的Bir和Cry型氧化锰.Bir和Cry型氧化锰在二甲醚燃烧反应中表现出优异的催化性能,且Cry型氧化锰的催化活性更高.