紫外光谱法实时测定腈水合酶的催化动力学

采用紫外光谱法研究了腈水合酶催化丙烯腈水合的过程,在不同丙烯腈初始浓度下,测定了催化过程中275nm紫外吸光度的变化,计算出丙烯酰胺的生成速率.用Michaelis-Menten方程对不同丙烯腈浓度下的Nocardiasp.腈水合酶催化速率进行了拟合,得到该酶以丙烯腈为底物的米氏常数(K_m)为8.46mmol/L,单位质量腈水合酶的催化速率常数(k_cat)为2398μmol/(min·mg).     

镍系胶体催化丁二烯聚合反应的研究Ⅰ: 催化剂的相态

研究了Ni(naph)~2-Al(i-Bu)~3-(BF~3·OEt~2+n-C~8H~1~7OH)催化体系的相态。通过Tyndall效应、电镜观察和超过滤实验,证明镍催化体系在溶有丁二烯的加氢汽油中以小颗粒分散,粒径在1～100nm之间,为胶体催化剂,属高度分散的多相催化体系。催化剂的活性中心位于胶粒表面,催化剂颗粒是无定形的。催化剂各组分配比影响胶粒形态,其中以较佳配比所得到的催化剂颗粒较小、分布均匀,催化丁二烯聚合反应活性高。     

原位合成氮掺杂石墨烯负载钯纳米颗粒用于催化香兰素高选择性加氢反应

通过原位合成法制备了氮掺杂石墨烯负载钯纳米颗粒催化剂Pd@N/C-2,用于催化香兰素选择性加氢反应.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等方法对Pd@N/C-2催化剂进行结构与性能的表征,分析表明石墨烯层在活性钯纳米颗粒表面起到了保护作用,提高了催化剂在反应条件下的稳定性,在五次循环回收实验后催化剂仍保持很高的反应活性.通过对石墨烯掺杂氮原子引入了催化反应的化学活性中心和金属纳米颗粒沉积的锚定中心,从而使石墨烯在加氢催化反应中的性能得到进一步提高.并且通过对溶剂的调控实现了香兰素分别高选择性生成香草醇和对甲基愈创木酚,在优化的反应条件下,香草醇和对甲基愈创木酚的产率分别为89%和99%.     

非均相TiCl_4/MgCl_2型Ziegler-Natta催化剂催化烯烃配位聚合机理研究进展

非均相TiCl_4/MgCl_2型Ziegler-Natta催化剂(负载型Ziegler-Natta催化剂)因其高聚合活性、高立构选择性及低制备成本,是目前聚烯烃领域重要的工业催化剂.本文综述了负载型Ziegler-Natta催化剂催化α-烯烃(乙烯、丙烯)和共轭二烯烃(丁二烯、异戊二烯)配位聚合机理的研究进展,包括TiCl_4在MgCl_2表面的吸附、钛的烷基化与还原、烷基铝的作用、活性中心数目、活性中心价态、活性中心模型、可能活性中心结构及催化机理、给电子体作用等.最后,展望了负载型Ziegler-Natta催化剂催化烯烃聚合的机遇与挑战.     

V（acac）3—AI（i—BU）2CI催化体系相态的研究

研究了V(acac)3-AI(i-BU)2CI催化体系的相态。通过Tyndall效应、电镜观察和超过渡实验,证明了在溶有丁二烯的甲苯溶剂中V(acac)3-AI(i-BU)2CI催化体系以小颗粒分散,粒径在1－100nm之间,为胶体催化剂,属于高度分散的多相催化体系。催化剂颗粒是无定形的,其活性中心位于胶粒表面,以较佳配比所得到的催化剂颗粒较小、分布均匀,对丁二烯聚合反应具有较高的催化活性。     

镓改性的铜基疏水催化剂用于CO2选择性加氢制二甲醚的研究(英文)

CO₂选择性加氢制二甲醚(DME)是实现CO₂资源化利用的重要途径之一.然而,该过程面临着多方面的挑战.比如,水分子会限制CO₂的高效转化并诱导铜颗粒的团聚,导致催化活性与稳定性不足.此外,沸石分子筛甲醇脱水催化剂的酸性过强容易造成甲醇过度脱水生成低碳烃,导致催化选择性不足.因此,开发高效稳定的CO₂加氢制DME催化剂十分必要.本文通过共水解法制备了一系列镓改性的疏水二氧化硅负载铜基催化剂,并通过优化疏水基团含量以及铜与镓的比例来进一步提高催化性能.通过X射线衍射、氢气程序升温还原、X射线光电子能谱和CO吸附红外光谱等方法进行表征,结果表明,镓物种对铜纳米颗粒的电子结构进行了调控,提升了催化剂上Cu^δ+物种的含量,从而抑制了逆水煤气转换反应,实现了CO选择性的降低.此外,水蒸气等温吸附、水蒸气程序升温脱附和水滴接触角测试等结果表明,引入疏水甲基基团可以调控催化剂表面的浸润性,提升水分子的扩散速率并抑制其二次吸附.在镓改性和甲基基团疏水修饰的协同作用下,Cu/Ga-SiO     

DNBP给电子体构象分析及在Ziegler-Natta丙烯聚合中作用机理研究

首次采用TINKER构象搜索和DFT结构优化相结合方法,基于对Ziegler-Natta丙烯聚合催化体系邻苯二甲酸正丁酯(DNBP)给电子体快速搜索出的1 023种构象,筛选出其优势构象,减少了给电子体初始稳定结构搭建模型的盲目性和随机性.采用DFT方法,对DNBP两种构象与MgCl2载体相互作用及丙烯插入立体选择性机理进行了研究.结果表明,DNBP构象影响其在MgCl2表面的吸附,s-顺、反式构象可以单齿、桥连和螯合方式吸附在MgCl2(110)表面;s-顺、顺式仅存在桥连吸附.双氯原子缺陷载体模型上TiCl4吸附的稳定性高于DNBP,成为可能的活性中心;给电子体对活性位的作用与其吸附方式有关,DNBP以桥连方式吸附在Ti的邻位,可将无规活性中心有效转化为等规活性中心,而螯合方式不能改善催化剂的立体结构和区域选择性.     

邻苯二甲酸正丁酯给电子体构象分析及在Ziegler-Natta丙烯聚合中作用机理研究

首次采用TINKER构象搜索和DFT结构优化相结合方法,基于对Ziegler-Natta丙烯聚合催化体系邻苯二甲酸正丁酯(DNBP)给电子体快速搜索出的1 023种构象,筛选出其优势构象,减少了给电子体初始稳定结构搭建模型的盲目性和随机性.采用DFT方法,对DNBP两种构象与MgCl_2载体相互作用及丙烯插入立体选择性机理进行了研究.结果表明,DNBP构象影响其在Mg Cl2表面的吸附,s-顺、反式构象可以单齿、桥连和螯合方式吸附在MgCl_2(110)表面;s-顺、顺式仅存在桥连吸附.双氯原子缺陷载体模型上Ti Cl4吸附的稳定性高于DNBP,成为可能的活性中心;给电子体对活性位的作用与其吸附方式有关,DNBP以桥连方式吸附在Ti的邻位,可将无规活性中心有效转化为等规活性中心,而螯合方式不能改善催化剂的立体结构和区域选择性.     

固定化对恶臭假单胞菌腈水合酶催化特性的影响

酶法代替铜催化法使丙烯腈转化制内烯酰胺的研究,70年代起在国外开始进行.近年来,国内也相继开展了这方面的工作.他们筛选得到的恶臭假单胞菌JP-1具有较高腈水合酶活力,其完整细胞的腈水合酶催化特性也已进行了研究.本文研究了采用海藻酸钙包埋法制备的恶臭假单胞菌固定化细胞的酶学性质.     

环烷酸钴-氯二异丁基铝催化体系相态的研究

研究了Co(naph) 2 Al(i Bu) 2 Cl催化体系的相态 .通过Tyndall效应、电镜观察和超过滤实验 ,证明了Co(naph) 2 Al(i Bu) 2 Cl催化体系在溶有丁二烯的苯溶剂中以纳米级小颗粒分散 ,在较佳配比时 ,粒径在 1～10 0nm之间 ,为胶体催化剂 ,属于高度分散的多相催化体系 .催化剂的活性位位于胶粒表面 ,催化剂颗粒是无定形的 .以较佳配比得到的催化剂颗粒较小、分布均匀 ,催化丁二烯聚合反应活性高 .归纳出胶体催化剂的制备特点为外观类似于均相催化体系 ,但是制备方法 (各组分配比、加入顺序、陈化等 )对催化活性有明显的影响 .并给出将胶体催化动力学作均相动力学近似的条件 ,在聚合反应初期 ,且单体浓度比烷基铝以及其他填加物浓度大 2～ 3数量级     

Structure sensitivity of selective acetylene hydrogenation over the catalysts with shape-controlled palladium nanoparticles

The structure sensitivity of acetylene hydrogenation on catalysts with controlled shape of palladium nanoparticles was studied. Palladium particles of cubic (Pd_cub), cuboctahedral (Pd_co) and octahedral (Pd_oct) shapes were obtained by a colloidal method. Poly(N-vinyl)pyrrolidone (PVP) was used as the stabilizer of colloidal solutions. In order to eliminate the effect of the polymer on the properties of the catalyst, PVP was removed from the surface of the particles after their transfer to the support by simultaneous treatment with ozone and UV radiation. This allowed complete cleaning of the catalyst surface from the organic stabilizer without any change in the morphology of particles. The effectiveness of this treatment method was confirmed by X-ray photoelectron spectroscopy and scanning electron microscopy. It was found experimentally that the shape of nanoparticles does not influence the catalyst selectivity, but the activity decreases in the order Pd_oct > Pd_co > Pd_cub. Since octahedrons consist of (111) faces, the cubes contain only (100) faces, and the cuboctahedrons are composed of faces of both types, Pd₁₁₁ is more active than Pd₁₀₀. Calculations with the use of a statistical method showed that the ～3-nm Pd octahedrons are nanoparticles with optimum shape and size, giving maximum catalyst activity.     

RuB-PVP胶态催化剂的制备及苯选择加氢性能研究

系统研究了制备时间、Ru/PVP(聚乙烯吡咯烷酮)比及钌浓度对PVP稳定的RuB胶态催化剂粒径及分布的影响; 制备了粒径在1.3～3.9 nm的RuB-PVP催化剂, 研究了不同粒径的催化剂对苯选择加氢反应的影响. 结果表明RuB粒径越小, 催化剂的苯选择加氢性能越好. 在粒径为1.3 nm的RuB-PVP催化剂上, 环己烯得率达到16.8%. 在无机添加剂ZnSO₄的存在下, 环己烯得率可进一步提高至23.2%. 在相同实验条件下, 无PVP稳定的RuB催化剂上的苯选择加氢性能则远低于RuB-PVP胶态催化剂.     

The catalytic hydration of nitriles to amides using a homogeneous platinum phosphinito catalyst

New homogeneous catalysts for the hydration of nitriles to amides are described. The catalyst precursors are coordination compounds of Pt(II) with secondary phosphine oxides. They contain a hydrogen bridged mono-anionic didentate phosphinito group, together with a third phosphine oxide ligand and a monodentate anionic ligand, either hydride or chloride. Reacting the chloride with silver ion, or the hydride with water gives a cationic species which is the active catalyst. On coordination to the cation the nitrile becomes susceptible to nucleophilic attack. The hydrolysis gives the amide as the sole product, and there is no tendency towards further hydrolysis to the acid. The effects of substituents on phosphorus are investigated, and a reaction mechanism is suggested. The most active catalyst, [PtH(PMe₂OH)(PMe₂O)₂H], 2a, is derived from dimethylphosphine oxide, and this precursor catalyses the hydration of acrylonitrile to acrylamide with a turnover number of 77,000, without addition to the C=C double bond.     

Phase state of iron system colloidal catalyst in butadiene polymerization

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分散聚合水基聚苯胺乳胶微球制备与表征

水溶性空间稳定剂聚乙烯吡咯烷酮（PVP）存在时，采用分散聚合制备水溶性单分散的聚苯胺(PAn)乳胶粒子，采用透射电子显微镜（TEM）观察粒子形态及尺寸；利用紫外-可见吸收光谱对胶体分散体系进行表征.实验结果表明，当PAn含量较少（w< 16.78％）时， PAn-PVP复合乳胶粒子呈米粒状；当PAn含量较大（w >23.22％）时， PAn-PVP复合乳胶粒子呈球形.     

Immobilized copper(II) on nitrogen‐rich polymer‐entrapped Fe3O4 nanoparticles: a highly loaded and magnetically recoverable catalyst for aqueous click chemistry

A heterogeneous magnetic copper catalyst was prepared via anchoring of copper sulfate onto multi‐layered poly(2‐dimethylaminoethyl acrylamide)‐coated magnetic nanoparticles and was characterized using various techniques. The catalyst was found to be active, effective and selective for one‐pot three‐component reaction of alkyl halide, sodium azide and alkyne, known as copper‐catalyzed click synthesis of 1,2,3‐triazoles. As little as 0.3 mol% of catalyst was found to be effective under the optimum conditions. The catalyst could also be recycled and reused up to seven times without significant loss of activity. Thermal stability, high loading level of copper on catalyst, broad diversity of alkyl/benzyl/allyl bromide/chloride and alkyl/aryl terminal alkynes without isolation of azide intermediate, and good to excellent yields of products make this procedure highly economical. Copyright © 2015 John Wiley & Sons, Ltd.     

聚乙烯吡咯烷酮稳定的钯纳米粒子催化加氢

Nanosized colloidal platinum was prepared by reduction of H2PtCl6 in methanol-water mixture by refluxing. The particle size and morphology were characterized by transmission electron microscopy and electron diffraction. The influence of polyvinylpyrrolidone (PVP) molecular mass (MM),PVP concentration,and reduction time on platinum particle size was investigated. Small (1-2 nm) Pt particles are formed in the case of PVP with MM=1.2×104. With increasing polymer MM and decreasing polymer concentration,large aggregates from small particles appear. High catalytic activity of the obtained colloidal platinum in hydrogenation of acetylene compounds is shown. The effect of Pt particle size on the catalytic activity was studied.