氮掺杂有序介孔碳负载超小尺寸铂纳米颗粒催化硝基苯类化合物选择加氢

氮掺杂有序介孔碳材料不仅具有高的比表面积、大的孔容和均一可调的孔径等优点,其骨架中丰富的氮原子还可以对材料的物理化学性质、配位金属电荷密度等进行调控,是一类优异的催化剂载体.本文利用软模板(嵌段共聚物F127为模板),以间氨基苯酚为碳源和氮前体,制备出较高含氮量(9.58 wt%)和比表面积(417 m2/g),以及规则孔径分布的介孔碳材料.结果表明,制备的材料具有三维立方相结构.以该碳材料作为载体,使用传统浸渍氢气还原的策略负载纳米铂颗粒.发现氮掺杂的载体能够有效控制金属纳米颗粒的尺寸,可实现超小尺寸Pt纳米颗粒的有效负载(1.0±0.5 nm),且纳米颗粒均匀分布于介孔碳材料的孔道中.相比而言,使用相同负载方法的情况下,以不掺氮的介孔碳材料为载体,纳米粒子的尺寸较难控制(4.4±1.7 nm)且会发生孔道外颗粒聚集的情况.研究表明,骨架中的氮原子与金属间弱的相互作用对纳米粒子有稳定作用.这对制备超小尺寸的金属纳米粒子催化剂具有一定的指导意义.此外,由于纳米粒子的尺寸将大大影响催化剂活性中心的暴露程度,进而影响催化剂活性.因此,我们以硝基苯类化合物的氢化反应来评价该催化剂的催化性能.在室温和1 MPa H2的温和条件下,氮掺杂的介孔碳负载催化剂表现出了优异的催化性能.反应0.5 h,对氯硝基苯可完全转化,且选择性高达99%.相比而言,商业化的Pt/C催化剂上反应的转化率和选择性分别为89%和90%.其它传统催化剂的比较,如Pt/SiO2,Pt/TiO2,同样表明,氮掺杂介孔碳负载的催化剂具有更优异的催化性能.在相同反应条件下,Pt/SiO2催化剂只能得到46%的转化率和93%的选择性,而Pt/TiO2催化剂虽然能够实现完全转化,但选择性也仅为91%.由此可见,氮掺杂的负载催化剂可大大提高反应活性和选择性,能有效抑制脱氯现象的发生.这种高的催化性能可能与催化剂的介孔结构、氮功能化载体以及超小尺寸的Pt纳米粒子的稳定有关.由于氮原子和介孔孔道的限域作用,氮掺杂介孔碳负载的催化剂也具有良好的催化稳定性,循环使用10次后,催化活性和选择性几乎没有下降.结果表明,循环使用后的催化剂金属粒子尺寸变化不大,进一步表明氮掺杂介孔碳载体对金属纳米颗粒的稳定作用.     

纳米镍在硝基苯加氢中催化性能的研究

纳米镍在硝基苯加氢中催化性能的研究左东华，张志琨，崔作林（青岛化工学院纳米材料研究所，青岛２６６０４２）关键词纳米镍，催化加氢，硝基苯．硝基化合物加氢还原是化工生产中的一个重要化工单元反应，现今工业生产中大多采用Ｒａｎｅｙ－Ｎｉ作为催化剂。但由于在Ｒ...     

硝基苯催化加氢制备对氨基苯酚

研究了ＳｉＯ２,ＺＳＭ－５,活性炭,γ－Ａｌ２Ｏ３及改性γ－Ａｌ２Ｏ３载体,催化剂的制备方法,还原温度及添加剂等对硝基苯催化加氢制对氨基苯酚反应的影响。以改性γ－Ａｌ２Ｏ３为载体时ＰＡＰ收率可达８３％。以ＺＳＭ－５为载体,催化剂的最佳还原温度为２００℃,ＰＡＰ收率为７５％。?     

担载铂催化剂用于硝基苯催化加氢制对氨基苯酚的研究

研究了以活性炭、γＡ１２Ｏ３、γ－Ａ１２Ｏ３－ＴiＯ２为载体,用浸渍法制备的铂含 量为１％的担载铂催化剂,用于硝基苯催化加氢制对氨基苯酚。发现Ｐｔ／γ－Ａ１２Ｏ３－ＴiＯ２催化剂有较高的活性、选择性和较长的寿命,催化剂循环使用１０次后,对氨基酚的率仍高于８０％,优于常用的Ｐt／Ｃ催化剂 。测定了催剂的比表面积、孔结构以 及活性金属铂的分散度,发现孔结构与催化剂性能之间没有规律性的关系;而铂在γ－Ａ１２     

MIL-101限域Au纳米颗粒催化对硝基苯酚加氢反应

利用MIL-101有序纳米孔道的限域能力,制备出一系列尺寸较小且分散度均匀的Au纳米颗粒Au@MIL-101催化剂,通过X射线衍射、高分辨透射电子显微镜、物理吸附仪和原子发射光谱仪对该催化剂进行了表征.该催化剂在温和的反应条件下对对硝基苯酚加氢反应表现出良好的催化活性.     

硝基苯催化加氢制对氨基苯酚的合成工艺研究进展

介绍了硝基苯在酸性介质中一步加氢重排的反应机理及模型。以提高对氨基苯酚产率和纯度为宗旨，在大量文献调研的基础上提出了控制副反应的几种方法，并讨论了改进对氨基苯酚产量和纯度的可能途径。引用文献22篇。     

微乳法制备纳米Ru/NaY催化剂及其催化对苯二酚加氢

采用曲拉通X-100(Triton X-100)/正己醇/正庚烷/RuCl_3·3H_2O水溶液构成微乳液,以水合肼为还原剂,制备了纳米Ru颗粒,再破乳将其负载于NaY分子筛得到M-Ru/NaY催化剂.通过XRD、BET、XPS、SEM、TEM及DSC分析方法对催化剂进行了表征.表征结果表明,M-Ru/NaY催化剂具有金属钌平均粒径小,分布均匀,高度分散等优点.以对苯二酚加氢制1,4-环己二醇为探针反应,对微乳法和传统浸渍法制备的催化剂活性和选择性进行了比较,深入研究了催化剂用量,反应温度,氢气压力对对苯二酚加氢活性的影响及最佳反应时间的确定.实验结果表明,M-Ru/NaY催化剂在反应温度150℃,氢气压力4.0 MPa,m(M-Ru/NaY)∶m(对苯二酚)=0.2∶1,溶剂为异丙醇,此条件下反应30 min,对苯二酚转化率为100%,1,4-环己二醇的选择性高达92.6%.还考察了M-Ru/NaY催化剂的稳定性.最后,探讨了对苯二酚加氢反应路径.     

两种制备铂纳米颗粒方法的比较

用乙醇回流及NaBH4还原两种方法制备了Pt纳米颗粒,用UV Vis光谱、TEM对铂纳米颗粒进行了表征,比较了两种合成方法的特点.     

杨梅单宁接枝胶原纤维负载Pt催化剂的制备及其催化硝基苯加氢的研究

以杨梅单宁接枝胶原纤维为载体,制备了新型负载铂(Pt)纳米催化剂。杨梅单宁作为桥分子,通过其邻位酚羟基与Pt(IV)形成五元螯合环并固定在胶原纤维上。还原过程中,杨梅单宁能有效地抑制Pt纳米颗粒的团聚。通过扫描电镜(SEM)、透射电镜(TEM)、X-射线光电子分光光谱(XPS)以及X-射线衍射(XRD)等分析手段对该催化剂的物化性能进行了表征,结果表明该催化剂具有规整的纤维结构,且在胶原纤维的外表面形成了具有高分散性、平均粒径在2.8±0.5nm的Pt(0)纳米颗粒。该催化剂用于硝基苯催化加氢反应中,在较温和的条件下显示出了较高的催化活性(TOF=1097mol/(molPt·h))、高选择性(98%)以及较低的活化能(Ea=30.49kJ/mol)。通过改变胶原纤维表面杨梅单宁的接枝度,可以有效控制催化剂对硝基苯的催化反应速率。该催化剂重复使用5次后,催化活性没有降低,表明该催化剂具有良好的重复使用特性。     

超细Co-B非晶态合金的制备及其催化乙腈加氢性能

报道了 一种用 于乙腈加 氢的 新 型 复合 型 催化 剂 超细 Ｃｏ Ｂ 非 晶 态合 金（ 粒 径 ６０ ｎ ｍ左右） , 其催 化性能显 著优于 其它 Ｃｏ 基催 化剂． 以此代替 工业用 Ｒａｎｅｙ Ｎｉ , 不 仅可 提高 对乙 胺的选择性 ,而且可 显著减轻 环境污 染． 通 过一系列 表征,讨 论了乙腈 在催化 剂活性位 的吸附 模式及催化加氢 反应机 理,由此对 其催化 性能与催 化剂结 构的关系 进行了说 明．     

二烯酸稳定的Pt金属纳米粒子的制备及催化加氢活性

制备了4-(双(4-(4-丁氧基苯乙烯基)苯基)氨基)苯甲酸(简称二烯酸,Dienoic Acid)保护的铂纳米颗粒,通过UV-Vis,TEM,XRD对其进行了表征.以间苯氧基苯甲醛的催化加氢反应为模型研究了其催化性能及影响催化活性的因素.实验结果表明:金属纳米粒子粒径随金属/稳定剂摩尔比的下降而减小,而催化加氢反应活性随金属/稳定剂摩尔比的上升而增加.在常压、40℃、n(醛)/n(催化剂)=523条件下,反应10 h可以获得纯度大于99%的间苯氧基苯甲醇.     

Hydrogenation of 2,4-Dinitrotoluene to 2,4-Diaminotoluene over Platinum Nanoparticles in a High-Pressure Slurry Reactor

A practical and convenient synthesis of the fungicidal natural compound farinomalein is described starting from readily available ethyl 3-methyl-2-oxobutyrate and triethyl phosphonoacetate, employing a Horner–Wadsworth–Emmons condensation as the key step.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Chemoselective Hydrogenation of Functionalized Nitroarenes and Imines by Using Carbon Nanofiber‐Supported Iridium Nanoparticles

The reaction of three types of carbon nanofibers (CNFs; platelet: CNF‐P, tubular: CNF‐T, herringbone: CNF‐H) with Ir₄(CO)₁₂ in mesitylene at 165 °C provided the corresponding CNF‐supported iridium nanoparticles, Ir/CNFs (Ir content=2.3–2.6 wt. %). Transmission electron microscopy (TEM) studies of these Ir/CNF samples revealed that size‐controlled Ir nanoparticles (average particle size of 1.1–1.5 nm) existed on the CNFs. Among the three Ir/CNF samples, Ir/CNF‐T showed an excellent catalytic activity and chemoselectivity towards hydrogenation of functionalized nitroarenes and imines; the corresponding aniline derivatives were obtained with high turnover numbers at ambient temperature under 10 atm of H₂, and the catalyst is reusable. Ir/CNF‐T was also effective for the reductive N‐alkylation of anilines with carbonyl compounds.     

A Reusable Co Catalyst for the Selective Hydrogenation of Functionalized Nitroarenes and the Direct Synthesis of Imines and Benzimidazoles from Nitroarenes and Aldehydes

The use of abundantly available transition metals in reactions that have been preferentially mediated by rare noble metals, for example, hydrogenations, is a desirable aim in catalysis and an attractive strategy for element conservation. The observation of novel selectivity patterns with such inexpensive metal catalysts is especially appealing. Herein, we report a novel, robust, and reusable cobalt catalyst that permits the selective hydrogenation of nitroarenes in the presence of highly hydrogenation‐sensitive functional groups, as well as the direct synthesis of imines from nitroarenes and aldehydes or ketones in the presence of such substituents. Furthermore, we introduce the first base‐metal‐mediated direct synthesis of benzimidazoles from nitroarenes and aldehydes. Functional groups that are easy to hydrogenate are again well tolerated.     

Selectivity Control on Hydrogenation of Substituted Nitroarenes through End‐On Adsorption of Reactants in Zeolite‐Encapsulated Platinum Nanoparticles

Platinum nanoparticles encapsulated into zeolite Y (Pt@Y catalyst) exhibit excellent catalytic selectivity in the hydrogenation of substituted nitroarenes to form the corresponding aromatic amines, even after complete conversion. With the hydrogenation of p‐chloronitrobenzene as a model, the role of zeolite encapsulation toward perfect selectivity can be attributed to constraint of the substrate adsorbed on the platinum surface in an end‐on conformation. This conformation results in the activation of only one adsorbed group, with little influence on the other one in the molecule. Owing to a much lower apparent activation energy of Pt@Y for the hydrogenation of a separately adsorbed nitro group than that of the adsorbed chloro group, the Pt@Y catalyst can prevent hydrodechlorination of p‐chloronitrobenzene under mild conditions. Moreover, such a conformation results in a reduced adsorption energy of target p‐chloroaniline on the platinum surface; thus suppressing the reactivity of hydrodechlorination of p‐chloroaniline to circumvent further C−Cl bond breakage.     

Facile Fabrication of Platinum Nanoparticles Supported on Nitrogen-doped Carbon Nanotubes and Their Catalytic Activity

A facile impregnation method under mild condition is designed for synthesis of highly dispersed Pt nanoparticles with a narrow size of 4-7 nm on nitrogen-doped carbon nanotubes （CNx）. CNx do not need any pre-surface modification due to the inherent chemical activity. The structure and nature of Pt/CNx were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy spectrum. All the experimental results revealed that the large amount of doped nitrogen atoms in CNx was virtually effective for capturing the Pt（IV） ions. The improved surface nitrogen functionalities and hydrophilicity contributed to the good dispersion and immobi- lization of Pt nanoparticles on the CNx surface. The Pt/CNx served as active and reusable catalysts in the hydrogenation of allyl alcohol. This could be attributed to high dispersion of Pt nanoparticles and stronger interaction between Pt and the supports, which prevented the Pt nanoparticles from aggregating into less active Pt black and from leaching as well.     

Platinum Nanoparticles: The Crucial Role of Crystal Face and Colloid Stabilizer in the Diastereoselective Hydrogenation of Cinchonidine

The preparation of stable metal nanoparticles requires a strong interaction between the (organic) stabilizer and the metal surface that might alter the catalytic properties. This behavior has been described as “poisoning” since the stabilizer normally decreases the catalytic activity due to site blocking. Here we show a striking influence of the stabilizer on the selectivity in the hydrogenation of cinchonidine (CD) over poly(acrylic acid) (PAA)‐stabilized Pt nanoparticles with well‐defined shape distributions. In the hydrogenation of the heteroaromatic ring of cinchonidine in toluene, the diastereomeric excess of the (S)‐hexahydrocinchonidine increased upon increasing Pt{111}/Pt{100} ratio, but this distinct shape selectivity was observed only after the oxidative removal of PAA at 473 K. The use of the as‐prepared nanoparticles inverted the major diastereomer to R, and this isomer was formed also in acetic acid. This striking change in the diastereoselectivity indicates that poly(acrylic acid), which remains on the Pt surface after preparation, interacts with CD during hydrogenation almost as strongly as the solvent acetic acid. The PAA stabilizer plays a dual role: it allows one to control the size and shape of the nanoparticles during their synthesis, and it affects the rate and diastereoselectivity of the hydrogenation of CD probably through a “surface‐localized acidification”.     

Supramolecular Regulation of Catalytic Activity for an Amphiphilic Pyrene-Ruthenium Complex in Water

A switchable catalytic system has been designed and constructed with a host−guest interaction between cucurbituril (CB) and an amphiphilic metal complex pyrene−ruthenium (Py−Ru). Py−Ru can self-assemble into positively charged nanoparticles in water, and exhibits an enhanced catalytic efficiency in the transfer hydrogenation of NAD⁺ to NADH. After forming an inclusion complex with CB, Py−Ru aggregates are broken, leading to a decrease in catalytic efficiency, which can be recovered by competitive replacement with amantadine. This supramolecular strategy provides an efficient and flexible method for constructing reversible catalytic system, which also extends the application scope of the host−guest interaction.     

易分离的高效纳米铂氢化催化剂

近年来纳米贵金属的优异催化性能得到了人们的关注,但是纳米粒子在使用、贮藏过程中存在团聚现象。在制备过程中加入稳定剂可以延缓其团聚,但给纳米粒子的分离带来了困难。有献报道利用水溶性表面活性剂聚乙二醇(PEG)的乙二醇链段可以稳定Rh纳米粒子,可是因其分子量过