CeO2纳米层对多层载体x-CeO2/3DOM Al2O3负载纳米Au催化剂催化柴油炭烟燃烧活性的影响

与汽油车相比,柴油车具有CO2排放低、寿命长和经济性好等优点,所以近年来受到广泛关注并被大量使用.但是,柴油车在使用过程中会产生大量炭烟颗粒物(PM),对大气环境和人类健康造成很大威胁.因此,开展这方面的基础研究具有重要的科学意义及环境保护意义.催化柴油炭烟燃烧反应是一个气-固-固多相深度氧化反应,由于PM的粒径远大于传统催化剂,导致PM不能进入催化剂孔道内部,造成催化剂活性比表面积利用率较低.设计并制备大孔径的三维有序大孔结构(3DOM)的催化剂,能够减小反应扩散阻力,增加催化剂与炭烟颗粒物的有效接触,加快反应进行.另外,可以通过在3DOM氧化物表面担载其它活性组分,提高催化剂的氧化还原性能,进而提高其活性.CeO2有很好的储放氧性能,在柴油车尾气净化催化剂中较为常见,但是单一的CeO2热稳定性较差,高温下容易烧结,使得比表面积减小,并且失去储氧能力,造成催化剂失活.文献中较常见的解决办法是在CeO2中掺杂其它阳离子,如Zr4+,Pr3+,Al3+,La3+及Y3+等离子,以提高CeO2的抗高温烧结能力.此外,研究报道的催化剂对催化柴油炭烟颗粒物燃烧的峰值温度已经远低于炭烟颗粒物的自燃温度,但是对颗粒物的起燃温度仍普遍较高.我们前期研究结果表明,担载纳米Au颗粒催化剂能够显著降低炭烟燃烧的起燃温度.本文采用胶体晶体模板法制备了3DOM Al2O3载体,利用微孔膜-氨沉淀法担载不同量的活性组分CeO2,制备出一种负载型x-CeO2/3DOM Al2O3催化剂,它既可减少稀土元素用量,降低成本,又因为Al2O3的机械强度较高,还能保证催化剂的机械强度足够好.为了进一步降低催化剂催化炭烟燃烧的起燃温度,利用还原沉积法在多层载体x-CeO2/3DOM Al2O3上负载纳米Au催化剂,制备出不同厚度的CeO2纳米层负载Au催化剂(Au/x-CeO2/3DOM Al2O3).利用X射线衍射、扫描电镜、透射电镜、H2程序升温还原和O2程序升温脱附等方法研究了催化剂的结构及物化性质与催化剂活性之间的关系,提出了消除PM反应的可能机理.结果表明,Al3+离子能够部分进入到CeO2中,形成Al-Ce固溶体.由于Al离子半径小于Ce离子,Al3+掺杂后能引起CeO2晶格发生畸变,产生大量缺陷,形成大量氧空位,促进晶格氧的移动,从而使催化剂具有更大的储放氧能力.在Au/x-CeO2/3DOM Al2O3催化剂中,CeO2担载量过高时,氧化铈纳米层较厚,活性组分容易烧结,不利于催化剂活性提高;而CeO2担载量过低,则CeO2纳米层较稀薄,催化剂的氧化还原性能受限,催化剂活性也不高.因此,CeO2的担载量应适当.此外,Au和CeO2之间的强相互作用能够增加Au纳米颗粒表面活性氧物种的数量,从而促进柴油炭烟燃烧反应.活性测试结果表明,担载纳米Au颗粒后,催化剂催化柴油炭烟燃烧的起燃温度均明显降低,在所制备的系列催化剂中Au/20％CeO2/3DOM Al2O3催化剂展示了最高的催化活性,T10,T50和T90分别为267,372和426 oC.     

Synthesis of Fe_3O_4@SiO_2@polymer nanoparticles for controlled drug release

Novel multifunctional nanoparticles containing a magnetic Fe3O4@SiO2 sphere and a biocompatible block copolymer poly(ethylene glycol)-b-poly(aspartate)(PEG-b-PAsp) were prepared.The silica coated on the superparamagnetic core was able to achieve a magnetic dispersivity,as well as to protect Fe3O4 against oxidation and acid corrosion.The PAsp block was grafted to the surface of Fe3O4@SiO2 nanoparticles by amido bonds,and the PEG block formed the outermost shell.The anticancer agent doxorubicin(DOX) was loade...     

磁性纳米粒子负载钯催化有机合成反应研究进展

磁性纳米粒子负载钯催化的有机合成反应,由于具有催化活性高,催化剂在外加磁场作用下即可快速分离和重复使用等特点,已引起了人们的广泛关注.综述了近年来磁性纳米粒子负载钯催化有机合成反应的研究进展,载体包括Fe3O4纳米粒子、有机小分子修饰的磁性纳米粒子、SiO2包覆的磁性纳米粒子、碳修饰磁性纳米粒子、羟基磷灰石包覆的磁性纳米粒子和有机高分子修饰的磁性纳米粒子等.     

Rapid monitoring of the nature and interconversion of supported catalyst phases and of their influence upon performance: CO oxidation to CO2 by gamma-Al2O3 supported Rh catalysts

Spatially and temporally resolved energy-dispersive EXAFS (EDE) has been utilised in situ to study supported Rh nanoparticles during CO oxidation by O2 under plug-flow conditions. Three distinct phases of Rh supported upon Al2O3 were identified by using EDE at the Rh K-edge during CO oxidation. Their presence and interconversion are related to the efficiency of the catalysts in oxidising CO to CO2. A metallic phase is only found at higher temperatures (>450 K) and CO fractions (CO/O2 > 1); an oxidic phase resembling Rh2O3 dominates the active catalyst under oxygen-rich conditions. Below about 573 K, and in CO-rich environments, high proportions of isolated Rh(I)(CO)2 species are found to co-exist with metallic Rh nanoparticles. Alongside these discrete situations a large proportion of the active phase space comprises small Rh cores surrounded by layers of active oxide. Confinement of Rh to nanoscale domains induces structural lability that influences catalytic behaviour. For CO oxidation over Rh/Al2O3 there are two redox phase equilibria alongside the chemistry of CO and O adsorbed upon extended Rh surfaces.     

Liquid-phase oxidation of benzothiophene and dibenzothiophene by cumyl hydroperoxide in the presence of catalysts based on supported metal oxides

The liquid-phase oxidation of benzothiophene and dibenzothiophene by cumyl hydroperoxide in the presence of supported metal oxide catalysts was carried out in octane in an N₂ atmosphere at 50–80°C. The cumyl hydroperoxide, benzothiophene, and dibenzothiophene conversions and the yield of sulfones were determined for catalysts of various natures. In the presence of MoO₃/SiO₂, the most efficient and most readily regenerable catalyst, the benzothiophene conversion was ～60% and the dibenzothiophene conversion was as high as 100% upon almost complete consumption of cumyl hydroperoxide. The influence of unsaturated and aromatic compounds (oct-1-ene, toluene) on the catalytic effect was studied. The kinetics of substrate oxidation and cumyl hydroperoxide decomposition and an analysis of the cumyl hydroperoxide conversion products suggested a benzothiophene and dibenzothiophene oxidation mechanism including the formation of an intermediate complex of the hydroperoxide with the catalyst and the substrate and its transformation via heterolytic and homolytic routes.     

Synthesis and characterization of poly(divinylbenzene)-coated magnetic iron oxide nanoparticles as precursor for the formation of air-stable carbon-coated iron crystalline nanoparticles

Maghemite (gamma-Fe2O3) nanoparticles of 15 +/- 3 nm diameter were prepared by nucleation of gelatin/iron oxide followed by growth of gamma-Fe2O3 films onto these nuclei. The gamma-Fe2O3 nanoparticles were coated with polydivinylbenzene (PDVB) by emulsion polymerization of divinylbenzene (DVB) in an aqueous continuous phase containing the gamma-Fe2O3 nanoparticles. The PDVB-coated gamma-Fe2O3 nanoparticles, dispersed in water, were separated from homo-PDVB nanoparticles using the high gradient magnetic field (HGMF) technique. The influence of DVB concentration on the amount of PDVB coating, on the size and size distribution of the coated gamma-Fe2O3 nanoparticles and on their magnetic properties, has been investigated. Air-stable carbon-coated iron (alpha-Fe/C) crystalline nanoparticles of 41 +/- 12 nm diameter have been prepared by annealing the PDVB-coated gamma-Fe2O3 nanoparticles at 1050 degrees C in an inert atmosphere. These nanoparticles exhibit high saturation magnetization value (83 emu g(-1)) and excellent resistance to oxidation. Characterization of the PDVB-coated gamma-Fe2O3 and of the alpha-Fe/C nanoparticles has been accomplished by TEM, HRTEM, DLS, FTIR, XRD, thermal analysis, zeta-potential, and magnetic measurements.     

Sonochemical preparation of supported hydrodesulfurization catalysts

Sonochemical preparation of Co and Ni promoted MoS(2) supported on alumina was achieved by high-intensity ultrasonic irradiation of isodurene solutions containing molybdenum carbonyl, dicobalt octacarbonyl, elemental sulfur, and Al(2)O(3) or Ni-Al(2)O(3) under Ar flow. The sonochemically prepared catalysts were characterized by elemental analysis, XPS, SEM, TEM, and XEDS, and hydrodesulfurization (HDS) activity evaluated for thiophene and dibenzothiophene substrates. The TEM studies on the sonochemically prepared catalysts indicate the formation of layered hexagonal MoS(2) (lattice fringes approximately 6.2 A) on the alumina support. The sonochemically prepared Co-Mo-S/Al(2)O(3), Ni-Mo-S/Al(2)O(3), and Co-Ni-Mo-S/Al(2)O(3) are extremely active catalysts for the HDS of thiophene and dibenzothiophene, with activities severalfold those of comparable commercial catalysts under identical conditions. The layered structure of MoS(2) remained intact after 120 h of HDS, and the catalyst is reusable.     

高催化活性Pd-Co3O4/MWCNTs催化剂对甲醇氧化的电催化性能

以Co(NO3)3·6H2O为钴源,聚乙二醇(PEG)20000为表面活性剂,与多壁碳纳米管(MWCNTs)混合后通过水热氧化法成功地合成了表面均匀分布纳米絮状Co3O4的MWCNTs复合物,进一步还原Pd的前驱体而制备得到Pd-Co3O4/MWCNTs复合催化剂.利用扫描电镜(SEM)、透射电镜(TEM)及X射线粉末衍射(XRD)等手段对样品的形貌和晶型结构进行了表征,结果表明Pd纳米粒子为面心立方晶体结构,均匀地分布在Co3O4修饰的MWCNTs表面.用循环伏安法和计时电流法表征结果表明:催化剂Pd-Co3O4/MWCNTs具有较大的电化学活性表面积,在碱性介质中对甲醇氧化具有更高的电催化活性和稳定性.研究结果表明,过渡金属氧化物纳米Co3O4颗粒在提高直接甲醇燃料电池(DMFC)催化性能研究中具有十分重要的作用,是一类很有潜力的载体催化剂.     

Controllable preparation of highly dispersed TiO2 nanoparticles for enhanced catalytic oxidation of dibenzothiophene in fuels

The aggregation of nanoparticle catalysts is one of the main problems in catalytic reactions. In this study, a series of TiO₂ nanoparticle catalysts with various dispersions were prepared and applied in the catalytic oxidation of dibenzothiophene (DBT) systems. Compositions and structures of the as‐prepared samples were analyzed by means of wide‐angle X‐ray diffraction, Raman and X‐ray photoelectron spectroscopies. The dispersions of TiO₂ nanoparticles were controlled by calcining at various temperatures and verified using transmission electron microscopy. It was found that the activities of TiO₂ nanoparticles in the catalytic oxidation of DBT were positively correlated with the dispersions. TiO₂ nanoparticles calcined at 500 °C (500‐TiO₂) showed the best catalytic activity and the oxidation of DBT reached 99.8% under mild conditions. Based on the results of GC–MS analysis, radical trapping experiments and electron spin resonance spectra, ^?O₂^? radicals were proved to be the main active species in the oxidation process, and a mechanism is proposed. Meanwhile, the recycling performance of 500‐TiO₂ was investigated, and no obvious decrease was observed after six recycles.     

在光催化还原CO2中具有高催化效率的八面体Cu2O修饰的TiO2纳米管

光催化还原CO2生成烃类燃料是一种可同时解决全球变暖和能源危机问题的最有效途径之一。尽管这方面的研究已经取得了一定的进展,但是整体的光催化转换效率还非常低。因此,需要发展更加高效的催化剂。由于半导体材料禁带宽度与太阳光谱相匹配,人们已经对其进行了广泛研究。其中TiO2因具有无毒、强氧化性以及良好的光学和电学性质等而成为最主要的研究对象。但是对于光催化还原CO2反应来说, TiO2仍存在很多不足,如只能吸收太阳光谱中的紫外光,光生载流子会快速结合,以及光生空穴的强氧化能力等,这些都限制了其光催化还原CO2的效率。采用窄禁带宽度半导体修饰TiO2是解决上述不足的有效途径之一。本文采用简单的电化学方法成功制备了一种由窄禁带半导体Cu2O修饰的TiO2纳米管(TNTs)的复合物,并运用扫描电子显微镜(SEM)、X射线衍射(XRD)以及X射线光电子能谱(XPS)表征了所制备复合物的形貌、化学组成和结晶度。表征结果显示,所制备的TiO2为整齐排列的纳米管阵列结构;复合物中的纳米颗粒为Cu2O;当电化学沉积Cu2O的时间为5 min时,得到的Cu2O纳米颗粒初步呈类八面体结构。随着沉积时间的增加, Cu2O颗粒尺寸增加,具有八面体结构。 XRD和XPS结果表明, TiO2纳米管为锐钛矿,八面体Cu2O纳米颗粒的主要暴露晶面为(111)面。我们还进一步研究了不同量Cu2O纳米颗粒修饰的TiO2纳米管复合物在可见光以及模拟太阳光下光催化还原CO2的能力。在可见光下,由于自身的禁带宽度,纯净的TiO2纳米管没有任何光催化还原CO2的能力;经过Cu2O纳米颗粒的修饰,复合物显现出明显的光催化还原CO2的能力,其中经过30 min Cu2O沉积的TNTs具有最高的光催化效率。在模拟太阳光下,经过15 min Cu2O沉积的TNTs具有最高的光催化效率。在所有光催化还原CO2过程中,主要碳氢产物为甲烷。为了深入地理解该复合体系在还原CO2中的高催化效率,我们对催化剂进行了进一步的表征。紫外-可见漫反射光谱表明, Cu2O八面体纳米颗粒的沉积将TNTs的吸收光谱拓展到了可见光区域,提高了复合物对太阳光的吸收能力。此外,我们还通过测试所制样品的光电流反应、荧光发射光谱以及电化学阻抗谱,研究了催化剂中光生电子和空穴的分离和迁移能力。结果表明,适量的Cu2O沉积提高了复合物对光的吸收能力,增加了光生载流子的数量,从而使更多的光生载流子参与光催化反应。综上,本文首次报道了八面体Cu2O纳米颗粒修饰TNTs复合物的光催化还原CO2的能力。在一定量的Cu2O纳米颗粒修饰下,该复合物在光催化还原CO2生成烃类反应中表现出高效性。经过一系列详细的表征和讨论,我们认为其高效性主要源于三个方面：(1) TNTs的管状结构为反应物的吸附提供了大量的活性位点,同时一维的管状结构更有利于光生载流子的运载,从而提高了电子和空穴的分离;(2) Cu2O纳米颗粒的修饰提高了催化剂对光的吸收,促进催化剂最大程度地利用太阳光;(3) TiO2和Cu2O之间导带以及价带位置的匹配,在减少光生载流子复合的同时也降低了TiO2价带上空穴的氧化能力,从而抑制了CO2还原产物的再氧化过程。     

CeO2/NaY催化剂的氧合及其催化氧化脱硫性能

采用等体积浸渍法制备了一系列CeO₂/NaY催化剂,重点考察了焙烧温度和铈负载量对催化剂活性组分结构及性能的影响。通过拉曼（Raman）光谱、X射线衍射（XRD）、低温N₂吸附-脱附（BET）、高分辨透射电子显微镜（HR-TEM）以及氢气程序升温还原（H₂-TPR）等技术对催化剂的结构、形貌和化学性能进行了表征分析。结果表明,焙烧温度与铈负载量对于铈物种在分子筛载体表面及孔道内的分散形态和与载体的相互作用有着重要影响,进而影响催化剂中铈物种的氧合性能与氧化脱硫性能。在常温常压下的氧合性能测试,催化剂最大储氧量为每克催化剂1.44 mmol O₂。在反应温度100 ℃,催化剂用量0.20 g,以正辛烷为溶剂二苯并噻吩初始浓度为500 μg·g^-1的模拟油样20 mL,氧气流量为50 mL·min^-1的条件下,反应240 min二苯并噻吩转化率可达90.10%,二苯并噻吩被氧化为二苯并噻吩砜。因此,发展稀土改性分子筛催化剂,应用于以分子氧为氧化剂的油品氧化深度脱硫,对探究绿色高效的油品氧化脱硫技术具有积极意义。     

用Dawson型聚氧钨酸乳液催化氧化燃油超深度脱硫

合成了Dawson型聚氧钨酸乳液催化剂Q18P2W18,Q18P2W17,和Q18P2W12.采用红外光谱和固体核磁技术对其进行了表征,并用于温和条件下H2O2氧化4,6-二甲基二苯并噻吩(4,6-DMDBT)、二苯并噻吩(DBT)、苯并噻吩(BT)和2,5-二甲基噻吩(2,5-DMT)等含硫化合物的反应中.结果表明,...     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.     

New metal complexes supported on Fe3O4 magnetic nanoparticles as recoverable catalysts for selective oxidation of sulfides to sulfoxides

Fe₃O₄ nanoparticles were coated with aminopropyltriethoxysilane and subsequently reacted with isatin to obtain imine‐bonded Fe₃O₄ nanoparticles. The addition of ZrOCl₂?8H₂O or CuCl₂ led to the formation of complexes of Zr(IV)/isatin@Fe₃O₄ or Cu (II)/isatin@Fe₃O₄ as new magnetically separable catalysts. The synthesized catalysts were characterized using various techniques. These catalysts are shown to be efficient for chemo‐selective oxidation of sulfides to sulfoxides using hydrogen peroxide as oxidative agent. This system has many advantages, such as excellent level of reusability of magnetic catalysts, high yields, simplicity of separation of catalysts using an external magnet, environmental benignity and ease of handling. Copyright © 2016 John Wiley & Sons, Ltd.     

New Cu-based catalysts supported on TiO2 films for Ullmann S(N)Ar-type C-O coupling reactions

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).     

十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛（英文）

苯甲醛是一种用途广泛的重要化学品,通过O2氧化甲苯制取苯甲醛是最佳生产途径,也是近几十年来工业界迫切需要的反应之一.虽然该反应在苄基上结合一个氧再脱除两个氢即可,对该反应的多相催化过程也已经研究了几十年,但其性能仍远远低于工业要求.当前的工业过程主要有甲苯氯化水解法和甲苯均相氧化法两种,但都存在严重的环境污染和腐蚀问题,且产品中含有少量卤素,阻碍了其在诸如香水或食品中的高端应用.近年来,以O2作为氧化剂及Pd,Au,Pt,Ag,Ru等贵金属或它们间的合金为催化剂的甲苯液相氧化反应研究取得了一些很好的进展,但仍然不能在高甲苯转化率下高选择性地得到苯甲醛.本课题组曾报道了一种高效的混相催化体系,以O2作为氧化剂将甲苯专一地催化氧化为苯甲醛,其中十六烷基膦酸-氧化铁(HDPA-FeOx)纳米颗粒处在甲苯和水的界面上,稳定了该O/W类皮克林乳液(Pickering).为了进一步提高催化剂晶格氧的移动性以提升催化活性,本文采用Mn, Co, Ni, Cu, Cr, Mo, V和Ti等一系列金属氧化物对催化剂HDPA-Fe Ox进行掺杂,同时使用一种特殊的纳米Al2O3作为载体,大大地增加了催化剂制备的便捷性和保证了催化剂在实际应用中的稳定性.TEM和XRD结果表明,Al2O3负载了金属氧化物后,其形貌仍为纳米棒状结构,并只能观察到Al2O3的晶相衍射峰,表明金属氧化物均匀地负载在其表面.BET结果表明,负载后的催化剂的孔结构与载体Al2O3类似.FT-IR结果表明,HDPA很好地吸附在了催化剂表面.TG结果表明,催化剂中HDPA含量与加入量相符,质量分数为~5%.结合前期工作可知,HDPA能够调整Fe M纳米棒表面催化性质,且以1 HDPA/nm2的密度为最佳,此时,甲苯液相氧化为苯甲醛的催化性能最佳.催化性能测试结果表明,催化剂吸附了HDPA后,甲苯的转化率显著增加,且只生成苯甲醛.在所考察的第二种掺杂金属中,以Ni的效果为最好.该催化剂在最佳反应条件下,甲苯转化率为83%(TOF=0.027nm–2·s–1),苯甲醛选择性为~100%.而Cr,Mo,V和Ti等高价金属则抑制了该反应,这也说明通过掺杂第二种金属调变晶格氧的活动性可影响反应性能.经过优化后,最佳反应条件为:p H值为2.5,反应温度为180°C.原位FT-IR结果表明, 180°C下,甲苯在吸附有HDPA的催化剂表面能够发生化学吸附,苄基C–H键解离并与晶格氧产生结合,形成了C6H5–CH2–O–Fe中间物种,该物种脱附即得苯甲醛.该温度下,表面HDPA对甲苯的化学吸附不可缺.     

Fe3O4@MCM-48–SO3H:合成苯并[f]色烯并[2,3-d]嘧啶酮的高效、可磁性分离纳米催化剂（英文）

Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM‐48. The sulfonic acid‐functionalized nanoparticles were evaluated as catalysts for the synthesis of 5‐aryl‐1H‐benzo[f]chromeno[2,3‐d]pyrimidine‐2,4(3H,5H)‐dione derivatives in terms of activity and recyclability. Their catalytic activities were compared with that of the homogeneous acid catalyst 1‐methylimidazolium hydrogen sulfate ([HMIm][HSO4]). The activity of Fe3O4@MCM‐48–SO3H was comparable to those of the other heter‐ogeneous and homogeneous catalysts.     

甲烷部分氧化制合成气反应Pt/Al_2O_3和Pt/CeO2/Al_2O_3催化剂的研究(英文)

研究了Ｐｔ／Ａｌ２Ｏ３和Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３催化剂对甲烷部分氧化制合成气反应的催化活性，发现Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３显示了比Ｐｔ／Ａｌ２Ｏ３更高的甲烷转化率和合成气选择性。用Ｈ２ＴＰＲ，Ｈ２ＴＰＤ，ＳＥＭ和ＸＲＤ等手段和技术对催化剂进行了表征。ＣｅＯ２与Ｐｔ之间存在较强的相互作用（ＳＭＳＩ），这种作用促进了Ｐｔ在催化剂表面的分散，抑制了Ｐｔ在催化剂表面的迁移，大大降低了催化剂在反应中的完全燃烧活性，提高了催化剂的部分氧化活性和选择性，避免了因催化剂床层局部温度过高而导致催化剂活性下降或失活，提高了催化剂的稳定性。同时，在反应过程中，ＣｅＯ２通过促进水蒸气变换反应（ＷＧＳＲ）的进行使反应体系迅速达到平衡，提高了催化剂对Ｈ２的选择性。     

CO oxidation mechanism on CeO(2)-supported Au nanoparticles

Density functional theory was used to study the CO oxidation catalytic activity of CeO(2)-supported Au nanoparticles (NPs). Experimental observations on CeO(2) show that the surface of CeO(2) is enriched with oxygen vacancies. We compare CO oxidation by a Au(13) NP supported on stoichiometric CeO(2) (Au(13)@CeO(2)-STO) and partially reduced CeO(2) with three vacancies (Au(13)@CeO(2)-3VAC). The structure of the Au(13) NP was chosen to minimize structural rearrangement during CO oxidation. We suggest three CO oxidation mechanisms by Au(13)@CeO(2): CO oxidation by coadsorbed O(2), CO oxidation by a lattice oxygen in CeO(2), and CO oxidation by O(2) bound to a Au-Ce(3+) anchoring site. Oxygen vacancies are shown to open a new CO oxidation pathway by O(2) bound to a Au-Ce(3+) anchoring site. Our results provide a design strategy for CO oxidation on supported Au catalysts. We suggest lowering the vacancy formation energy of the supporting oxide, and using an easily reducible oxide to increase the concentration of reduced metal ions, which act as anchoring sites for O(2) molecules.     

活性炭负载TiO2光催化氧化二苯并噻吩的研究

以活性炭负载的TiO2为光催化剂,H2O2为氧化剂,30W紫外灯为光源,对含二苯并噻吩（DBT）的模型硫化物进行光催化氧化脱硫研究。考察了TiO2的煅烧温度、负载量、催化剂用量、H2O2用量和光照时间对DBT去除率的影响。实验结果表明,用溶胶 凝胶法制备的TiO2 /活性炭催化剂对DBT具有很好的光催化效果。最佳反应条件为,催化剂煅烧温度400℃,TiO2的负载量为32％,催化剂用量0.7g/100mL, H2O2最佳用量为10mL,即O/S（摩尔比）为14。在最佳反应条件下,光照时间8h,DBT去除率为90％, 此反应为一级动力学反应。