Surfactant-modified polypropylene as a catalyst for oxidation of mercaptans

Surface modification of polypropylene by soluble metallophthalocyanine was performed. The effect of pretreatment of polypropylene on the degree of surface anchoring of the macrocycle was shown. The catalytic activity of the hybrid materials produced in the oxidation reaction of sodium diethyldithiocarbamate was determined.     

PEDOT-supported Pd nanoparticles as a catalyst for hydrazine oxidation

Composite poly-3,4-ethylenedioxythiophene (PEDOT)/palladium (Pd) films were obtained by chemical deposition of dispersed palladium nanoparticles into PEDOT conducting polymer matrix. The amounts of palladium particles incorporated into PEDOT films were estimated by electrochemical quartz crystal microbalance measurements. It was shown that palladium loading depends on the time a PEDOT film is exposed in the solution, containing Pd(II)-ions, on the concentration of Pd(II) ions and the film thickness. X-ray photoelectron spectroscopy data have confirmed the presence of metallic palladium in the polymer. The morphology of pristine and composite films as well as the size of Pd nanoparticles and their distribution were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). From SEM images, it was found that Pd particles decorated PEDOT globular structures as quasi-spherical particles, and their mean size was dependent on synthesis conditions. The nanoparticles were non-uniformly dispersed on the polymer surface. The comparison of TEM images of composite PEDOT/Pd films obtained for different times of metal loading was made. The remarkable effect of loading time on the size of particles has been established: the mean size of dominating palladium particles was close to 6–10 nm for 30 s of metal deposition, and it was getting larger with the increase of deposition time (close to 15–30 nm for 120 s). It is most likely that with prolongation of synthesis time, the deposition of palladium predominantly proceeds on the already deposited palladium clusters, resulting in the extension growth of their size. Catalytic properties of PEDOT/Pd composite films were studied in respect to hydrazine oxidation by cyclic voltammetry and voltammetry on rotating disk electrode. The obtained data allow to conclude that the process of hydrazine oxidation on PEDOT/Pd composites takes place predominantly on palladium particles, located on the surface or in the near-surface layers of the polymer. The diffusion nature of the limiting current of hydrazine oxidation on composite PEDOT/Pd film in phosphate buffer solution рН = 6.86 was confirmed, and hydrazine diffusion coefficient was calculated. The increase of the limiting currents of hydrazine oxidation with the increase of Pd deposition time was observed, resulting from the increase of the active surface area of palladium particles, acting as microelectrodes. The electroanalytical applications of these nanocomposite materials for the determination of hydrazine were demonstrated.     

Electrochemical oxidation of vanillic acid by electro-Fenton process: Toward a novel route of protocatechuic acid electrosynthesis

The electrochemical oxidation of vanillic acid (VA) in acetone–water mixtures, was studied by electro-Fenton (EF) process in an undivided electro-chemical cell equipped with a carbon fiber cloth as cathode and Pt anode. The objective was the conversion of VA into protocatechuic acid (PCA) well known by its high added value. To our knowledge, the EF method was not used in organic electrosynthesis. The influence of several operating parameters, such as applied current, initial VA concentration and volumic percentage of acetone was investigated. The evolution of the concentrations of VA and its main oxidation product PCA during electrolyses was monitored by means of high performance liquid chromatography (HPLC). The experimental data indicated that the kinetics of VA disappearance follow a pseudo first and zero orders for initial VA concentrations respectively equals to 6.5 and (10, 20, 30) mmol L⁻¹. The maximum PCA concentration increases with volumic percentage of acetone and initial VA concentration. Under optimal experimental conditions of applied current (20 mA) and volumetric percentage of acetone (20%), the increase in the initial VA concentration leads to a linear increase in the maximum of PCA concentration. The very good selectivity rate of the oxidation of VA to PCA by the EF process, was interpreted by the stabilizing effects of acetone and especially the complexation of PCA by the iron ions.     

CoSALEN as a new catalyst for oxidation of fullerene C60

The effect of CoSALEN on anti-oxidative properties of fullerene C₆₀ in the presence of O₂ in cumene was investigated. A comparison was made between the role of the CoSALEN as a catalyst in the C₆₀ oxidation and oxidation in the presence of an initiator, i.e., AIBN. A mechanism is proposed for the catalytic role of CoSALEN in oxidation of C₆₀. Oxidation of octadecylaminofullerene C₆₀ at the same conditions reveals that oxidation could be a result of hydroperoxidation of the unreacted sites of C₆₀. We conclude that C₆₀ as well as its amino-derivatives enhance the efficiency of CoSALEN in the oxidation of cumene due to their radical scavenging property of their unreacted double-bond sites.     

基于N-掺杂碳包覆Fe3N复合材料的高效异相电芬顿降解有机物

水污染导致的缺水危机、水质恶化和生态环境破坏等问题,严重影响人的健康及社会的和谐可持续发展.异相电芬顿技术因催化剂可循环利用、宽pH适用范围等优点而广受关注.常见的催化剂以铁、铁氧化物等铁基材料为主,存在金属颗粒分布不均匀、铁元素易溶出、铁循环易受阻和H2O2选择性和转化效率低等问题,严重制约该技术的发展.尽管可以通过...     

Supported ruthenium catalyst as an effective catalyst for selective oxidation of toluene

The investigation comprised an evaluation of the use of the catalyst 1%Ru/TiO₂ in the liquid-phase conversion of toluene to benzyl alcohol and benzaldehyde. Transmission electron microscopy (TEM) and N₂ adsorption-desorption isotherms were deployed to delineate the properties of the supported catalysts. The findings indicated a good catalytic performance by 1%Ru/TiO₂ under green reaction conditions. This performance was deemed a consequence of the spread and loading of Ru on the TiO₂. The reaction conditions such as temperature, reaction time, type of support, catalyst preparation method, and activating quantity) were optimized to achieve superior reaction parameters. Catalyst produced via sol-immobilization has higher activity than the one prepared with the wet-impregnation method, which lead to a transformation rate of up to 9.5%, with the selectivity for benzyl alcohol at 92%.     

钴/碳纤维电化学催化氧化甲苯性能研究

以纤维状活性碳吸附Co2+作为电极,在水溶液体系中,高效吸附-电化学催化氧化两步联动法矿化处理气态甲苯。实验结果显示,甲苯通过电化学反应器后能够被有效的降解。在电流密度为0.05 A·cm-2,电解电压为12 V,鼓气速率为80 L·h-1的条件下,甲苯的去除率达90%以上。甲苯降解后的主要产物为苯甲酸。     

Electrochemical water oxidation by photo-deposited cobalt-based catalyst on a nano-structured TiO2 electrode

A cobalt-based catalyst was directly photo-deposited on the surface of a widely used n-type nano-structured semiconductor(TiO 2).Different thicknesses of the TiO 2 films as well as different time of photo-deposition of the Co-based catalyst on TiO 2 films have been optimized.It was found that the electrode with 3 layers of TiO 2 film(in 8 m thickness) and 1 hour photo-deposition of the cobalt-based catalyst by light irradiation from a 500 W Xenon lamp gave the highest current density(～5 mA/cm 2).Using this cobalt-modified TiO 2 film as a working electrode in an electrochemical device,highly efficient water oxidation has been demonstrated in a pH 7.0 aqueous solution with low overpotential.     

Graphene-supported hemin as a highly active biomimetic oxidation catalyst

Well supported: stable hemin-graphene conjugates formed by immobilization of monomeric hemin on graphene, showed excellent catalytic activity, more than 10 times better than that of the recently developed hemin-hydrogel system and 100 times better than that of unsupported hemin. The catalysts also showed excellent binding affinities and catalytic efficiencies approaching that of natural enzymes.     

Platinum-containing hyper-cross-linked polystyrene as a modifier-free selective catalyst for L-sorbose oxidation.

Impregnation of hyper-cross-linked polystyrene (HPS) with tetrahydrofuran (THF) or methanol (ML) solutions containing platinic acid results in the formation of Pt(II) complexes within the nanocavities of HPS. Subsequent reduction of the complexes by H2 yields stable Pt nanoparticles with a mean diameter of 1.3 nm in THF and 1.4 nm in ML. The highest selectivity (98% at 100% conversion) measured during the catalytic oxidation of L-sorbose in water is obtained with the HPS-Pt-THF complex prior to H2 reduction. During an induction period of about 100 min, L-sorbose conversion is negligible while catalytic species develop in situ. The structure of the catalyst isolated after the induction period is analyzed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. Electron micrographs reveal a broad distribution of Pt nanoparticles, 71% of which measure less than or equal to 2.0 nm in diameter. These nanoparticles are most likely responsible for the high catalytic activity and selectivity observed. The formation of nanoparticles measuring up to 5.9 nm in diameter is attributed to the facilitated intercavity transport and aggregation of smaller nanoparticles in swollen HPS. The catalytic properties of these novel Pt nanoparticles are highly robust, remaining stable even after 15 repeated uses.     

Aerobic oxidation of alcohols using bismuth bromide as a catalyst

We developed an environmentally friendly method for aerobic oxidation of alcohols using a commercially available, relatively benign bismuth salt as a catalyst. We found that the catalytic combination of BiBr₃ with nitric acid is key for enhancing the reactivity. The reaction proceeds well under air, making the use of pure oxygen unnecessary. Each of the primary or secondary alcohols tested was oxidized to the corresponding aldehydes or ketones using this protocol.     

CoAPO5 as a water oxidation catalyst and a light sensitizer

We report the first use of cobalt aluminophosphate (CoAPO5) as a water oxidation catalyst. A decrease in the overvoltage by about 0.2 V with respect to catalyst free FTO has been observed. Additionally, we show that CoAPO5, deposited on ITO or Pt, can also act as a photo-electro-catalyst, as it generates enhanced oxidation currents in the presence of light starting from a bias of +0.8 V vs. Ag/AgCl.     

Nitrogen‐doped C60 as a robust catalyst for CO oxidation

The O₂ activation and CO oxidation on nitrogen‐doped C₅₉N fullerene are investigated using first‐principles calculations. The calculations indicate that the C₅₉N fullerene is able to activate O₂ molecules resulting in the formation of superoxide species ( ) both kinetically and thermodynamically. The active superoxide can further react with CO to form CO₂ via the Eley–Rideal mechanism by passing a stepwise reaction barrier of only 0.20 eV. Ab initio molecular dynamics (AIMD) simulation is carried out to evidence the feasibility of the Eley–Rideal mechanism. In addition, the second CO oxidation takes place with the remaining atomic O without any activation energy barrier. The full catalytic reaction cycles can occur energetically favorable and suggest a two‐step Eley–Rideal mechanism for CO oxidation with O₂ catalyzed by the C₅₉N fullerene. The catalytic properties of high percentage nitrogen‐doped fullerene (C₄₈N₁₂) is also examined. This work contributes to designing higher effective carbon‐based materials catalysts by a dependable theoretical insight into the catalytic properties of the nitrogen‐doped fullerene. © 2017 Wiley Periodicals, Inc.     

Molten salt-assisted synthesis of bulk CoOOH as a water oxidation catalyst

Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing temperature,and its size can reach dozens of microns.X-ray absorption near edge structure and XPS studies demonstrate that the Co valence state of CoOOH-750 is trivalent,and X-ray Absorption Fine Structure shows that it had a higher symmetry and lower disorder degree,indicating that CoOOH-750 has higher crystallinity and Co~(3+).The results of electrochemical tests show that CoOOH-750 exhibited the best oxygen-evolution-reaction(OER)catalytic activity.     

Highly porous cellular copper as a catalyst for ozone oxidation of organic water pollutants

The synthesis of high-porosity cellular copper and structural features of its surface were studied. Results obtained in studying the activity of high-porosity copper catalyst during ozone oxidation of organic substances dissolved in water are given by an example of oxalic and benzoic acids.     

Efficient anchorage of Pd nanoparticles on carbon nanotubes as a catalyst for hydrazine oxidation

A simple method is devised to deposit well-dispersed Pd nanoparticles on multi-walled carbon nanotubes (CNTs). Pd nanoparticles (1–3 nm) prepared in ethanol were transferred to toluene solution and modified by organic molecule benzyl mercaptan which acts as a cross linker between Pd nanoparticles and CNTs. The morphology and structure of the resulting Pd/CNT nanocomposite were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results show that Pd nanoparticles were highly dispersed and effectively anchored on CNTs. The excellent electrocatalytic activity of the Pd/CNT nanocomposite for the oxidation of hydrazine was demonstrated by cyclic voltammetry.     

Cobalt hydroxides immobilized on ionites as catalyst for water-to-oxygen oxidation

A way of preparation of dioxygen-evolving catalysts by immobilization of cobalt compounds on ion-exchange resins is proposed. Immobilized cobalt hydroxides are more selective in the reaction of water-to-oxygen oxidation than massive ones and, when prepared as mixture with Al(III), Fe(III), Sn(IV) or Ce(IV), they become even more selective.

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. , , Al(III), Fe(III), Sn(IV), Ce(IV) .

     

高效SnO2纳米片催化剂用于CO氧化

SnO2是一种具有丰富表面缺位氧的n型半导体,其晶格氧亦可还原.另外其熔点高达1630oC,具有较高的热稳定性能.在过去的几十年中, SnO2主要用作气敏材料.而其作为催化材料的性能,特别是用于大气污染治理则鲜见报道.在过去的几年中,本课题组系统研究了SnO2的催化化学,发现利用传统共沉淀法制备的SnO2纳米粉末,在焙烧温度高于500 oC时,其比表面积通常低于20 m2/g,因而限制了其氧化活性.在SnO2晶格中掺杂Fe、Cr、Mn、Ce和Ta等形成固溶体可有效提高其比表面积并产生更多的活性氧物种,因而其对CO和CH4的氧化活性及稳定性大幅度提高.本课题组近期研究结果表明,采用熔盐法制备的高纯SnO2纳米棒单晶比SnO2纳米颗粒和纳米微球等具有更优异的CO氧化活性,260 oC即可完全氧化CO.且在240–260 oC狭窄温度区间发生转化率突跃,表现出类似贵金属的催化行为.值得指出的是, SnO2纳米棒的比表面积(1 m2/g)远低于其他几种形貌的材料,且无活泼氧存在.但研究表明SnO2纳米棒具有优先暴露的(110)活泼晶面,是导致其活性优良的主要原因.另外,我们采用简单共沉淀法成功制备了高比表面介孔Cu-Sn复合氧化物纳米片(196 m2/g),其在140 oC即可将CO完全氧化,且具有优良的抗水失活性能.因此, SnO2的形貌是影响其催化活性的主要因素之一,但迄今未见较系统深入的研究.在上述工作基础上,本文通过水热法,不添加任何有机模板剂,成功制备了厚度约10 nm的介孔SnO2纳米片和纳米棒及纳米颗粒混合物样品;采用常规共沉淀法制备了SnO2纳米颗粒.并将以上三种不同形貌的SnO2纳米材料用于CO氧化.利用SEM、XRD、N2吸附-脱附、H2-TPR和XPS探讨了不同形貌SnO2催化剂的体相结构和表面性质及其对催化性能的影响.与SnO2纳米颗粒相比,介孔SnO2纳米片具有高的比表面积、孔体积及更活泼的氧中心,因此后者CO氧化活性远高于前者.在空速18000 mL/(g·h)时, SnO2纳米片在260 oC即可完全氧化CO.而SnO2纳米颗粒的CO完全氧化温度高于360 oC. SnO2纳米棒和纳米颗粒的混合样品虽然其比表面积和孔体积及表面活性氧的活性仅略高于SnO2纳米颗粒,但XRD定量结果表明,其具有更多的暴露(110)活泼晶面,因而活性也高于SnO2纳米颗粒. SnO2纳米片催化剂的寿命及抗水性能测试结果表明,该催化剂具有良好的稳定性,且水蒸气仅对其活性产生可恢复的影响.进一步优化其性能, SnO2纳米片有可能用于实际汽车尾气状况下的CO催化清除.     

Alumina-supported cobalt phosphide as a new catalyst for preferential CO oxidation at high temperatures

Abstract

Novel alumina-supported cobalt phosphide catalysts (designated as CoP-3, CoP-10, CoP-20 and CoP-40) prepared from the precursors with Co loadings of 3, 10, 20 and 40?wt% by H₂-temperature-programmed reaction were investigated as potential catalysts for preferential CO oxidation (PROX) in excess H₂ at high temperatures. It was found that the catalytic activities of these Co₂P/γ-Al₂O₃ catalysts were related to their Co loadings. The CoP-10 catalyst showed the best PROX performance in temperature range of 220–240?°C, which was attributed to its optimal microstructures (high surface area, small particle size and big amount of active site).     

Amorphous oxide as a novel efficient catalyst for direct selective oxidation of methanol to dimethoxymethane

We report for the first time the use of an amorphous oxide catalyst for the selective oxidation of methanol in the gas phase, leading at 553 K to the production of dimethoxymethane with a selectivity as high as 90% at high methanol conversion (68%).