Decomposition of acetic acid by advanced oxidation processes

Decomposition of acetic acid, known as a non-degradable organic compound, was conducted for several advanced oxidation processes such as TiO₂-UV-H₂O₂, Fe²⁺-H₂O₂-UV, UV-H₂O₂ and TiO₂-UV system. Acetic acid was efficiency decomposed within 120 minutes of UV radiation under the initial concentration of 500 ppm. The initial chemical oxygen demands (COD _cr ) tended to increase as H₂O₂ was added in most reactions. However, the initial COD _cr was not increased as H₂O₂ was consumed for the oxidation of iron salt in the photo-Fenton oxidation process. COD _cr and concentration of acetic acid rapidly decreased as the mole ratio of hydrogen peroxide increased owing to rapid decomposition of the reactant at the beginning of reaction. All reactions show first order pseudo reaction rate. The COD _cr removal rate and the decomposition efficiency of acetic acid were fastest in the UV-H₂O₂ process.     

First insights into the borohydride oxidation reaction mechanism on gold by electrochemical impedance spectroscopy

Direct borohydride fuel cells (DBFC) exhibit some potential regarding the powering of small portable electronic devices, thanks to their high energy density as well as the facile and safe storage of borohydride salts. However, DBFC are hindered because (i) the borohydride oxidation reaction (BOR) is complex, (ii) its mechanism imperfectly determined yet and (iii) no practical electrocatalyst exhibits both fast BOR kinetics and high faradaic efficiency. In this context, we characterized the BOR mechanism for polycrystalline bulk gold (a classical model BOR electrocatalyst) in the rotating disk electrode (RDE) setup. Modeling cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) data, we propose a simplified reaction pathway, the theoretical behavior of which agrees with the experimental findings. This pathway includes at least a first irreversible electrochemical step (E) for BH₄⁻ oxidation, which competes with the electrochemical adsorption reaction (EAR) of OH⁻ anions at high potentials.     

Highly selective modification of silicon oxide structures fabricated by an AFM anodic oxidation

Anodic oxidation via atomic force microscopy is a promising method for creating submicron-sized silicon dioxide patterns on a local surface. The area patterned by AFM anodic oxidation (AAO) has different chemical properties from the non-patterned area, and thus site-selective modification of patterned surfaces is quite possible. In this study, we combined the AAO with self-assembly method and/or wet chemical etching method for the fabrication of positive and/or negative structures. These locally modified surfaces could be used to the site-selective arrangement and integration of various materials based on a pre-described pattern.      

氧化石墨烯对氰酸酯树脂固化动力学的影响

以自制GO(氧化石墨烯)作为BCE(双酚A型氰酸酯)的改性剂制备相应的改性树脂。采用非等温DSC(差示扫描量热)法、Kissinger法、Crane法和升温速率-温度(β-T)外推法研究了GO对BCE固化动力学的影响,确定了纯BCE和GO/BCE体系的固化工艺条件和动力学参数。结果表明:纯BCE体系的凝胶温度为180.0℃、固化温度为201.0℃和后处理温度为221.1℃;GO/BCE体系的凝胶温度为158.8℃、固化温度为195.7℃和后处理温度为214.3℃;纯BCE和GO/BCE固化体系的活化能分别为102.38 kJ/mol和81.68 kJ/mol,反应级数分别为0.93和0.91。     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

Novel oxidation reaction at ambient temperature and atmospheric pressure with electric discharge and oxide surface

We investigated a novel oxidation reaction with surface-oxygen and lattice-oxygen induced using a non-equilibrium electric discharge at ambient temperature. We employed MgO, ZrO₂, and TiO₂ for this novel reaction. Methane was oxidized easily and converted into H₂, CO, and CO₂ by the surface-oxygen and lattice-oxygen of oxide with activation of discharge at ambient temperature without gas-phase oxygen. The oxide itself was stable after the reaction. Among these oxides, the tetragonal phase and amorphous phase of ZrO₂ showed remarkably high activity for methane oxidation. Consequently, up to 8% of surface and lattice oxygen of the oxide was consumed by methane oxidation induced by electric discharge. The non-equilibrium electric discharge activated both the surface-oxygen and the lattice-oxygen of the oxides and methane molecules in the gas phase. After these reactions, the oxide surface vacant sites were recovered partially through steam post-treatment. Hydrogen formed simultaneously with steam decomposition. Other reactions were also studied by changing the reaction gas: methane into carbon monoxide, carbon monoxide with oxygen, and carbon monoxide with steam. Furthermore, the correlation of reactivity between the feed gas and surface oxygen was studied. Emission spectra under a CH₄ atmosphere with electric discharge showed complex peaks caused by carbon monoxide formation at 280-500 nm at 0-4 min, suggesting that surface oxygen on oxides was probably consumed within 4 min from the start of the reaction.     

In situ Raman spectroscopy studies of bulk and surface metal oxide phases during oxidation reactions

Bulk V-P-O and model supported vanadia catalysts were investigated with in situ Raman spectroscopy during n-butane oxidation to maleic anhydride in order to determine the fundamental molecular structure-reactivity/selectivity insights that can be obtained from such experiments. The in situ Raman studies of the bulk V-P-O catalysts provided information about the bulk crystalline phases, the hemihydrate precursor and its transformation to vanadyl pyrophosphate. However, the Raman experiments could not provide any molecular structural information about the amorphous and surface phases also present in this bulk metal oxide catalyst because of the strong Raman scattering from the crystalline phases. In contrast, in situ Raman studies of the model supported vanadia catalysts, where the active phase is present as a two-dimensional surface metal oxide overlayer, provided new insights into this important hydrocarbon oxidation reaction. In addition, the surface properties of the supported vanadia catalysts could be molecularly engineered to probe the role of various functionalities upon the structure-reactivity/selectivity relationship of n-butane oxidation to maleic anhydride. These fundamental studies revealed that the oxidation of n-butane required only one surface vanadia site and that the critical rate determining step involved the bridging V---O---P or V---O-support bonds. The selective oxidation of n-butane to maleic anhydride could occur over one surface vanadia site as well as multiple adjacent surface vanadia sites, but the reaction is more efficient with multiple sites. The n-butane oxidation TOF increased with the introduction of both surface Brönsted and Lewis acid sites, but only the surface Lewis acid sites increased the maleic anhydride selectivity.     

Absolute determination of reaction mechanisms by in situ measurements of reaction intermediates

This paper presents a general methodology to determine reaction mechanisms using in situ measurement of concentration and reaction rate of intermediates. The criteria for testing the validity of a reaction sequence are discussed. An example is given for a heterogeneous catalytic reaction, the decomposition of ozone on manganese oxide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Oxidation of multiwalled carbon nanotubes by nitric acid

The oxidation of MWCNTs in nitric acid was monitored using sample weight, Raman spectrum, solubility, morphology and alignment. The influence of the acid concentration, temperature and oxidation duration on the monitored parameters was assessed. A new method, based on optical microscopy is proposed for the determination of MWCNT solubility in concentrated aqueous-suspensions. The investigations revealed that the solubility is determined not only by the functional groups on the MWCNT, but also by the functionalized amorphous carbon generated during the digestion of the nanotubes. High solubility (20–40 mg/ml) is obtained only after prolonged exposure (24–48 h) in concentrated acid (60%). But in these conditions 60–90% of the MWCNTs are lost. Furthermore the MWCNTs are strongly fragmented and covered by amorphous carbon after 48 h of oxidation. It was found that the solubility correlates well with the area ratio of the G and D bands from the Raman spectrum. SEM examination of the MWCNT films showed extended alignment after 24 h of oxidation.     

Partial oxidation of toluene to benzaldehyde and benzoic acid over model vanadia/titania catalysts: role of vanadia species

Pure and K-doped vanadia/titania prepared by different methods have been studied in order to elucidate the role of vanadia species (monomeric, polymeric, bulk) in catalytic toluene partial oxidation. The ratio of different vanadia species was controlled by treating the catalysts in diluted HNO₃, which removes bulk vanadia and polymeric vanadia species, but not the monomeric ones, as was shown by FT-Raman spectroscopy and TPR in H₂. Monolayer vanadia species (monomeric and polymeric) are responsible for the catalytic activity and selectivity to benzaldehyde and benzoic acid independently on the catalyst preparation method. Bulk V₂O₅ and TiO₂ are considerably less active. Therefore, an increase of the vanadium concentration in the samples above the monolayer coverage results in a decrease of the specific rate in toluene oxidation due to the partial blockage of active monolayer species by bulk crystalline V₂O₅. Potassium diminishes the catalyst acidity resulting in a decrease of the total rate of toluene oxidation and suppression of deactivation. Deactivation due to coking is probably related to the Brønsted acid sites associated with the bridging oxygen in the polymeric species and bulk V₂O₅. Doping by K diminishes the amount of active monolayer vanadia leading to the formation of non-active K-doped monomeric vanadia species and KVO₃.     

Pd/C催化有机锡试剂和酰氯偶联反应的研究

制备了活性炭负载钯催化剂,并用于有机锡试剂与取代肉桂酰氯交叉偶联合成查耳酮化合物的反应中。考察了催化剂的催化性能,用XPS方法对催化剂进行了表征,还对反应机理进行了研究和探讨。     

The role of functional groups on graphene oxide in epoxy nanocomposites

The role of functional groups on the surface of graphene oxide (GO) upon its ability to reinforce an epoxy resin has been investigated. It is known that a base-washing process removes oxidative debris from as-prepared GO and reduces the number of functional groups in the material. Both as-prepared (aGO) and base-washed graphene oxide (bwGO) fillers were incorporated into an epoxy resin matrix and the mechanical properties of the different nanocomposites were investigated. The best levels of reinforcement were found with the addition of low loadings of aGO while the bwGO gave inferior levels of reinforcement at the same loading level. Raman spectroscopy was used to both assess the dispersion of the fillers and efficiency of stress transfer to the GO in the nanocomposites during deformation. It was found that for a given filler loading the aGO materials had the most uniform dispersion of filler and the largest Raman band shifts per unit strain, indicating the importance of the presence of functional groups in both dispersing the GO and giving good interfacial stress transfer in the nanocomposites.     

Solvent free oxidation of alcohols catalyzed by KMnO4 adsorbed on Kieselguhr

Efficient and selective oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones catalyzed by potassium permanganate supported on Kieselguhr reagent under solvent free conditions are reported.     

The heterogeneous reaction between soot and NO2 at elevated temperature

Two commercial soot samples are analysed by temperature programmed desorption mass spectroscopy (TPD-MS) in order to determine the functional groups at their surface. A systematic approach has been developed, which assures that all functional groups decomposing between 100 °C and 900 °C can be distinguished and assigned. For the understanding of the mechanism of the reaction between soot and NO₂ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and TPD-MS are applied. Both spectroscopic techniques monitor the formation of new species. The reaction with NO₂ results in the formation of an acidic functional group, which decomposes into CO₂ and NO at 140 °C. It is proven that NO₂ reacts directly with the carbon surface. Pre-existing functional groups do not interfere. From these results the reaction sequence has been concluded.     

枞酸氧化反应及其抗氧剂的研究

采用紫外分光光度分析方法研究了枞酸在聚乙烯膜上的氧化反应,考察了MBP,FMH,DBH,DSB3,DSB65种抗氧剂对枞酸氧化反应的影响,提出了用抗氧化值AO考核抗氧剂的抗氧化能力。实验结果表明,枞酸氧化反应动力学在初期阶段呈表观一级,后期受氧化膜影响不呈表观一级。当反应温度为35,40,45,50,55℃时,5种抗氧剂都表现出不同程度的抗氧化能力,其中MBP,DBH,DSB6抗氧剂的抗氧化能力显著,在35℃下其抗氧化值AO分别是109.92,50.93,209.84。     

Total oxidation catalysts based on manganese or copper oxides and platinum or palladium I: Characterisation

Temperature-programmed reduction (TPR), oxidation (TPO), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to characterise catalysts based on manganese oxides, copper oxides or one of them mixed with platinum or palladium-supported on γ-alumina. The catalysts were characterised before and after they had been exposed either to high temperature in the presence of steam or to sulphur dioxide. Raman spectroscopy, XRD, XPS and TPR performed on the fresh samples of MnO_x, mixed MnO_x–Pt and MnO_x–Pd revealed the presence of a mixture of manganese oxides, particularly Mn₂O₃. In the fresh mixed MnO_x–Pd and CuO_x–Pd samples, Pd catalysed the reduction of both MnO_x and CuO_x, whereas Pt only catalysed the reduction of MnO_x. After hydrothermal treatment at 900°C of the MnO_x, mixed MnO_x–Pt and MnO_x–Pd samples, there was a formation of new manganese oxide phase, Mn₃O₄ detected by Raman spectroscopy. TPR revealed increasing interaction between the metal oxides and the noble metals in the hydrothermally treated mixed MnO_x–Pd and CuO_x–Pd samples, and also the appearance of interaction in the treated mixed CuO_x–Pt sample. The sulphur adsorbed in all the MnO_x samples formed sulphate, which was more difficult to reduce than the oxides. Also, the reduction temperature of sulphates was lowered when noble metals are present.     

聚乙二醇重氮树脂在聚乙烯膜材料表面的自组装及亲水改性

用铬酸氧化法在聚乙烯薄膜的表面引入了羧基阴离子,合成了端基阳离子性的聚乙二醇重氮树脂,用静电自组装并辅以紫外光照射的方法,在聚乙烯薄膜的表面引入了共价键连接的聚乙二醇分子链.用紫外-可见分光光度法研究了重氮树脂及其静电自组装体系的光分解性质,得到重氮基团的分解速率常数kd=0.021 4 s-1.红外分析表明,紫外光照射后聚乙烯薄膜表面连接的聚乙二醇分子链可耐DMF-ZnC l2-H2O三元极性溶剂的刻蚀.由于在聚乙烯薄膜的表面引入了亲水性的聚乙二醇分子链,其表面接触角从改性前的104°降至48°.     

Observation of strain effect on the suspended graphene by polarized Raman spectroscopy

We report the strain effect of suspended graphene prepared by micromechanical method. Under a fixed measurement orientation of scattered light, the position of the 2D peaks changes with incident polarization directions. This phenomenon is explained by a proposed mode in which the peak is effectively contributed by an unstrained and two uniaxial-strained sub-areas. The two axes are tensile strain. Compared to the unstrained sub-mode frequency of 2,672 cm⁻¹, the tension causes a red shift. The 2D peak variation originates in that the three effective sub-modes correlate with the light polarization through different relations. We develop a method to quantitatively analyze the positions, intensities, and polarization dependences of the three sub-peaks. The analysis reflects the local strain, which changes with detected area of the graphene film. The measurement can be extended to detect the strain distribution of the film and, thus, is a promising technology on graphene characterization.     

The improved electrocatalytic activity of palladium/graphene nanosheets towards ethanol oxidation by tin oxide

Tin oxide (SnO₂)/graphene nanosheets (GNS) composite was prepared by a simple chemical-solution method as the catalyst support for direct ethanol fuel cells. Then the SnO₂-GNS composites supporting Pd (Pd/SnO₂-GNS) catalysts were synthesized by a microwave-assisted reduction process. The Pd/SnO₂-GNS catalysts were characterized by using X-ray diffraction, transmission electron microscopy and energy-dispersive spectroscopy techniques. The electrocatalytic performances of Pd/SnO₂-GNS catalysts for ethanol oxidation were studied by cyclic voltammetric and chronoamperometric measurements. It was found that compared with Pd/GNS, the Pd/SnO₂-GNS catalyst showed superior electrocatalytic activity for ethanol oxidation when the mass ratio of SnCl₂·2H₂O precursor salt to graphite oxide was about 1:2.     

The effect of ambient humidity on the electrical properties of graphene oxide films

ABSTRACT: We investigate the effect of water adsorption on the electrical properties of graphene oxide (GO) films using the DC measurement and AC complex impedance spectroscopy. GO suspension synthesized by a modified Hummer's method is deposited on Au interdigitated electrodes. The strong electrical interaction of water molecules with GO films was observed through electrical characterizations. The DC measurement results show that the electrical properties of GO films are humidity- and applied voltage amplitude dependent. The AC complex impedance spectroscopy method is used to analyze the mechanism of electrical interaction between water molecules and GO films in detail. At low humidity, GO films exhibits poor conductivity and can be seen as an insulator. However, at high humidity, the conductivity of GO films increases due to the enhancement of ion conduction. Our systematic research on this effect provides the fundamental supports for the development of graphene devices originated from solution-processed graphene oxide.