On the reactivity of Mo species for methane partial oxidation on Mo/HMCM-22 catalysts

By characterizing fresh and used Mo/HMCM-22 catalysts with ICP-AES, XRD, NH3-TPD technique, UV - Vis DRS and UV Raman spectroscopy, the reactivity of Mo species for methane partial oxidation into formaldehyde were directly studied with a new point of view. By comparing the fresh and used catalysts, it was found that the tetrahedral Mo species bonding chemically to the support surface were practically unchanged after the reaction, while the polymolybdate octahedral Mo species, which had a rather weak interaction with the MCM-22 zeolite, leached out during the reaction, especially when the Mo loading was high. Correspondingly, it was found from the time-on-stream reaction data that the HCHO yield remained unchanged, while COx decreased with the reaction time during the reaction. By combining the characterization results and the reaction data, it can be drawn that the isolated tetrahedral molybdenum oxo-species (T-d) is responsible for HCHO formation, while the octahedral polyoxomolybdate species (O-h) will lead to the total oxidation of methane.

Reactivity of Pt/Al2O3 and Pt/CeO2/Al2O3 catalysts for partial oxidation of methane to syngas

The ceria modified Pt/CeO2/Al2O3 and Pt/Al2O3 catalysts were studied in the partial oxidation of methane to syngas. The SEM, XRD, TPR and TPD techniques were used for the catalyst characterization. The addition of ceria could enhance the Pt dispersion and decrease the Pt crystallise size; the activity and selectivity of catalyst for partial oxidation were improved significantly, and the methane total oxidation was suppressed sharply. The ceria effect was also discussed in a detailed way.

FT-IR spectroscopic study of the oxidation of chlorobenzene over Mn-based catalyst

Adsorption and oxidation of chlorobenzene on Al(2)O(3), TiO(2)-Al(2)O(3), and MnO(x)/TiO(2)-Al(2)O(3) have been studied by in situ Fourier transform infrared (FT-IR) spectroscopy. At room temperature, chlorobenzene is only physisorbed on Al(2)O(3), TiO(2)-Al(2)O(3), and MnO(x)/TiO(2)-Al(2)O(3), and gives the same IR spectrum as that for liquid-phase chlorobenzene. On Al(2)O(3) no further interaction and reaction take place with treatment, at higher temperatures (up to 773 K), while phenolates are observed for TiO(2)-Al(2)O(3) and MnO(x)/TiO(2)-Al(2)O(3) at 773 K. When the adsorbed chlorobenzene coexists with oxygen, formates are detected for Al(2)O(3), while acetates are additionally observed for TiO(2-)Al(2)O(3) above 573 K. For MnO(x)/TiO(2-)Al(2)O(3), maleates are present at 573 And 673 K, while formates and acetates develop at 473 and 573 K. Almost all IR bands due to formates, acetates, and maleates disappear at 773 K, indicating that these oxygen-containing species are potential intermediates for the total oxidation of chlorobenzene.

Catalytic oxidation of chlorobenzene on supported manganese oxide catalysts

Total oxidation of chlorinated aromatics on supported manganese oxide catalysts was investigated. The catalysts have been prepared by wet impregnation method and characterized by XRD and TPR. Among the catalysts with the supports of TiO(2), Al(2)O(3) and SiO(2), titania supported catalyst (MnO(x)/TiO(2)) gives the highest catalytic activity. MnO(x)/TiO(2) (Mn loading, 1.9 wt.%) shows the total oxidation of chlorobenzene at about 400 degreesC. The activity can be stable for over 82 h except for the first few hours. At lower Mn loadings for MnO(x)/TiO(2), only one reduction peak appears at about 400 degreesC due to the highly dispersed manganese oxide. With the increase of Mn loading, another reduction peak emerges at about 500 degreesC, which is close to the reduction peak of bulk Mn(2)O(3) at 520 degreesC. TPR of the used catalyst is totally different from that of the fresh one indicating that the chemical state of the active species is changed during the chlorobenzene oxidation. The characterization studies of MnO(x)/TiO(2) showed that the highly dispersed MnO(x) is the precursor of the active phase, which can be converted into the active phase, mainly oxychlorinated manganese (MnO(y)Cl(z)), under working conditions of chlorobenzene oxidation. (C) 2001 Elsevier Science B.V. All rights reserved.

Oxidative destruction of chlorobenzene and o-dichlorobenzene on a highly active catalyst: MnOx/TiO2-Al2O3

A highly active catalyst, MnOx/TiO2-Al2O3, was prepared by impregnating MnOx species on TiO2-modified Al2O3. The TiO2 species in TiO2-Al2O3 support is in a monolayer dispersion, and the MnOx species is again highly dispersed on TiO2-Al2O3 Support. The total oxidation of chlorobenzene and o-dichlorobenzene on MnOx/TiO2-Al2O3 catalyst can be achieved at 300 degreesC and 250 degreesC respectively, at the space velocity of 8000 h(-1). The activity of MnOx/TiO2-Al2O3 catalyst (Mn loading 11.2 wt%) is gradually increased in the first 10-20 h and then keeps stable at least for the measured 52 h at 16,000 h(-1). Furthermore, no chlorinated organic byproducts are detected in the effluent during the oxidative destruction of chlorobenzene and o-dichlorobenzene. It is proposed that the partially chlorinated and highly dispersed manganese oxide on a monolayer TiO2-modified Al2O3 is responsible for the high and stable activity for the total oxidation of chlorinated aromatics. (C) 2001 Academic Press.

Rapid quantification of total microcystins in cyanobacterial samples by periodate-permanganate oxidation and reversed-phase liquid chromatography

Microcystins (MCs) comprise a family of more than 80 related cyclic hepatotoxic heptapeptides. Oxidation of MCs causes cleavage of the chemically unique C-20 beta-amino acid (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda) amino to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB), which has been exploited to enable analysis of the entire family. In the present study, the reaction conditions (e.g. concentration of the reactants. temperature and pH) used in the production of MMPB by oxidation of cyanobacterial samples with permanganate-periodate were optimized through a series of well-controlled batch experiments. The oxidation product (MMPB) was then directly analyzed by high-performance liquid chromatography with diode array detection. The results of this study provided insight into the influence of reaction conditions on the yield of MMPB. Specifically, the optimal conditions, including a high dose of permanganate (>= 50 mM) in saturated periodate solution at ambient temperature under alkaline conditions (pH similar to 9) over 1-4 h were proposed, as indicated by a MMPB yield of greater than 85%. The technique developed here was applied to determine the total concentration of MCs in cyanobacterial bloom samples, and indicated that the MMPB technique was a highly sensitive and accurate method of quantifying total MCs. Additionally, these results will aid in development of a highly effective analytical method for detection of MMPB as an oxidation product for evaluation of total MCs in a wide range of environmental sample matrices, including natural waters, soils (sediments) and animal tissues. (C) 2009 Elsevier B.V. All rights reserved.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

Gas phase catalytic partial oxidation of toluene in a microchannel reactor

Gas phase partial oxidation of toluene over V/Ti oxide catalysts has been successfully performed in a microchannel reactor, which provides very good mass and heat transfer conditions. With the elimination of hot spots, which are known as the most negative factors for partial oxidation of hydrocarbons, steady and uniform reaction conditions can be achieved in the catalyst bed by using, the microreactor. Since the best performance of the catalysts might be exploited, the selectivity of partial oxidation products of toluene has remarkably increased compared to the traditional packed fixed-bed reactor, even without the bother of modifying the catalysts, diluting the reactants or catalysts with inert contents to avoid hot spots or improve the diffusion and mixing. Furthermore, in virtue of its inherent safety features, when using pure oxygen as oxidant, the reactions were handled safety within the explosion limits in the microreactor. With TiO2 carried V2O5 as catalysts, the total selectivity of benzaldehyde and benzoic acid reaches around 60%, and the toluene conversion is about 10%. The conversion can go up without violent decline of selectivity, unlike most fixed bed reactors. Space time yield of 3.12 kg h(-1) L-1 calculated on the basis of the channel volume has been achieved. The influence of operating conditions has been investigated in detail in the microreactor. (c) 2005 Elsevier B.V. All rights reserved.

Formation and structure of composite coating of HDA and micro-plasma oxidation on A3 steel

Composite coatings were obtained on A3 steel by hot dipping aluminum(HDA) at 720 ℃ for 6 min and micro-plasma oxidation(MPO) in alkali electrolyte. The surface morphology, element distribution and interface structure of composite coatings were studied by means of XRD, SEM and EDS. The results show that the composite coatings obtained through HDA/MPO on A3 steel consist of four layers. From the surface to the substrate, the layer is loose Al2O3 ceramic, compact Al2O3 ceramic, Al and FeAl intermetallic compound layer in turn. The adhesions among all the layers are strengthened because the ceramic layer formed at the Al surface originally, FeAl intermetallic compound layer and substrate are combined in metallurgical form through mutual diffusion during HDA process.Initial experiment results disclose that the anti-corrosion performance and wear resistance of composite coating are obviously improved through HDA/MPO treatment.

Correlation between Discharging Property and Coatings Microstructure during Plasma Electrolytic Oxidation

The voltage-current properties during plasma electrolytic discharge were determined by measuring the current density and cell voltage as functions of processing time and then by mathematical transformation. Correlation between discharge I-V property and the coatings microstructure on aluminum alloy during plasma electrolfic oxidation was determined by comparing the voltage-current properties at different process stages with SEM results of the corresponding coatings. The results show that the uniform passive film corresponds to a I-V property with one critical voltage, and a compound of porous layer and shred ceramic particles corresponds to a I-Vproperty with two critical voltages. The growth regularity of PEO cermet coatings was also studied.

Biosensor with Total Internal reflection Imaging Ellipsometry

In order to monitor multiple protein reaction processes simultaneously, a biosensor based on imaging ellipsometry operated in the total internal reflection mode is proposed. It could be realised as an automatic analysis for protein interaction processes with real-time label-free method. Its principle and methodology as well as a demonstration for its applications are presented.

Amorphous Coatings Deposited on Aluminum Alloy by Plasma Electrolytic Oxidation

Amorphous [Al-Si-O] coatings were deposited on aluminum alloy by plasma electrolytic oxidation (PEO). The process parameters, composition, micrograph, and mechanical property of PEO amorphous coatings were investigated. It is found that the growth rate of PEO coatings reaches 4.44 mu m/min if the current density is 0.9 mA/mm(2). XRD results show that the PEO coatings are amorphous in the current density range of 0.3-0.9 mA/mm(2). EDS results show that the coatings are composed of O, Si and At elements. SEM results show that the coatings are porous. Nano indentation results show that the hardness of the coatings is about 3 - 4 times of that of the substrate, while the elastic modulus is about the same with the substrate. Furthermore, a formation mechanism of amorphous PEO coatings was proposed.

Effect of diffusion on coating microstructure and oxidation resistance of aluminizing steel

The effect of diffuse treatment on coating microstructure and oxidation resistance at high-temperature of hot-dip aluminum were studied by means of TEM, SEM and XRD. The results show that, the diffusion temperature has significant effect on structure of coatings and its oxidation resistance. After diffusion at 750 degreesC, the coating consists of thick outer surface layer (Fe2Al5+ FeAl2), thin internal layer (FeAl + stripe FeAl2), and its oxidation resistance is poor. After diffusion at 950 degreesC, the outer surface layer is composed of single FeAl2 phase, the internal layer is composed of FeAl phase, and its oxidation resistance declines due to the occurrence of early stage internal oxidation cracks in the coating. After diffusion at 850 degreesC, the outer surface layer becomes thinner and consists of FeAl2 Fe2Al5(small amount), the internal layer becomes thicker and consists of FeAl+spherical FeAl2, and the spheroidized FeAl2 phase in the internal layer and its existing in FeAl phase steadily improve the oxidation resistance of the coating.

Revelation of a Functional Dependence of the Sum of Two Uniaxial Strengths/Hardness on Elastic Work/Total Work of Indentation

Dimensional and finite element analyses were used to analyze the relationship between the mechanical properties and instrumented indentation response of materials. Results revealed the existence of a functional dependence of (engineering yield strength sigma(E,y) + engineering tensile strength sigma(E,b))/Oliver & Pharr hardness on the ratio of reversible elastic work to total work obtained from an indentation test. The relationship links up the Oliver & Pharr hardness with the material strengths, although the Oliver & Pharr hardness may deviate from the true hardness when sinking in or piling up occurs. The functional relationship can further be used to estimate the SUM sigma(E,y) + sigma(E,b) according to the data of an instrumented indentation test. The sigma(E,y) + sigma(E,b) value better reflects the strength of a material compared to the hardness value alone. The method was shown to be effective when applied to aluminum alloys. The relationship can further be used to estimate the fatigue limits, which are usually obtained from macroscopic fatigue tests in different modes.

Electrochemical Impedance Spectroscopy Of Peo Coating On Aluminum Alloy In Nacl Solution

Various Plasma Electrolytic Oxidation (PEO) ceramic coatings were prepared on LY12 aluminum alloy by adjusting the concentration of sodium silicate solution. Optical microscope (OM), XRD and EIS were used to study their morphology, composition and anti corrosion behavior in NaCl solution. Increasing concentration of sodium silicate leads to the increase of the total coating thickness while too high and too low concentration lead to the decrease of inner dense layer. The main composition of PEO coatings prepared in 20, 40 and above 60g/L concentration solution are correspondingly alumina, alumina with mullite, and amorphous phase. The corrosion resistance is determined by the inner dense layer. Increasing the thickness of inner dense layer can improve the anti-corrosion performance. PEO coating's corrosion resistance in acidic, alkaline and neutral NaCl solution is proved and the corrosion mechanism involved is also discussed.