Catalytic epoxidation of olefin over supramolecular compounds of molybdenum oxide clusters and a copper complex

The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.

Compounded Surface Modification of ZK60 Mg Alloy by High Current Pulsed Electron Beam+Micro-plasma Oxidation

In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of ZK60 Mg alloy after single MPO and HCPEB＋MPO compounded treatment were investigated by SEM. The results showed that the density of the ceramic layer of HCPEB＋MPO-treated ZK60 Mg alloy was improved and defects were reduced compared to that under MPO treatment alone. Surface modified layer of ZK60 Mg alloys treated by HCPEB＋MPO was divided into three zones, namely the top loose ceramic zone, middle compact zone and inside HCPEB-induced melted zone. Corrosion resistance of ZK60 Mg alloy before and after the compounded surface modification was measured in a solution of 3.5% NaCl by potentiodynamic polarization curves. It was found that the corrosion current density of ZK60 Mg alloys could be reduced by about three orders of magnitude, from 311μA/cm^2 of the original sample to 0.2μA/cm^2 of the HCPEB＋MPO-treated sample. This indicates the great application potential of the HCPEB＋MPO compounded surface modification technology in improving the corrosion resistance of ZK60 Mg alloys in the future.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

Preparation of M2O3-CeO2(M=La,Fe,and Al) Compoundoxide Catalyst and Its Degradation Performance

As one of the most active rare earths,CeO2 has caused extensive concern due to its multifunctional properties.CeO2-based compound oxide of M2O3-CeO2(M=La,Fe,and Al)were prepared by coprecipitation and impregnation methods.The photocatalytic performance of the samples for the degradation methylene blue was studied under UV and visible light irradiation.The effects of constituents on the properties of the CeO2-based catalysts were investigated by XRD,TEM,BET,and UV-Vis spectrophotometer.The highest degradation of methylene blue under 230W UV light was almost 100%at 50 min by La2O3/Fe2O3-CeO2/γ-Al2O3 catalyst and 99.42%at 50 min by Fe2O3-CeO2/γ-Al2O3 catalyst.The methylene blue removal efficiency under indoor natural light reaches 93.81%by La2O3/Fe2O3-CeO2/γ-Al2O3 catalyst and 92.34%by Fe2O3-CeO2/γ-Al2O3 catalyst at 50 min.The order of catalytic degradation activity is La2O3/Fe2O3-CeO2/γ-Al2O3>Fe2O3-CeO2/γ-Al2O3>La2O3-CeO2/γ-Al2O3>Al2O3,owing to their structural features.The doping of La^3+or Fe3+onto CeO2/γ-Al2O produced much more oxygen vacancies under light irradiation and reduced the energy laps of CeO2 with value of 2.86 ev,which improved the photocatalytic redox performance of the composite oxide.

Syntheses，Structures and Properties of Some New Composition Perovskite Compounds：Sr0．6Bi0．4FeO2．7，Sr1－xBixFeO3－y and Ba1．5Pt0．5Mn2O6

New composition perovskite-type compounds with formula Sr0.6Bi0.4FeO2.7,Sr1-xBixFeO3-y(x=0.1 to 0. 9 in interveral of 0.1),and Ba1.5Pt0.5Mn2O6 have been synthsized and structurally characterized.The crystal structure of Sr0.6Bi0.4FeO2.7has been determined by X-ray single crystal diffraction,and the data of neutron powder diffraction collected at both room temperature and elevated temperature(380℃).The compound Sr0.6Bi0.4FeO2.7 crystallizes in the cubic space group of Pm3m with Z=1,a=3.9330(6) at room temperature,a=3.9498(6)A at 380℃.The magnetic structure from the neutron powder diffraction data collected at room temperature is consistent with a simple G-type antiferromagnetism and has a magnetic moment of 4.98 μB per Fe atom.The structures of Sr1-xBixFeO3-y with x other than 0.4 were also refined from the X-ray powder diffraction data.The data were consistent with a tetragonal cell when x=0.1,a rhombohedral cell when x= 0.9,and a cubic cell for x=0.2～0.8.From single crystal X-ray diffraction data,Ba1.5Pt0.5Mn2O6 crystallizes in hexagonal space group of P63mc with a= 5.7722 (6),c=4.4504(9),V=128.42(2),Z=1.The Sr(1-x)BixFeO(3-y)are found to be a good electronic and ionic conductor.

Effect of metal doping into Ce_(0.5)Zr_(0.5)O_2 on catalytic activity of MnO_x/Ce_(0.5-x)Zr_(0.5-x)M_(0.2x)O_y/Al_2O_3 for benzene combustion

The research investigated the effect of doping two metals separately or together into Ce0.5Zr0.5O2 on the catalytic activity of MnOx/Ce0.5-xZr0.5-xM0.2xOy/Al2O3 （M=Y, Mn, Y and Mn） for catalytic combustion of benzene. The prepared catalysts were characterized by X-ray diffraction （XRD）, surface area analysis, oxygen storage capacity （OSC）, and H2-temperature programmed reduction （H2-TPR）. Catalytic test was performed on a conventional fixed bed flow reactor. The characterization results revealed that Y and Mn ions entered into the ceria-zirconia mixed oxides framework, which improved the textural properties and greatly promoted the MnOx dispersion on the support surface. The complete conversion temperature of benzene on MnOx/Ce0.4Zr0.4Y0.1Mn0.1Oy/Al2O3 was 563 K, and the selectivity of carbon dioxides was 99%. This catalyst could be applied in a wide range of GHSV and wide concentration condition, showing great potential for application.

Ozonation of o-phenylenediamine in the presence of hydrogen peroxide by high-gravity technology

The study herein investigated the effectiveness of simultaneous use of ozone and hydrogen peroxide(O_3/H_2O_2 process) to degrade o-phenylenediamine(o-PDA) in a simulated wastewater. A rotor–stator reactor(RSR) was employed to create a high-gravity environment in order to enhance ozone-liquid mass transfer rate and possibly improve the degradation rate of o-PDA. The degradation efficiency of o-PDA(η) as well as the overall gas-phase volumetric mass transfer coefficient(KGa) were determined under different operating conditions of H_2O_2 concentration, initial o-PDA concentration, temperature of reaction, initial p H and rotation speed of RSR in attempt to establish the optimal conditions. Chemical oxygen demand reduction rate(rCOD) of wastewater treated at a particular set of conditions was also analyzed. Additionally, the intermediate products of degradation were identified using a gas chromatography-mass spectrometer(GC/MS) to further evaluate the extent of o-PDA degradation as well as establish its possible degradation pathway. Results were validated by comparison with those of sole use of ozone(O_3 process), and it was noted that η, KGa and rCODachieved by O_3/H_2O_2 process was 24.4%,31.6% and 25.2% respectively higher than those of O_3 process, indicating that H_2O_2 can greatly enhance ozonation of o-PDA. This work further demonstrates that an RSR can significantly intensify ozone-liquid mass transfer rate and thus provides a feasible intensification means for the ozonation of o-PDA as well as other recalcitrant organics.

Structural and Mechanistic Aspects of Mn-oxo and Co-based Compounds in Water Oxidation Catalysis and Potential Applications in Solar Fuel Production

To address the issues of energy crisis and global warming, novel renewable carbon-free or carbon-neutral energy sources must be identified and developed. A deeper understanding of photosynthesis is the key to provide a solid foundation to facilitate this transformation. To mimic the water oxidation of photosystem II oxygen evolving complex, Mn-oxo complexes and Co-phosphate catalytic material were discovered in solar energy storage. Building on these discoveries, recent advances in solar energy conversion showed a compelling working principle by combing the active Mn-oxo and Co-based catalysts in water splitting with semiconductor heteronanostructures for effective solar energy harnessing. In this review the appealing systems including Mn-oxo tetramer/Nafion, Mn-oxo dimer/TiO2, Mn-oxo oligomer/WO3, Co-Pi/Fe2O3, and Co-Pi/ZnO are summarized and discussed. These accomplishments offer a promising framework and have a profound impact in the field of solar fuel production.

Novel Air Purification System for Installation in Air Handling Units： Development, Assembly and Experimental Analysis

Nowadays, people pass 90% of their time in closed spaces, therefore, an increasing care in the creation and upkeep of healthier environments as a personal and as professional level become a major issue. The present project has as goal the verification and optimization of the implicit need of an OCRAMclima~ AHU （air handling units） in IAQ （indoor air quality） and its effectiveness in treatment and/or air purification, having as basis the legal national and European requirements for IAQ. This work was based on the study of the state of the art of the techniques in air purification and in the evaluation of their performance, culminating in the production of the prototype OCRAMclima~ NPS （nano purifying system）. The purifying phenomena involved are UVGI （ultraviolet germicidal irradiation） and catalytic ionization of air. The performance test was accomplished in a closed loop circuit, which results, obtained by an independent IAQ analyst, were satisfactory, indicating the viability of application of this system to indoor air disinfection. The outcome revealed that the conjugating of both phenomena, the air sterilizing by UV and catalytic ionization, is efficient when used for air purification, mainly for volatile organic compounds and bioaerosols.

STUDY ON FORMATION MECHANISM OF ADHERING LAYER FORMED ON TOOL FACE

The appearance of adhenng layer formed on tool face, its composition and distributionare analysed when Ca-S free-cutting stainless steel is machined. Cutting temperature field and itsrelation with formation of the layer is also studied. The result shows that, the layer can be formed under proper temperature condition, the stable cutting temperature field keeps the stable layer, itsthickness and composition distribution along rake face depend on the corresponding cutting tem-perature field. The theoretical model of the layer formation is set up.

Preparation of some new arylseleno compounds and application in the oxidation of olefins

Fifteen pyridine and substituted benzene diselenides,seleninic acids and seleninic anhydrides have been synthesized.Among them,4,4'-dipyridinediselenide,bis(2,4-dimethoxyphenyl)diselenide, 2,4-dimethoxyphenyl seleninic acid,2-pyridineseleninic acid,2-pyridineseleninic anhydride,4-pyridine- seleninic anhydride,2-nitrophenyl seleninic anhydride and 4-nitrophenyl seleninic anhydride were new compounds.Their regioselective oxidation or dehydrogenation of β-pinene,3β-benzoyloxycholest- 5-ene and androstan-3-one have been studied and compared.2-Pyridineseleninic anhydride is a more efficient oxidant than the others;most of the substituted benzeneseleno derivatives did not give the expected products.

Perfluoroalkylation of aromatic compounds with perfluoroalkyl radical generated from the oxidation of sodium perfluoroalkanesulfinate

Sodium perfluoroalkanesulfinates [R_fSO_2Na(1), Rf=CI(CF_2)_n; a, n=4; b, n=6; c, n=8] on oxidation with various single eletron oxidizing agents, such as Mn (OAc)_3·2H_2O and Ce (SO_4)_2, yielded perfluoroalkyl radicals capable of perfluoroalkylating aromatic compounds to give a mixture of o-and p-monoperfluoroalkylated products. Thus, this reaction provides a new method for the synthesis of o-and p-monoperfluoroalkyl substituted aromatic compounds.

Direct Electrochemical Extraction of Ti_5Si_3 from Ti/Si-Containing Metal Oxide Compounds in Molten CaCl_2

Direct electrochemical extraction of TisSia from pressed cathode pellets comprising of powdered Ti/Si- containing metal oxide compounds was investigated by using molten salt electro-deoxidation technology. Three groups of mixtures including TiO2 mixed with SiO2, Ti-bearing blast furnace slag （TBFS） mixed with TiO2, and TBFS mixed with high-titanium slag （HTS） were prepared at the same stoichiometric ratio （Ti ： Si = 5 ： 3） corresponding to the target composition of Ti5Si3, and used as the starting materials in this experiment, respec- tively. The pressed porous cylindrical pellet of the Ti/Si-contalning compounds served as a cathode, and two different anode systems, i.e., the inert solid oxide oxygen-ion-conducting membrane （SOM） based anode system and graphite-based anode system were used contrastively. The electrochemical experiment was carried out at 900--1050℃ and 3.0--4.0V in molten CaCl2 electrolyte. The results show that the oxide components were electro-deoxidized effectively and Ti5Si3 could be directly extracted from these complex Ti/Si-containing metal oxide compounds.

An investigation on catalytic performance and reaction mechanisms of Fe/OMS-2 for the oxidation of carbon monoxide, ethyl acetate, and toluene

The octahedral molecular sieve(OMS-2)-supported Fe( xFe/OMS-2: x = 1, 3, 5, and 10) catalysts were prepared using the pre-incorporation method. Physicochemical properties of the as-synthesized materials were characterized by means of various techniques, and their catalytic activities for CO, ethyl acetate, and toluene oxidation were evaluated. Among all of the samples, performed the best, with the reaction temperature required to achieve 90% conversion( T 90%) being 160 ℃ for CO oxidation, 210 ℃ for ethyl acetate oxidation, and 285 ℃ for toluene oxidation. Such a good catalytic performance of 5Fe/OMS-2 was associated with its high(Mn^(3+) + Mn^(2+)) content and adsorbed oxygen species concentration, and good lowtemperature reducibility and lattice oxygen mobility as well as strong interaction between Fe and OMS-2. In addition, catalytic mechanisms of the oxidation of three pollutants over the 5Fe/OMS-2 catalyst were also studied. It was found that CO, ethyl acetate or toluene was first adsorbed, then the related intermediates were formed, and finally the formed intermediates were completely converted into CO_(2) and H_(2)O.

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al_2O_3

High-surface-area mesoprous powders of γ-Al2O3 doped with Cu^2＋, Cr^3＋, and V^3＋ ions were prepared uia a modified sol-gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al2O3 and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane （DCE） was studied in the temperature range of 250-400℃. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2＋- and Cr^3＋-containing catalysts showed 100% conversion at 300℃ and 350℃, V3＋-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride （C2H3Cl） and hydrogen chloride （HCl） at all temperatures, Cu- and Cr-doped catalysts showed siguiticantly stronger capability for deep oxidation to CO2.

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1：2：4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the Ce O2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.

On-board measurements of gaseous pollutant emission characteristics under real driving conditions from light-duty diesel vehicles in Chinese cities

A total of 15 light-duty diesel vehicles（LDDVs） were tested with the goal of understanding the emission factors of real-world vehicles by conducting on-board emission measurements. The emission characteristics of hydrocarbons（HC） and nitrogen oxides（NOx） at different speeds, chemical species profiles and ozone formation potential（OFP） of volatile organic compounds（VOCs） emitted from diesel vehicles with different emission standards were analyzed. The results demonstrated that emission reductions of HC and NOxhad been achieved as the control technology became more rigorous from Stage I to Stage IV. It was also found that the HC and NOxemissions and percentage of O2 dropped with the increase of speed, while the percentage of CO2 increased. The abundance of alkanes was significantly higher in diesel vehicle emissions, approximately accounting for 41.1%–45.2%, followed by aromatics and alkenes. The most abundant species were propene,ethane, n-decane, n-undecane, and n-dodecane. The maximum incremental reactivity（MIR）method was adopted to evaluate the contributions of individual VOCs to OFP. The results indicated that the largest contributors to O3 production were alkenes and aromatics, which accounted for 87.7%–91.5%. Propene, ethene, 1,2,4-trimethylbenzene, 1-butene, and1,2,3-trimethylbenzene were the top five VOC species based on their OFP, and accounted for 54.0%-64.8% of the total OFP. The threshold dilution factor was applied to analyze the possibility of VOC stench pollution. The majority of stench components emitted from vehicle exhaust were aromatics, especially p-diethylbenzene, propylbenzene, m-ethyltoluene, and p-ethyltoluene.

Synthesis and Characterization of ZnO Nanowires and ZnO–CuO Nanoflakes from Sputter-Deposited Brass(Cu_(0.65)–Zn_(0.35)) Film and Their Application in Gas Sensing

A novel method was presented for synthesis of ZnO and ZnO-CuO composites in the form of nanowires, nanorods and nanoflakes on oxidized silicon substrates. Further, the use of the synthesized nanostructures for gas sensing was demonstrated. Pure brass （Cu0.65-Zn0.35） films were deposited on oxidized Si substrate by radio frequency （RF） diode sputtering. Subsequently, these films having thickness in the range of 100-200 nm were oxidized in different oxidizing ambient in the temperature range of 300-550 ℃. The effect of temperature, time and oxidizing ambient on the growth of nanostructures was investigated by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD） and photoluminescence （PL） techniques. The nanostructures surface was analyzed by X-ray photoelectron spectroscopy （XPS）. The synthesized nanowires had diameter in the range of 60-100 nm and length up to 50 μm. Based on these observations, the growth mechanism has been suggested. For the nanorods, the diameter was observed to be -150 nm. Samples having dense nanowires, nanorods and nanoflakes were used as a gas sensing material. The performance Of the sensor was investigated for different nanostructured materials for various volatile organic compounds （VOCs）, It was observed that ZnO- CuO nanoflakes were more sensitive to VOC sensing compared to ZnO nanowires and nanorods.