Green epoxidation of cyclooctene with molecular oxygen over an ecofriendly heterogeneous polyoxometalate-gold catalyst Au/BW<Subscript>11</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

An ecofriendly heterogeneous polyoxometalate (POM)-gold catalyst Au/BW₁₁/Al₂O₃ was synthesized and used for solvent-free epoxidation of cyclooctene under mild reaction conditions using molecular oxygen as an oxidant and t-butyl hydroperoxide (TBHP) as an initiator. The catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), induced coupled plasma optical emission spectrometry (ICP-OES), and Brunauer-Emmett-Teller (BET). The catalyst showed good conversion and high selectivity without use of solvents or environmentally harmful oxidants. Moreover, the catalyst is recyclable up to three cycles with no significant loss in selectivity towards epoxide.     

Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> as indicator of heavy metal enrichment in Zhujiang (Pearl River) estuary sediments

A part of the heavy metals in estuary and coastal zone occurs naturally in the environment; the other part is due to human activity; so the directly measured concentration of heavy metal does not automatically indicate anthropogenic enrichment. Fe₂O₃ was used in this study as conservative tracer to distinguish natural components from anthropogenic components of heavy metal sediment concentration in the Zhujiang estuary. Compared with clay and Al₂O₃, Fe₂O₃ is more suitable as reference element. The final results showed that two zones in the Zhujiang estuary were seriously contaminated by heavy metals. One nearby the Humen mouth; the other around the west coast of the estuary. The horizontal distribution of heavy metals indicates that Zn, Ni and Cu have wider contaminating areas than TiO₂, V and Cr in the estuary.     

Discovery of ultrahigh-T spinel-garnet granulite with pure CO<Subscript>2</Subscript> fluid inclusions from the Altay orogenic belt,NW China

We first report discovery of the spinel-garnet-orthopyroxene granulite with pure CO₂ fluid inclusions from the Fuyun region of the late Paleozoic Altay orogenic belt in Central Asia, NW China. The rock is characterized by an assemblage of garnet, orthopyroxene spinel, cordierite, biotite, plagioclase and quartz. Symplectites of orthopyroxene and spinel, and orthopyroxene and cordierite indicate decompression under UHT conditions. Mineral chemistry shows that the orthopyroxenes have high X_Mg and Al₂O₃ contents (up to 9.23 wt%). Biotites are enriched in TiO₂ and X_Mg and are stable under granulite facies conditions. The garnet and quartz from the rock carry monophase fluid inclusions which show peak melting temperatures of around-56.7°C, indicating a pure CO₂ species being presented during the ultrahigh-T metamorphism in the Altay orogenic belt. The inclusions homogenize into a liquid phase at temperatures around 15.3–23.8°C translating into CO₂ of the order of 0.86–0.88 g/cm³. Based on preliminary minerals paragenesis, reaction textures and petrogenetic grid considerations, we infer that the rock was subjected to UHT conditions. The CO₂-rich fluids were trapped during exhumation along a clockwise P-T path following isothermal decompression under UHT conditions. Project supported by the National Basic Research Program (973) of China (No. 2001CB409801), the Exemplary Young Teacher Education and Scientific Research Award Plan of China University, and Postdoctoral Fund of China (No. 2003033033), Postdoctoral Fund of Zhejiang Province, and Starting Fund of Education Ministry, China     

Catalytic properties of CuO/Sn0.9Ti0.1O2 and CuO/Sn0.7Ti0.3O2 in NO＋CO reaction

Using SnxTi1-xO2 as carriers, CuO/Sn0.9Ti0.1O2 and CuO/Sn0.7Ti0.3O2 catalysts with different loading amounts of copper oxide (CuO) were prepared by an impregnation method. The catalytic properties of CuO/Sn0.9Ti0.1O2 and CuO/Sn0.7Ti0.3O2 were examined using a microreactor-gas chromatography (GC) NO CO reaction system and the methods of BET (Brun- auer-Emmett-Teller), TG-DTA (themogravimetric and differential thermal analysis), X-ray diffraction (XRD) and H2-temperature programmed reduction (TPR). The results showed that NO conversions of Sn0.9Ti0.1O2 and Sn0.7Ti0.3O2 were 47.2% and 43.6% respectively, which increased to 95.3% and 90.9% at 6 wt% CuO loading. However, further increase in CuO loading caused a decrease in the catalytic activity. The nitrogen adsorption-desorption isotherm and pore-size distribution curve of Sn0.9Ti0.1O2 and Sn0.7Ti0.3O2 represented type IV of the BDDT (Brunauer, Deming, Deming and Teller) system and a typical mesoporous sample. There were two CuO diffraction peaks (2θ 35.5° and 38.7°), and the diffraction peak areas increased with increasing CuO loading. TPR analysis also detected three peaks (α, β and γ) from the CuO-loaded catalysts, suggesting that the α peak was the reduction of the highly dispersed copper oxide, the β peak was the reduction of the isolated copper oxide, and the γ peak was the reduction of crystal phase copper oxide. In addition, a fourth peak (δ) of the catalysts meant that the SnxTi1-xO2 mixed oxides could be reductive.     

Preparation of Cu/ZnO/Al2O3 catalysts in a solvent-free routine for CO hydrogenation

The synthesis of methanol and dimethyl ether (DME) from CO hydrogenation has been investigated on Cu-based catalysts. A series of Cu/ZnO/Al₂O₃ catalysts were prepared using a solvent-free routine which involved a direct blend of copper/zinc/aluminum salts and citric acid, followed by calcination at 450 °C. The calcination processes were monitored using thermogravimetry differential scanning calorimetry (TG-DSC). Catalysts were further characterized using N₂ adsorption, scanning electronic microscopy (SEM), X-ray diffraction (XRD), N₂O oxidation followed by H₂ titration, and temperature-programmed reduction with H₂ (H₂-TPR). The reduction processes were also monitored with in-situ XRD. The physicochemical properties of catalysts depended strongly on the types of precursor salts, and catalysts prepared using Al acetate and Cu nitrate as starting materials had a larger surface area, larger exposed metallic copper surface area, and lower reduction temperature. The CO hydrogenation performances of these catalysts were compared and discussed in terms of their structures. Catalysts prepared with copper nitrate, zinc and aluminum acetates exhibited the highest catalytic activity.     

Impact of diesel emission fluid soaking on the performance of Cu-zeolite catalysts for diesel NH<Subscript>3</Subscript>-SCR systems

Diesel emission fluid (DEF) soaking and urea deposits on selective catalytic reduction (SCR) catalysts are critical issues for real diesel engine NH₃-SCR systems. To investigate the impact of DEF soaking and urea deposits on SCR catalyst performance, fresh Cu-zeolite catalyst samples were drilled from a full-size SCR catalyst. Those samples were impregnated with DEF solutions and subsequently hydrothermally treated to simulate DEF soaking and urea deposits on real SCR catalysts during diesel engine operations. Their SCR performance was then evaluated in a flow reactor with a four-step test protocol. Test results show that the DEF soaking leached some Cu from the SCR catalysts and slightly reduced their Cu loadings. The loss of Cu and associated metal sites on the catalysts weakened their catalytic oxidation abilities and caused lower NO/NH₃ oxidation and lower high-temperature N₂O selectivity. Lower Cu loading also made the catalysts less active to the decomposition of surface ammonium nitrates and decreased low-temperature N₂O selectivity. Cu loss during DEF impregnation released more acid sites on the surface of the catalysts and increased their acidities, and more NH₃ was able to be adsorbed and involved in SCR reactions at medium and high temperatures. Due to lower NH₃ oxidation and higher NH₃ storage, the DEF-impregnated SCR catalyst samples showed higher NO _x conversion above 400 °C compared with the non-soaked one. The negative impact of urea deposits during DEF impregnation was not clearly observed, because the high-temperature hydrothermal treatment helped to remove the urea deposits.     

Science Letters：Nitrogen doping of activated carbon loading Fe2O3 and activity in carbon-nitric oxide reaction

Nitrogen doping of activated carbon loading Fe2O3 was performed by annealing in ammonia, and the activity of the modified carbon for NO reduction was studied in the presence of oxygen. Results show that Fe2O3 enhances the amount of surface oxygen complexes and facilitates nitrogen incorporation in the carbon, especially in the form of pyridinic nitrogen. The modified carbon shows excellent activity for NO reduction in the low temperature regime (<500 °C) because of the cooperative effect of Fe2O3 and the surface nitrogen species.     

Study of transport behavior for Fe-doping La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> perovskite manganese

Systematic studies of the transport properties of La_0.67Ca_0.33Mn_1?xFe _x O₃ (x=0–0.3) systems showed that with increasing Fe-doping contentx the resistance increases and the insulator-metal transition temperature moves to lower temperature. For small doping content, the transport property satisfies metal transport behavior below the transition temperature, and above the transition temperature it satisfies the small polaron model. This behavior can be explained by Fe³⁺ doping, which easily forms Fe³⁺?O^2??Mn⁴⁺ channel, suppressing the double exchange Mn³⁺?O^2??Mn⁴⁺ channel and enhancing the spin scattering of Mn ions induced by antiferromagnetic clusters of Fe ions.     

Integrated direct air capture and CO<Subscript>2</Subscript> utilization of gas fertilizer based on moisture swing adsorption

A new concept of low-cost direct air capture technology integrated with a fertilization system is proposed, as an alternative to the application of air derived CO₂. A moisture swing sorbent can elevate the CO₂ concentration from 400 parts per million (ppm) to several thousand ppm, and this can be used to cultivate plants. Desorption isotherms were determined and are described well by a Langmuir model. The adsorption rate constant and the desorption rate constant were gained at 25 °C, 35 °C, and 45 °C under 1000 ppm concentration of CO₂. In accelerated cultivation experiments, the effects of CO₂ concentration, light intensity, and spectrum on the CO₂ uptake rate of the plants were investigated. A multi-bed desorption system which is capable of providing a continuous and stable CO₂ supply for a greenhouse is demonstrated based on the desorption characteristic and CO₂ uptake feature of plants. An energy and cost assessment for the integrated system was performed and the results indicated that minimum energy requirements and cost estimate of CO₂ are 35.67 kJ/mol and 34.68 USD/t, respectively. This makes direct air capture a competitive and sustainable carbon source for agriculture.     

Optimization Strategies for Selective CO2 Electroreduction to Fuels

Capturing CO₂ from the atmosphere and converting it into fuels are an efficient strategy to stop the deteriorating greenhouse effect and alleviate the energy crisis. Among various CO₂ conversion approaches, electrocatalytic CO₂ reduction reaction (CO₂RR) has received extensive attention because of its mild operating conditions. However, the high onset potential, low selectivity toward multi-carbon products and poor cruising ability of CO₂RR impede its development. To regulate product distribution, previous studies performed electrocatalyst modification using several universal methods, including composition manipulation, morphology control, surface modification, and defect engineering. Recent studies have revealed that the cathode and electrolytes influence the selectivity of CO₂RR via pH changes and ionic effects, or by directly participating in the reduction pathway as cocatalysts. This review summarizes the state-of-the-art optimization strategies to efficiently enhance CO₂RR selectivity from two main aspects, namely the cathode electrocatalyst and the electrolyte.

     

CaO+SiO2+Al2O3+MgO+FeO 五元渣系中FeO 活度的研究

Activities of FeO in CaO-SiO2-Al2O3-MgO-FeO slags were determined at 1673 K by electrochemical of the solid electrolyte cell： Mo [Mo＋MoOu[ZrO2（MgO）[Fe＋（CaO-SiO2-Al2O3-MgO-FeO）＋Ag[Fe. The influences of slag compositions and basicity on FeO activities were analyzed. The results reveal that, for slags of fixed （%CaO）/（%SiO2） ratio, MgO and Al2O3 content, there was an increase of FeO activities with increase of FeO content. For slags with constant {（%CaO）＋ （%MgO）}/（%SiO2） ratio, fixed FeO and A1203 content, FeO activities decreased when MgO content increased from 5% to 10%, and increased with the increase of MgO content when it was over 10%. The FeO activities increased when （%CaO）/（%SiO2） ratio changed from 1.03 to 1.30 in the slags of constant MgO, FeO and Al2O3 content.     

高能球磨法制备的含铁TiO2的穆斯堡尔谱研究

1Introduction Oxide dilutedmagneticsemiconductors(O DMS)havedrawnmuchattentioninthelastdecadebecause thesematerialsappeartohavegreatpotentialforuse inspin dependentelectronicdevices[1].Recently,iron cobalt dopedtitaniumdioxideswithroomtemperature ferromagnetismhavebeenreported[2].Specially,the resultsofmagneticpropertiesofFexTi1-xO2(x=0.065and0.250)indicatethatferromagnetismwitha Femagneticmomentislargerthantheonereported forCo[3].ThefabricationmethodsofFe Co doped TiO2includepulsedlaser…     

The Electrochemical Performance of Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 Nanocrystalline Hydrogen Storage Alloy as Metal Hydride Electrode

Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 nanocrystalline hydrogen storage materials are prepared by melt-spinning(MS).X-ray diffraction is used for the measurement of the nanocrystalline size.Compared to the electrode of polycrystalline alloys,the property of activation MH9metal hydride)electrode of the alloys with nanometer scale became worse and the inital discharge capacity decreased.It may be ascribed to the decrease of the total amount of rare earth metals and the increase of oxygen on the surface from the analysis of components of the alloys.After heat-treatment,the electrochemical performance of MH electrode of as-spun alloys could be improved,which could be attributed to the alleviation of the lattice strain.     

Low-Temperature Selective Catalytic Reduction of NO with NH<Subscript>3</Subscript> over Fe–Ce–O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Catalysts

In this study, we used a simple impregnation method to prepare Fe–Ce–O _x catalysts and tested them regarding their low-temperature (200–300 °C) selective catalytic reduction (SCR) of NO using NH₃. We investigated the effects of Fe/Ce molar ratio, the gas hourly space velocity (GHSV), the stability and SO₂/H₂O resistance of the catalysts. The results showed that the FeCe(1:6)O _x (Ce/Fe molar ratio is 1:6) catalyst, which has some ordered parallel channels, exhibited good SCR performance. The FeCe(1:6)O _x catalyst had the highest NO conversion with an activity of 94–99% at temperatures between 200 and 300 °C at a space velocity of 28,800 h^?1. The NO conversion for the FeCe(1:6)O _x catalyst also reached 80–98% between 200 and 300 °C at a space velocity of 204,000 h^?1. In addition, the FeCe(1:6)O _x catalyst demonstrated good stability in a 10-h SCR reaction at 200–300 °C. Even in the presence of SO₂ and H₂O, the FeCe(1:6)O _x catalyst exhibited good SCR performance.     

Phase diagram estimation of the Al2O3-SiO2-Re2O3 systems

Nine limiting binaries of Al₂O₃-SiO₂-Re₂O₃(Re=Nd, Sm, Gd and La) system are assessed. The binary diagrams or experimental information from Toropov, Mizuno, Aramaki, Bondar, Rolin and Coutures are optimized with the substitutional model of Kaufman and Nesor and the approximate formula of fusion free energy for rare earth element oxides of Wu and Pelton. The extracted Gibbs free energies of pure solid oxides and stoichiometric phases and the solution parameters are used to estimate the corresponding binaries, liquidus surfaces and a series of isothermal sections of four ternaries Al₂O₃-SiO₂-Nd₂O₃, Al₂O₃-SiO₂-Sm₂O₃, Al₂O₃-SiO₂-Gd₂O₃, and Al₂O₃-SiO₂-La₂O₃. In the Al₂O₃-SiO₂-Gd₂O₃ system samples as fired at exact temperature with different compositions were analyzed by X-ray diffractometer and the detected results are fitted with the calculation of isothermal sections. Supported by State Key Lab of High Performance Ceramics and Superfine Micro-structure (9517 and 9708)     

Preparation of ultrafine γ-Al2O3 particles in non-ionic water in oil microemulsions

Ultrafine γ-Al₂O₃ particles are synthesized in Triton X-100/n-hexanol/cyclohexane/water water in oil(w/o) microemulsion by mixing two separately prepared microemulsions containing Al(NO)₃ and (NH₄)₂CO₃ respectively. The ultrafine Al₂O₃ particles are characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) and their size and distribution are measured. The effects of water, surfactant and reactant concentrations on the particle size and distribution are studied. The results show that the particle size and distribution can be changed by varying the preparation conditions, and the size of the microemulsion droplets has a controlling effect on the size of the particles. A possible mechanism of ultrafine particles (UFPs) prepared by microemulsions is proposed.     

过冷液相区内轧制温度对Zr52.5Al10Ni10Cu15Be12.5大块金属玻璃表面形貌的影响

Surface morphologies of Zr52.5 Al10 Ni10 Cu15 Be12.5 bulk metallic glass after being rolled at both a temperature around T9 and near （ Tx - 50） K were investigated with a scanning electron microscopy. Macroscopic and microscopic observation results show that squamae, cracks, steps and wedges exist on the surface when the samples were rolled at temperatures around Ty. However, a smooth and fiat surface appears when the samples were rolled at temperatures near （ Tx - 50） K. These results indicate that the mode of deformation in the supercooled liquid region is a partially homogeneous flow at a temperature around T9, and a fully homogeneous one at temperatures near （ Tx - 50） K. According to the results, it is more feasible to roll the amorphous alloys at temperatures near （ Tx - 50） K to obtain parts with smooth and fiat surface.     

低温等离子体与催化剂氧化脱除甲醛的研究

分别采用等离子体与不同催化剂相结合对空气中甲醛的脱除进行实验研究。结果表明,Ag/CeO2催化剂能与等离子体结合高效氧化脱除甲醛,当气体组成为276×10-6HCHO、21%O2,1%H2O,N2为平衡气,空速为16 500 h-1、温度为70℃、压强为一个大气压、输入放电能量密度为108 J.L-1时,99%的甲醛被脱除,86%的甲醛被氧化成CO2。而在同样的条件下,Fe/TiO2和γ-Al2O3催化剂对甲醛的脱除率只为86%和78%。     

Influence of annealing conditions on the properties of Cu(In,Ga)Se<Subscript>2</Subscript> thin films fabricated by electrodeposition

Cu(In,Ga)Se₂ (CIGS) precursor films were deposited on Mo/glass by electrodeposition, and then annealed in Se vapor. The annealing temperature ranged from 450 °C to 580 °C, and two heating rates were selected. The results showed that the crystalline quality of the CIGS films and formation of the Cu-Se compound could be strongly influenced by the selenization temperature and heating rate. Raman spectroscopy and X-ray diffraction (XRD) analysis showed that when the selenization temperature was increased from 450 °C to 550 °C, the amount of binary CuSe phase decreased and the amount of Cu2Se increased. After annealing at 580 °C, a minimum amount of Cu_2?xSe compounds was obtained and the degree of CIGS film crystallinity was higher than in other samples. The relationship between the properties of the film and the heating rate was studied. XRD and Raman spectra showed a decrease in the Cu_2?xSe phase with increasing heating rate. Scanning electron microscopy (SEM) and XRD showed a remarkable increase in the grain size of CIGS during rapid heating.     

V2O5-CaCo3-Nb2O5掺杂对低损耗功率Mn-Zn铁氧体的影响

Effect of the content of dopants in the manganese-zinc ferrites on the low power loss is studied by measuring magnetic properties and observing the grain boundary structures. The Mn0.738Zn0.206Fe2.066O4 composition powders were prepared by using conventional ceramic powder processing technique. The microstructure of grain boundary was observed by scanning electron microscope （SEM）. It has been found that power loss is greatly dependent upon the content of the additives.