WC@TiO2核壳结构纳米复合材料制备与电催特征

Monotungsten carbide and titania nanocomposite with core-shell(WC@TiO2)structure was prepared by a new approach of spray drying and reduction-carbonization reaction,with titania nanopowder and ammonium metatungstate as precursors,methane as carbon source,and hydrogen as reduction gas.The sample was characterized by X-ray diffraction,scanning electron microscope,high resolution transmission electron microscope and X-ray energy dispersion spectroscopy.The results show that its crystal phase is composed of brookite,tungsten and monotungsten carbide.The morphology of the sample particle is irregular sphere-like,with a diameter smaller than 100 nm.Its chemical components are titanium,tungsten,carbon and oxygen.Monotungsten carbide nanoparticles lie on the surface of titania core and form an incomplete shell around titania core in the nanocomposite.The measurement with a microelectrode system of three electrodes shows that the sample is electrocatalytic active to nitrophenol in basic solution at room temperature.Its peak potential is at0.988 V(vs saturated calomel electrode (SCE)),which is more negative than the peak potential,0.817 V(vs SCE),of mesoporous monotungsten carbide, and its peak current is 8.809μA,which is higher than the peak current,4.058μA,of mesoporous monotungsten carbide.The hydrogen generation potential of the sample is at1.199 V(vs SCE),which is more negative than that of pure nanosized monotungsten carbide at1.100 V(vs SCE).These results show that the presence of titania in the sample can lower the peak potential of nitrophenol electrocatalysis and its hydrogen generation potential,and increase its peak current of nitrophenol electrocatalysis in basic solution at room temperature.This indicates a synergistic effect of titania and monotungsten carbide in electrocatalysis.     

合成的沸石活性污泥改进铵离子吸附和沉降性能(英文)

Municipal wastewater treatment plants typically exhibit two classic problems： high ammonium concen- tration in water after conventional biological treatment and, in some cases, poor activated sludge sediment ability. Potential solutions to these problems were investigated by adding a synthetic zeolite obtained from coal fly ash to different steps of activated sludge treatment. The experimental results for ammonium removal fit well with the theoretical adsorption isotherms of the Freundlich model with a maximum adsorption capacity of 13.72 mg.g-＇. Utiliza- tion of this kind of zeolite to improve activated sludge sediment ability is studied for the first time in this work. It is found that the addition of the zeolite （1 g. L-1） to an activated sludge with settling problems significantly enhances its sediment ability and comoact ability. This is confirmed by the sludge volume index （SVI）, which was reduced from 163 ml.g-1 to 70 ml.g-r, the V60 value, which was reduced from 894 ml.L-1 to 427 ml.L-1, and the zeta poten- tial （0, which was reduced from -19.81 mV to -14.29 mV. The results indicate that the addition of this synthetic zeolite to activated sludge, as an additional waste management practice, has a positive impact on both ammonium removal and sludge settleability.     

花椰菜中异硫氰酸酯提取物抗氧化活性研究(英文)

Isothiocyanates(ITCs) extracts were prepared from fresh broccoli.Their antioxidant properties were evaluated by using the in vitro bioassays,including superoxide anion radical( 2 O·-) ,hydroxyl radical(HO·-) and 2,2-diphenyl-1-picrylhydracyl(DPPH·) radical-scavenging methods,lipid peroxidation assay,and reducing power assay.The ITCs extracts exhibited significant dose-dependent antioxidant activities(P0.01) .Its antioxidant-stability was affected by temperature and storage condition,although it was more stable than vitamin C(Vc) .GC-MS iden-tified sulforaphane in the ITCs extracts.The antioxidant activity of sulforaphane was approximately one tenth to one fifth of that of Vc.Sulforaphane was experimented to be one of dominating contributors to antioxidant capacity of ITCs extracts.However,there was no direct antioxidant activity found for benzyl isothiocyanate(BITC) in vitro. Therefore,it could be concluded that the general group(-N=C=S) was not the essential part for the antioxidant activity of sulforaphane.It is suggested that the ITCs extracts from broccoli can be developed into a promising food additive for healthy food.     

大团囊虫草菌胞内多糖发酵优化和抗氧化活性研究(英文)

Cordyceps ophioglossoides is a valuable traditional medicinal material.We have found that intracellular polysaccharide(IPS) is the major biologically active ingredient in Cordyceps ophioglossoides.This study is the first time to optimize the yield of IPS from Cordyceps ophioglossoides.The optimal medium for IPS production consists of glucose 54.50 g·L·1,yeast powder 25.50 g·L·1,NaH2PO4 0.4 g·L·1 and K2HPO4 0.4 g·L·1.The suggested culture conditions are 24 ℃,initial pH 4.5 with a rotary speed of 120 r·min·1 for 168 h.The yield of IPS is 737.93 mg·L·1,which is 50% higher than the yield under the conditions prior to optimization.The anti-oxidative activities of IPS in Cordyceps ophioglossoides L2 are also characterized using various in vitro assay.The anti-oxidative activity may explain the reason why IPS from Cordyceps ophioglossoides can be used to fight against neurodegenerative dis-eases and menopausal symptoms.     

天然沸石和改性沸石在废水处理中的应用研究

综述了天然沸石和改性沸石在废水处理中的脱氮、除磷、除氟、除有机污染物和重金属污染物等的应用研究;探讨了沸石的高温改性、酸改性、碱改性、盐改性和复合改性等的改性沸石方法;并对能够使沸石再生的物理法、化学法、电化学法和生物法进行了比较。同时,对天然沸石和改性沸石在废水处理中的进一步发展提出了一定的看法和思考。     

天然沸石和改性沸石在废水处理中的应用研究

综述了天然沸石和改性沸石在废水处理中的脱氮、除磷、除氟、除有机污染物和重金属污染物等的应用研究;探讨了沸石的高温改性、酸改性、碱改性、盐改性和复合改性等的改性沸石方法;并对能够使沸石再生的物理法、化学法、电化学法和生物法进行了比较。同时,对天然沸石和改性沸石在废水处理中的进一步发展提出了一定的看法和思考。     

丁酸在含氯化钙双水相体系中的有效分离(英文)

One of the bottlenecks for bioproduction of butyric acid as bulk chemical is the difficulty in separating butyric acid from the fermentation broth,compared with the petroleum-based chemical synthesis method.In the present work,a novel separation methodology was developed based on an aqueous two-phase system with inor-ganic salts.Calcium chloride was screened out for effective separation of butyric acid from butyric acid-water-salt systems.Within appropriate concentration range of butyric acid and salt,butyric acid was enriched in the upper phase and most of calcium ions remained in the lower phase.This"salting out"effect is very efficient to separate butyric acid from the simulated butyrate fermentation broth,which consists of butyric acid and acetic acid with concentration ratio of 4︰1,so that the final ratio of butyric acid/acetic acid in the upper phase is improved to 9.87. The aqueous two-phase system was used to separate butyric acid from the actual fermentation broth with satisfac-tory result.     

可控热膨胀聚合物复合材料的挑战和机遇(英文)

负热膨胀(negative thermal expansion,NTE)材料可作为填料制备可控热膨胀复合材料.高质量聚合物复合材料的研发面临诸多挑战,包括NTE 填料与基体材料的相容性,NTE相的稳定性,颗料形貌和尺寸的控制及其对混合稗度的影响.本文对影响聚合物复合材料成型中存在的诸多可能存 在的问题进行了述评,讨论了对有望用作填料的NTE材料的要求,即对NTE填料颗粒尺寸和相容性进行合成控制.通过晶体前驱体到目标NTE相 的拓扑转变,可实现对颗粒尺寸的最优控制.     

温度对氨基酸同系物在盐酸二甲双胍水溶液中体积和黏度特性的影响(英文)

Density(ρ)and viscosity(η)are measured for glycine,DL-α-alanine DL-α-valine,and DL-α-leucine in 0.05,0.10,0.15 and 0.20 mol·L-1aqueous metformin hydrochloride at 308.15,313.15 and 318.15 K.The measured values are used to estimate some important parameters,such as partial molal volume Vφ,standard partial molal volume0Vφ,transfer volume 0 ΔVφ,hydration number nH,the second derivative of infinite dilution of partial molal volume with respect to temperature,viz.,2 0 2 Vφ /T,viscosity B-coefficient,variation of B with temperature,viz., dB/dT,free energy of activation per mole of solvent0 * 1 Δμand solute 0* 2 Δμof the amino acids.These parameters are interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.In addition,0Vφ, 0 ΔVφ,viscosity B-coefficient,ΔB and 0* 2 Δμare split into group contributions(3NH COO +-)and CH2 of the amino acids using their linear correlation and their behavior is discussed.     

单乙醇胺和二乙醇胺甲酸盐离子液体对水、甲醇和乙醇挥发度的影响(英文)

Vapor pressures were measured for six binary systems containing water, ethanol, or methanol with one of the two ionic liquids （ILs） at different component concentrations and temperatures using a quasi-static ebulliometer, with the ILs mono-ethanolammonium formate （[HMEA][HCOO]） and di-ethanolammonium formate （[HDEA][HCOO]）. The vapor pressures of the IL-containing binary systems are well correlated using the NRTL model with an overall average absolute relative deviation （AARD） of 0.0062. The effect of ILs on the vapor pressure depression of sol-vents at 0.050 mole fraction of IL is that [HDEA][HCOO]〉[HMEA][HCOO], and the vapor pressure lowering de-gree follows the order of water〉methanol〉ethanol. Further, the activity coefficients of three solvents （viz. water, ethanol, and methanol） for the binary systems{solvent （1）＋IL （2）}predicted based on the fitted NRTL parameters at T=333.15 K indicate that the two ILs generate a negative deviation from Raoult’s law for water and methanol and a positive deviation for ethanol to a varying degree, change the relative volatility of a solvent. [HMEA][HCOO] may be a promising entrainer to efficiently separate ethanol aqueous solutions by special rectification.     

Decomposition of NO on Tungsten Carbide and Molybdenum Carbide Surfaces

The decomposition of ¹⁵NO on C/W(111), C/W(110), and on monolayer and bulk C/Mo/W(111) surfaces is compared based on temperature-programmed desorption (TPD) and Auger electron spectroscopy (AES) measurements. Our results indicate that the decomposition of ¹⁵NO occurs readily over all surfaces, and the only ¹⁵N-containing reaction products are ¹⁵N₂ and ¹⁵N₂O under our experimental conditions. Much higher surface reactivity for ¹⁵NO decomposition was observed over the more open-structured C/W(111) surface, with a value of 0.68 ¹⁵NO/W, in contrast to the surface reactivity of 0.24 ¹⁵NO/W over the close-packed C/W(110) surface. The selectivity of these two ¹⁵N-containing reaction products depends on the structure of the substrates as well. The more open-structured C/W(111) surface favors the production of ¹⁵N₂, with a product selectivity of ¹⁵N₂ being approximately 87%. In contrast, the selectivity to ¹⁵N₂ is only about 52% on C/W(110). In addition, we have investigated the decomposition of ¹⁵NO on C/Mo surfaces that were epitaxially grown on W(111). The selectivity of ¹⁵N₂ on C/Mo/W(111) surfaces is 88%, which is very similar to that observed on C/W(111). Finally, the general similarity between the DeNOx chemistry on carbides and on Pt-group metals will also be discussed.     

碳化钨纳米晶薄膜电极在对硝基苯酚电化学还原中的催化性能

采用磁控溅射物理气相沉积和等离子体增强化学气相沉积技术,在金属镍基体上制备具有纳米晶结构的碳化钨薄膜;采用循环伏安、准稳态极化和恒电位阶跃等电化学方法研究了对硝基苯酚(PNP)在碳化钨纳米晶薄膜电极上电化学还原的特性和机理.研究表明,采用磁控溅射物理气相沉积技术制备得到的薄膜是由直径为20nm的WC1-X构成,在这种薄膜电极上,PNP电化学还原在电位为(0.95V(Vs. SCE)时,出现一个电流密度为6.0mA(cm(2还原峰,还原反应的表观活化能为12.0kJ(mol(1;而采用等离子体增强化学气相沉积技术制备得到的薄膜是由直径为35nm的纯相WC构成,PNP在该薄膜电极上电化学还原峰电位为(1.05 V(Vs. SCE),还原电流达10.0 mA(cm(2,表观活化能为10.9 kJ(mol(1. PNP在这两种碳化钨薄膜电极上都经过两步不可逆的电化学反应还原成对氨基苯酚,控制步骤为电极反应的电荷传递过程.     

WC/MMT纳米复合材料制备及其对PNP的电催化活性

以剥离后的蒙脱石(MMT)为载体,将浸渍法与原位还原技术相结合制备了碳化钨/蒙脱石(WC/MMT)纳米复合材料。采用X射线衍射、扫描电子显微镜和透射电子显微镜等手段对样品进行了表征。结果表明,剥离后蒙脱石的片层厚度为10～15 nm,层间距增大,边缘发生卷曲;复合材料由碳化钨(WC)、碳化二钨(W₂C)和蒙脱石组成,碳化钨颗粒均匀地分布于蒙脱石外表面。采用循环伏安法测试了样品对对硝基苯酚(PNP)的电化学还原性能,结果表明,WC/MMT纳米复合材料对对硝基苯酚具有良好的电催化活性,且具有较好的稳定性。蒙脱石是碳化钨基复合电催化材料良好的载体。     

Thermal Expansion of Tungsten Carbide at Low Temperature

The thermal expansion of WC from 20 to 900 K was measured in the a and c axial directions using high-resolution neutron powder diffraction. Third-order polynomials have been calculated from the expansion curves. The results complement and are compared with prior data in the 293 to 900 K region.     

Pervaporation of Acetaldehyde Aqueous Solution through Zeolite 3A-Polyurethane (PU) Composite Membrane

3A-filled hydrophilic polyurethane (PU) membranes were prepared by incorporating zeolite 3A into PU for pervaporation separation of acetaldehyde and water mixtures (acetaldehyde concentration 2 wt%–20 wt%). The composite membranes were characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The morphology and thermal stability of these membranes were also investigated. The effects of zeolite 3A on the sorption, diffusion, and pervaporation performance were evaluated. The swelling study showed that 3A-PU membrane had higher swelling degree in acetaldehyde aqueous solution than in pure water. And the swelling degree of the composite membrane in acetaldehyde solution increased with the 3A content. The permeation flux and water/acetaldehyde separation factor first increased and then decreased with increasing 3A content. The reason may be that a proper quantity of 3A will enlarge the free volume fraction of PU while excessive 3A lead to its poor dispersion. The highest permeation flux of the composite membrane could reach 223 g · m^?2 · h^?1 and the maximum water/acetaldehyde selectivity achieved 7.5. The calculation of sorption selectivity and diffusion selectivity showed that diffusion played a more important role in this process.     

Molybdenum Oxycarbide and Tungsten Oxycarbide Coatings on Silicon Carbide Fibers

The strength and toughness of fibrous composites depend on the interface properties which control the bonding between the fibers and matrices. One method of controlling the interface involves coating the fiber with an appropriate material. In a previous study, it was found that there is a definite advantage in using low coating temperatures to prevent fibers from degrading. We therefore were interested in a report that Mo₂C could be deposited from Mo(CO)₆ at temperatures as low as 300° to 475°C. Our studies indicated that the material was not Mo₂C, but an oxycarbide, which, with an analogous tungsten oxycarbide coating, was applied to SiC yarns. Both oxycarbides could be converted to the metals by heat-treating in N₂.     

Mechanism of the Adsorption of Ammonium Ions from Aqueous Solution by a Chinese Natural Zeolite

Abstract

The adsorption of ammonium ions onto a Chinese natural zeolite in an agitated batch adsorber was studied. A trial‐and‐error non‐linear method was developed to examine two widely used isotherms, the Langmuir and Freundlich. The data gained from the adsorption system fitted the Freundlich isotherm better. An ion exchange model, describing the relationship among the total metal ions in the solution, NH₄ ⁺ removed from the solution, and ions initially released from the zeolite, was developed for the adsorption system. In addition, a parameter of the ion exchange potential was defined to describe the adsorption mechanism. Ion exchange was the main mechanism that accounted for the adsorption of ammonium ions onto the Chinese natural zeolite.     

锌电积过程中聚苯胺/碳化钨阳极的结构变化及失效行为

研究了锌电积过程中聚苯胺/碳化钨(PANI/WC)阳极的结构变化和失效行为,采用加速电解寿命测试和仪器分析考察了PANI/WC阳极在锌电积过程中表面形貌和结构的变化. 结果表明,整个电解过程中槽电压从3.71 V降到3.57 V后急剧升高到10 V,即经历活化、稳定、迅速升高阶段. 随锌电积进行,阳极表面出现脱落、开裂,迅速进入失效阶段,而微观结构无明显变化. PANI/WC阳极失效主要是由包覆WC的PANI大量剥蚀而使WC裸露和阳极开裂导致的.     

羧酸钠Gemini表面活性剂水溶液的表面活性及其pH影响

羧酸钠Gemini表面活性剂C11pPHCNa与相同烷烃链的月桂酸钠(SL)水解产生的酸式分子,使水溶液表面张力曲线呈现下凹状,电导曲线的转折点明显向较大浓度偏移(SL曲线),甚至消失(C11pPHCNa曲线)。添加10mmol·L-1NaBr仅表现出盐效应,不影响其水解。在临界的pH=8.2时,它们的水解影响被初步抑制,表面张力曲线表现出通常的上凸状。在pH=12时,CMC、c20和γCMC分别为9.30×10-2mmol·L-1、3.33×10-3mmol·L-1和35.4mN·m-1(C11pPHCNa)以及25.1mmol·L-1、5.37mmol·L-1和37.2mN·m-1(SL)。