调变Ni／Mo／MgO催化剂中Ni／Mo比例可控合成薄壁碳纳米管

采用摩尔分数1%Ni及负载少量Mo的Ni/MO/MgO催化剂裂解甲烷合成薄壁碳纳米管.通过SEM、TEM、XRD和Raman光谱表征方法研究了碳纳米管直径和催化剂中Ni/Mo比例关系.实验发现:通过控制Ni/Mo比例可以调变催化剂颗粒大小以及活性相.TEM及XRD表征发现,随着Ni/Mo比例的降低,金属Mo相逐渐从NiMo合金相中析出.NiMo合金相对应的活性组分颗粒很小,容易催化裂解甲烷形成薄壁碳纳米管;而后析出的Mo相则主要形成了大管径厚壁的碳纳米管.当Ni/Mo比例为6时可以高选择性地获得窄分布,内径为1.3nm,外径为3.0nm的溥壁碳纳米管.Raman光谱进一步验证了碳纳米管含有较少的缺陷.薄壁碳纳米管形成的关键因素主要体现为碳在其表而的快速扩散以及小颗粒的碳纳米管催化剂活性相控制.     

Wet oxidation of acid brown dye by hydrogen peroxide using heterogeneous catalyst Mn-salen-Y zeolite: a potential catalyst

Catalytic wet hydrogen peroxide oxidation of acid dye has been explored in this study. Manganese(III) complex of N,N'-ethylene bis(salicylidene-aminato) (salenH(2)) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by FT-IR, XRD, TG/DTA and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that after 20 min at 30 degrees C, 0.175 M H(2)O(2) and 3g/L catalyst, about 90% dye removal was obtained. These studies indicate that manganese-salen complex immobilized on zeolite framework can act as a good heterogeneous catalyst for removal of dye from wastewaters.     

Synthesis of carbon nanofibres from a liquid solution containing both catalyst and polyethylene glycol

Carbon nanofibres (CNFs) exhibiting bamboo-like, hollow fibril morphology were prepared from a mixture of polyethylene glycol (PEG) and iron-based compounds such as Fe(2)(SO(4))(3)·nH(2)O, Fe(NO(3))·9H(2)O or FeO(OH) by a thermal process. These materials were well mixed in distilled water prior to thermal treatment in an air/nitrogen atmosphere. With increasing temperature, the mixture underwent solvent removal, dehydrogenation, thermal decomposition, carbonization and catalytic graphitization to form CNFs. Results show that CNFs can be formed with different PEG/catalyst ratios (100/1-1000/1 by weight) at 750?°C. The catalyst effect is discussed for the formation of bamboo-like CNFs. The diameter of the CNFs was about 30-50?nm while the length was a few micrometres.     

Immobilization and leaching characteristics of arsenic from cement and/or lime solidified/stabilized spent adsorbent containing arsenic

Solidification/stabilization (S/S) of hazardous iron oxide coated cement (IOCC) spent adsorbent containing arsenic (As(III)) was investigated in the present study. Cement and lime-based S/S effectiveness was evaluated by performing semi-dynamic leach tests. The S/S effectiveness was evaluated by measuring effective diffusion coefficients (D(e)) and leachability indices (LX). It was found that though cement or lime alone were efficient in preventing arsenic leaching (D(e) being in range of 10(-10) to 10(-12) for all the matrices) from the solidified matrices, the best combination for arsenic containment in the matrix was obtained when a mixture of cement and lime was used. The LX values for all the matrices were higher than 10, suggesting that the S/S treated arsenic sludge are acceptable for "controlled utilization". Calcite formation along with precipitation and conversion into non-soluble forms (calcium arsenite, calcium hydrogen arsenate hydrates, calcium hydrogen arsenates, etc.) were found to be the responsible mechanism for low leaching of arsenic from the solidified/stabilized samples. A linear relationship between cumulative fraction (CFR) of arsenic leached and square root of leach time (R(2) ranging from 0.90 to 0.94) suggested that the diffusion is the responsible mechanism for arsenic leaching. Thus, cement and lime show effective containment of the As(III) within the matrix thus indicating S/S by cement and lime, which is also a low-cost option, as a suitable management option for the toxic As(III) sludge.     

Synthesis and characterization of Ni–Mo bimetallic nitride from the mixture of nitrogen and hydrogen

A new method for the synthesis of Ni–Mo bimetallic nitrides was reported in the present paper. The bimetallic nitrides were successfully prepared by a temperature-programmed reaction between bimetallic oxide precursors and the mixed gases of N₂ and H₂ instead of NH₃. By adjusting pH values of the solution in the process of co-precipitation, pure NiMoO₄ or NiMoO₄ with excess MoO₃ was obtained, and then pure Ni₃Mo₃N or Ni₃Mo₃N with γ-Mo₂N was synthesized by nitriding the precursors. The structural properties of the precursors and their corresponding nitrides were investigated by means of X-ray diffraction (XRD), ultraviolet laser Raman spectroscopy, thermogravimetric (TG) analysis and chemical analysis of total nitrogen content.     

Use of an amorphous iron oxide hydrated as catalyst for hydrogen peroxide oxidation of ferulic acid in water

The abatement of ferulic acid (FA), a polyphenolic constituent of olive mill wastewater, is studied in the pH range 5.0-7.0 by using hydrogen peroxide and an amorphous iron oxide as catalyst. The effect of pH, catalyst load, hydrogen peroxide and substrate starting concentrations is assessed during the investigation. A suitable reaction scheme is developed and used to build a mathematical model which satisfactorily describes the system's behavior. Kinetic constants for the proposed scheme as well as the total active site concentration of the catalyst in the studied pH range are estimated. The occurrence of internal mass-transfer limitation for the adopted granulometric fraction of the catalyst is demonstrated.     

The structural transitions during leaching of Ni2Al3 phase in a Raney Ni-Al alloy

The microstructure transitions during leaching of a rapidly solidified Ni-Al alloy have been investigated by means of X-ray diffraction, transmission electron microscopic (TEM) and high resolution electron microscopic (HREM) techniques. Ni₂Al₃ was the main phase in the starting Ni-Al alloy. The microstructure of the Raney nickel catalyst consists of nano-scale nickel crystallites, residue of source phases surrounded by nano-scale boundary regions. The transformation during leaching of Ni₂Al₃ phase was an advancing interface type process. Clusters of AuCu-structure type face-centrered tetragonal Ni₃Al₂ as an intermediate phase seems to appear in the reaction front. Based on an analysis of the atomic configurations of phases Ni₂Al₃, Ni₃Al₂ and nickel, a reasonable explanation for the transition mechanism during leaching of Ni₂Al₃ phase and the arc characteristic of diffraction spots was proposed. The nickel crystallites generated during leaching obey an orientation relationship with the source Ni₂Al₃ phase, which is consistent with the Delannay's orientation relationship proposed for nickel and NiAl phases. The nano-scale structural characteristic of the Raney nickel catalyst, especially its porous structure at the boundary regions, provides an excellent hydrogenation catalytic activity and selectivity of the catalyst.     

Synthesis of beaded and entwined carbon nanofibers in Ni:Al alloy catalyst

This paper reports two new types of carbon nanofibers synthesis by thermal decomposition of n-hexane in presence of Ni-Al alloy in hydrogen atmosphere at 1100 degrees C. One type is "beaded fibers" in which spherical carbon beads (approximately 1 microm) are regularly grown from outer surface of fibers (approximately 0.3 microm). The other new microstructure is "entwined fibers" in which multiple nanofibers of diameter approximately 100 nm grow self-entwined like a braid of hair. Both bead-fiber bonding (in beaded fibers) and fiber-fiber interaction (in entwined fibers) are strong to be detached/unfolded by 30-min ultrasonication.     

A comparative study of the impurity segregation from commercially pure Ti, Ti6Al4V and Ti3Al8V6Cr4Zr4Mo

The surface composition of commercially pure Ti, Ti6Al4V and Ti3Al8V6Cr4Zr4Mo during annealing at different constant temperatures was experimentally investigated. Auger electron spectroscopy was used to monitor the APPHs of the specified elements present on the surfaces. The surfaces of Ti and its alloys were contaminated by oxygen and carbon, and the contamination is attributed to the continual uptake of the background gases, even in the UHV chamber. It was found that mainly C and S segregated at 400 °C, and Cl at higher temperatures (500–630 °C) for commercially pure Ti. However, S was the main segregating species for all three samples. The segregation of Al was measured for the Ti6Al4V and Ti3Al8V6Cr4Zr4Mo samples at higher temperatures. The linear least-square fit method was employed to determine the contribution of pure Ti and TiC from the measured APPH's. The AES fitting confirmed the formation of TiC on the surface at temperatures 400–500 °C.     

The interaction of N with atomically dispersed Ti, V, Cr, Mo, and Ni in ferritic steel

Since long, the nitriding process has been used to improve the mechanical properties of the surface of steel. However, results from the prevailing model for the nitriding of steel are still not in perfect agreement with experimental data. It is investigated if this can be attributed to the model assumption that there is no interaction between nitrogen atoms and alloying atoms in solution in the iron matrix. To this end, the interaction of N with atomically dispersed Ti, V, Cr, Mo, and Ni alloying element atoms in ferritic steel is calculated using Density Functional Theory. Results of the Density Functional Theory calculations agree well with experimental lattice parameter, Mössbauer spectroscopy, and internal friction data taken from literature. Deficiencies in prevailing atomistic models for Fe-Me-N configurations in steel (Me denotes the alloying element considered) are revealed and the initial stages of Me_xN precipitation in alloyed iron are elucidated. For all elements but Ti, the interaction with N is negligible or repulsive. Significant attractive interaction exists only if Ti is a second nearest neighbour of N (–0.22 eV). It is shown that this interaction is too small to significantly influence nitriding at typical nitriding temperatures (>500°C ). Consequently, in modelling the nitriding of steel at typical nitriding temperatures, interaction between the atomically dispersed alloying elements and nitrogen can be disregarded. Internal friction experiments evidence nitrogen in solution in the steel bonded with higher binding energy, also for the other alloying elements. We suggest that this nitrogen is bound in Fe-Me-N accumulations consisting of more than one alloying atom and one or more nitrogen atoms. For the modelling of nitriding of steel, these interactions must be taken into account.     

Kinetics of hydrogen evolution reaction on Zr0.5Ti0.5V0.6Cr0.2Ni1.2 alloy in KOH electrolyte

A hydrogen-storage alloy of the composition Zr_0.5Ti_0.5V_0.6Cr_0.2Ni_1.2 has been investigated for corrosion resistance and hydrogen-evolution reaction (HER) in KOH electrolyte of varying concentrations. Activation of the electrode by absorption of hydrogen takes place after prolonged cathodic polarization in the potential range of HER. Prior to activation, the open-circuit potential is about −0.4 V vs Hg/HgO, OH⁻, at which the alloy electrode tends to undergo corrosion with oxygen-reduction reaction (ORR) as the conjugate reaction. The corrosion-current density measured from Tafel polarization of ORR is found to be independent of KOH concentration and has an average value of about 30 μA cm⁻². Subsequent to activation, the open circuit potential of the electrode is shifted to about −0.93 V vs Hg/HgO, OH⁻, which is equal to the reversible potential of HER. The exchange current density values measured from Tafel polarization of HER are marginally higher in relation to the values obtained before the electrode is activated. Alternating-current impedance spectra in the Nyquist form contain two overlapped semicircles. The high-frequency semicircle is attributed to the electrode geometry, while the low-frequency semicircle is due to the charge-transfer reaction and double-layer capacitance. The impedance data are analyzed by a non-linear least square curve fitting technique and impedance parameters are evaluated.     

Direct determination of peracetic acid, hydrogen peroxide, and acetic acid in disinfectant solutions by far-ultraviolet absorption spectroscopy

In this paper we propose a rapid and highly selective far-ultraviolet (FUV) spectroscopic method for the simultaneous determination of peracetic acid (PAA), hydrogen peroxide, and acetic acid (AA). For this purpose we developed a novel FUV spectrometer that enables us to measure the spectra down to 180 nm. Direct determination of PAA, H(2)O(2), and AA, the three main species in disinfectant solutions, was carried out by using their absorption bands in the 180-220-nm region. The proposed method does not require any reagents or catalysts, a calibration standard, and a complicated procedure for the analysis. The only preparation procedure requested is a dilution of H(2)O(2) with pure water to a concentration range lower than 0.2 wt % in the sample solutions. Usually, the required concentration range can be obtained by the 10 times volume dilution of the actual disinfectant solutions. As the measured sample does not leave any impurity for the disinfection, it can be reused completely by using a circulation system. The detection limit for PAA of the new FUV spectrometer was evaluated to be 0.002 wt %, and the dynamic ranges of the measured concentrations were from 0 to 0.05 wt %, from 0 to 0.2 wt %, and from 0 to 0.2 wt % for PAA, H(2)O(2), and AA, respectively. The response time for the simultaneous determination of the three species is 30 s, and the analysis is applicable even to the flowing samples. This method may become a novel approach for the continuous monitoring of PAA in disinfectant solutions on the process of sterilization.     

Synthesis of C-axis-oriented AlN thin films on high-conducting layers: Al, Mo, Ti, TiN, and Ni

Thin piezoelectric polycrystalline films such as AlN, ZnO, etc., are of great interest for the fabrication of thin film bulk/surface acoustic resonators (TFBARs or TFSARs). It is well-known that the degree of c-axis orientation of the thin films correlates directly with the electromechanical coupling. However, the degree of c-axis orientation of the piezoelectric film is, in turn, influenced by other parameters such as the structure of the substrate material, the matter of whether the c-axis is up or down (polarity), and the growth parameters used. The correlation of these three aspects with the electromechanical coupling of the AlN-thin films, is studied here. Thin AlN films, prepared in a magnetron sputtering system, have been deposited onto thin Al, Mo, Ni, Ti, and TiN films. Such thin high-conducting layers are used to form the bottom electrode of TFBAR devices as well as to define a short-circuiting plane in TFSAR devices. In both cases, they serve as a substrate for the growth of the piezoelectric film. It has been found that the degree of orientation and the surface roughness of the bottom metal layer significantly affects the texture of the AlN films, and hence its electroacoustic properties. For this reason, the surface morphology and texture of the metal layers and their influence on the growth of AlN on them has been systematically studied. Finally, FBARs with both Al and Ti electrodes have been fabricated and evaluated electroacoustically.     

变压吸附制氧设备及其在双氧水生产工艺中的应用

将采用富氧与采用空气用于氢蒽醌氧化的效果进行了简单比较。详细介绍了VPSAZY590 /90型装置的指标参数、工艺流程与操作控制系统。最后就此装置与国产VPSA设备进行了比较 ,并分析了此装置的噪声问题     

AB2型LaMgNi3.7M0.3(M=Ni、Al、Mn、Co、Sn、Cu)贮氢合金的晶体结构及电极性能

系统研究了LaMgNi3.7M0.3（M=Ni、Al、Mn、Co、Sn、Cu）合金的组织结构和电化学性能。XRD和电子探针显微分析（EPMA）结果表明：该系列合金主相均为LaMgNi4相，其中含Mn、Cu和Co元素在LaMgNia合金相中有一定的固溶度，LaMgNi3.7Sn0.3合金中的Sn元素主要以LaNiSn相析出；XRD全谱拟合分析表明：LaMgNi3.7Al0.3中Al元素主要占据在LaNi5相的3g位置。合会化元素在LaMgNi4相中的固溶度从大到小的顺序是Mn〉Cu〉Co〉Al〉Sn。电化学实验表明，该系列合金经1～3次循环即可活化，最大放电容量由245．2mAh／g（M=Sn）变化至293．2mAh／g（M=Co），但合金电极的循环稳定性均较差。合金电极的高倍率放电性能（HRD900%）从大到小依次为Al〉Sn〉Cu〉Mn〉Ni〉Co，其中氢原子在合金中的扩散时合金电极的高倍率放电性能起主要作用。     

Structure and hydrolytic durability of a glass containing waste from spent tributyl phosphate reprocessing

The structure of the glass obtained by incorporation of the residue from reprocessing of the spent extractant, tributyl phosphate, into sodium aluminophosphate glass and the structural state of uranium in this glass were studied by vibration (IR, Raman) and X-ray absorption (XAFS) spectroscopy. An IR and Raman spectroscopic study shows that the structural network of the glasses is formed by ortho- and pyrophosphate groups linked by tetrahedral AlO₄ units. As follows from the XAFS data, uranium is present in the glass in the form of uranyl ions and of separate UO_2+x particles. The glass has high hydrolytic durability: The uranium leach rate determined in accordance with GOST (State Standard) R 52 126–2003 is of the order of 10^–8 g cm^–2 day^–1.     

Voltammetric reduction and determination of hydrogen peroxide at an electrode modified with a film containing palladium and iridium

Cyclic voltammetry of a mixture containing 0.2 mM Na2IrCl6, 0.1 mM PdCl2, 0.2 M K2SO4, and 0.1 M HCl between 1.2 and -0.3 V vs Ag/AgCl for five cycles at 50 mV s-1 yields a stable film on a glassy carbon electrode. The reduction of hydrogen peroxide in 0.1 M KCl is diffusion controlled at that modified electrode. Calibration curves obtained at a 100 mV s-1 scan rate are linear in the range 0.2-1.8 mM H2O2. The slope, 28 microA L mmol-1, is independent of film thickness. Since dissolved oxygen is reduced at about the same potential as H2O2, -0.3 V, at the modified electrode, it will act as an interferent in solutions that are not deaerated; however, the currents are additive. A second limitation of the described procedure is that with the KCl electrolyte the immobilized film must be reoxidized prior to each measurement. Preliminary data are described which suggest that this problem is alleviated by switching to a basic supporting electrolyte.     

Kinetics and products of reactions of MTBE with ozone and ozone/hydrogen peroxide in water.

Methyl-t-butyl-ether (MTBE) has become a prevalent groundwater pollutant due to its high volume use as a nationwide gasoline additive. Given its physicochemical properties, it requires new treatment approaches. Both aqueous O(3) and a combination of O(3)/H(2)O(2), which gives *OH, can remove MTBE from water, making use of O(3) a viable technology for remediation of groundwater from fuel contaminated sites. Rate constants and temperature dependencies for reactions of MTBE with O(3) or with *OH at pH 7.2, in a range of 21-45 degrees C (294-318K) were measured. The second-order rate constant for reaction of MTBE with O(3) is 1.4 x 10(18)exp(-95.4/RT) (M(-1)s(-1)), and for reaction of MTBE with *OH produced by the combination of O(3)/H(2)O(2) is 8.0 x 10(9)exp(-4.6/RT) (M(-1)s(-1)), with the activation energy (kJ mol(-1)) in both cases. At 25 degrees C, this corresponds to a rate constant of 27 M(-1)s(-1) for ozone alone, and 1.2 x 10(9) M(-1)s(-1) for O(3)/H(2)O(2). The concentration of *OH was determined using benzene trapping. Products of reactions of O(3) and O(3)/H(2)O(2) with MTBE, including t-butyl-formate (TBF), t-butyl alcohol (TBA), methyl acetate, and acetone, were determined after oxidant depletion. A reaction pathway for mineralization of MTBE was also explored. Under continuously stirred flow reactor (CSTR) conditions, addition of H(2)O(2) markedly increases the rate and degree of degradation of MTBE by O(3).