超化学计量比Ti-Zr-V-Mn-Cr-Ni贮氢电极合金相结构及电化学性能研究

研究了超化学计量比对钛基贮氢俣金相结构及电化学性能的影响 XRD及EDS分析表明,超化学计量比贮氢合金(Ti0.8Zr0.2)(V0.533Mn0.107Cr0.16Ni0.2)x(x=2,3,4.5,6)均主要由六方结掏的C14型Laves相和体心立疗结构的钒基固溶体相构成,随着x值的增大,两相的晶胞参数及晶胞体积均减小.电化学性能测试表明,当x的值在2-5范围内时,随着x值的增大,合金的最大放电容量、放电电位、高倍率放电性能(HRD)、循环稳定性、交换电流密度,I0以及极限电流密度,IL均提高.但继续增大x值后,除放电电位、高倍率放电性能和循环稳定性继续有所提高外,最大放电容量、交换电流密度I0以及极限电流密度,IL均减小.此外,随着化学计量比的增大,合金电极的活化渐趋困难.

Sr(Fe(1-x)Nb_x)O_(3-δ)陶瓷系统中非化学计量比参量δ的实验测定

本文描述了利用失重测量和EDTA滴定方法对Sr(Fe_(1-x)Nb_x)O_(3-δ)陶瓷系统当X取不同值时,非化学计量比参量δ的数值进行实验测定的过程和方法。

SiC材料升华法生长机理

讨论了SiC晶体升华法生长机理。从SiC晶体生长过程中的化学反应,热传输,物质传输以及缺陷的形成等方面进行了探讨。分析了化学计量比和保护气体压力对SiC单晶生长及其缺陷形成的影响。通过分析得到,要获得高质量的SiC单晶,必须有效地控制各种工艺参数。

改进的共沉淀法制备Bi系起导体原始粉末及其化学计量性研究

在研究水介质中草酸盐共沉淀法制备Bi—Pb—Sr—Ca—Cu—O系多元粉末的化学计量性基础上,提出了一种改进的共沉淀法.特色在于共沉淀反应在一种表面张力比水小的有机溶剂和水的混合溶液介质中(该有机溶剂体积分数大于90％)进行.从而克服了水介质中共沉淀制备Bi系超导粉末无法维持化学计量比的严重缺点,系统地研究了pH值、草酸浓度和陈化时间对沉淀产物化学计量比维持的影响.

非化学计量比铌酸锌微波介电陶瓷的低温烧结行为

采用固相烧结工艺制备低损耗、非化学计量比Zn1.01Nb2O6微波介电陶瓷。研究了添加不同量的Li2CO3–B2O3–V2O5(LBV)对Zn1.01Nb2O6陶瓷烧结温度、表面形貌以及微波介电性能的影响。结果表明:LBV作为助烧剂,在陶瓷烧结过程中产生了液相,当添加剂含量大于1.5%(质量分数)时,LBV与基体陶瓷发生了化学反应。液相的产生、副相LiZnNbO4的形成以及V5+的扩散共同改善了陶瓷的烧结行为,使烧结温度由1 175℃低至950℃。LBV加入到基体陶瓷后对微波介电性能影响较小。当LBV添加量为1.0%,并在950℃保温4 h后,Zn1.01Nb2O6陶瓷微波介电性能最优:εr=20.6,Q×f=90 472 GHz,τf=–85.9×10–6℃–1。

农牧交错区小叶锦鸡儿(Caragana microphylla)人工灌木林土壤碳氮磷化学计量特征

研究小叶锦鸡儿(Caragana microphylla)人工灌木林土壤化学计量特征,有助于阐明林下土壤养分分配及限制因素,为人工灌-草生态系统物质平衡和稳定维持提供理论依据。以内蒙古中部农牧交错区天然草地为对照(CK),比较相同林龄不同密度人工小叶锦鸡儿灌木林下0~50 cm土层土壤有机碳、总氮和总磷含量及其化学计量特征。结果表明(1)与天然草地相同,小叶锦鸡儿人工灌木林土壤SOC和TN在0~5 cm出现明显地"表聚性",且随着土壤深度的增加逐渐降低。(2)该研究区土壤释放P素能力较强且含量相对稳定,但C素和N素含量总体偏低;其间,C/P受控于土壤SOC含量,N/P受控于TN含量,C/N受林分密度影响较小,相对稳定。(3)在土壤养分平衡过程中,该地区低密度林(1200棵hm^-2)各土层C、N、P含量均显著高于中、高密度林,促进了土壤C素和N素的积累与循环,有助于改善土壤环境。

FTIR Spectroscopic Study of Broad Bean Diseased Leaves

[Objective] The aim was to indentify diseased leaves of broad bean by vibra- tional spectroscopy. [Method] In this paper, broad bean rust, fusarium rhizome rot, broad bean zonate spot, yellow leaf curl virus and normal leaves were studied using Fourier transform infrared spectroscopy combined with chemometrics. [Result] The spectra of the samples were similar, only with minor differences in absorption inten- sity of several peaks. Second derivative analyses show that the significant difference of all samples was in the range of 1 200-700 cm2. The data in the range of 1 200- 700 cm＇ were selected to evaluate correlation coefficients, hierarchical cluster analy- sis （HCA） and principal component analysis （PCA）. Results showed that the correla- tion coefficients are larger than 0.928 not only between the healthy leaves, but also between the same diseased leaves. The values between healthy and diseased leaves, and among diseased leaves, are all declined. HCA and PCA yielded about 73.3% and 82.2% accuracy, respectively. [Conclusion] This study demonstrated that FTIR techniques might be used to detect crop diseases.

Top-cited Articles in Chemical Engineering in Science Citation Index Expanded:A Bibliometric Analysis

This study aimed to identify and to analyze characteristics of top-cited articles published in the Web of Science chemical engineering subject category from 1899 to 2011.Articles that have been cited more than 100 times were assessed regarding publication outputs,and distribution of outputs in journals.Five bibliometric indicators were used to evaluate source countries,institution and authors.A new indicator,Y-index,was created to assess quantity and quality of contribution to articles.Results showed that 3828 articles,published between 1931 and 2010,had been cited at least 100 times.Among them 54% published before 1991,and 49% top-cited articles originated from US.The top eight productive institutions were all located in US.The top journals were Journal of Catalysis,AIChE Journal,Chemical Engineering Science and Journal of Membrane Science.Y-index was successfully applied to evaluate publication character of authors,institutions,and countries/regions.

Experimental and Theoretical Study of Deprotonation of DNA Adenine Cation Radical

Among all the DNA components, extremely redox-active guanine （G） and adenine （A） bases are subject to facile loss of an electron and form cation radicals （G＋＂ and A＋＇） when exposed to irradiation or radical oxidants. The subsequent deprotonation of G＋＇ and A＋＇ can invoke DNA damage or interrupt hole transfer in DNA. However, compared with intensive reports for G＋, studies on the deprotonation of A＋ are still limited at present. Herein, we investigate the deprotonation behavior of A＋. by time-resolved laser flash photolysis. The deprotonation product of A（N6-H）＇ is observed and the deprotonation rate constant, （2.0±0.1）×10 7 s-1, is obtained at room temperature. Further, the deprotonation rate con- stants of A＋. are measured at temperatures varying from 280 K to 300 K, from which the activation energy for the N6-H deprotonation is determined to be （17.1±1.0） kJ/mol by Arrhenius equation. In addition, by incorporating the aqueous solvent effect, we perform density functional theory calculations for A＋ deprotonation in free base and in duplex DNA. Together with experimental results, the deprotonation mechanisms of A＋ in free base and in duplex DNA are revealed, which are of fundamental importance for understanding the oxidative DNA damage and designing DNA-based electrochemical devices.

Structural and Infrared Spectroscopic Study on Solvation of Acetylene by Protonated Water Molecules

The effect of solvation on the conformation of acetylene has been studied by adding one water molecule at a time. Quantum chemical calculations of the n＋ （C2H2）（H2O）n （n=1-5） clusters indicate that the H2O molecules prefer to form the OH...Tr interaction rather than the CH...O interaction. This solvation motif is different from that of neutral （C2H2）（H2O）n （n=1-4） clusters, in which the H2O molecules prefer to form the CH...O and OH...C Hbonds. For the H＋（C2H2）（H2O）n cationic clusters, the first solvation shell consists of one ring structure with two OH...Tr H-bonds and three water molecules, which is completed at n=4. Simulated infrared spectra reveal that vibrational frequencies of OH... H-bonded O-H stretching afford a sensitive probe for exploring the solvation of acetylene by protonated water molecules. Infrared spectra of the H＋ （C2H2）（H2O）n （n=1-5） clusters could be readily measured by the infrared photodissociation technique and thus provide useful information for the understanding of solvation processes.

Alkaloids from an algicolous strain of Talaromyces sp.

Compounds isolated and identified in a culture of the alga-endophytic fungus Talaromyces sp. cf- 16 included two naturally occurring alkaloids, 2-[（S）-hydroxy（phenyl）methyl]-3-mcthylquinazolin-4（3H）- one （la） and 2-[（R）-hydroxy（phenyl）methyl]-3-methylquinazolin-4（3H）-one （lb）, that were identified for the first time. In addition, seven known compounds （2-8） were obtained from the culture. Following chiral column chromatography, compounds la and lb were identified as enantiomers by spectroscopic analyses and quantum chemical calculations. Bioassay results showed that 5 was more toxic to brine shrimp than the other compounds, and that 3-6 could inhibit Staphylococcus aureus.

Oxidation of chalcopyrite in air-equilibrated acidic solution: Inhibition with phenacyl derivatives

The effects of 4-(2-hydroxyphenyl)-2-(morpholin-4-yl)-1,3-thiazole(Pr02), 1-(3,5-dibromo-2-hydroxyphenyl)-1-oxoethan-2-yl-N,N-diethyldithiocarbamate(Pr04) and 1-(5-bromo-2-hydroxy-3-methylphenyl)-1-oxoethan-2-yl-Oethyl xanthate(Pr06) on the aqueous oxidation of chalcopyrite(CuFeS2) in air-equilibrated solution at a temperature of 25 ℃ and a pH of 2.5 were studied. The effects were investigated by using potentiodynamic polarization, electrochemical impedance spectroscopy(EIS), scanning electron microscopy coupled with energy dispersive X-ray(SEM/EDX) analysis, aqueous batch experiments, Fourier transform infrared(FTIR) spectroscopy, Raman scattering and quantum chemical calculations. It is found that the anodic current densities decrease in the order of EtOH > Pr02 > Pr04 > Pr06. These results, along with those of the EIS measurements, show that Pr02, Pr04 and Pr06 are effective anodic inhibitors of chalcopyrite aqueous oxidation. Both Raman scattering and FTIR spectroscopy indicate that the elemental sulfur, polysulfide and ferric oxyhydroxides that form on the surface of the mineral are not responsible when it comes to the aqueous oxidation inhibition of chalcopyrite. Quantum chemical calculations show that the adsorption of the tested compounds on the chalcopyrite surface is energetically favorable and so, it can explain the inhibiting effects that were observed.

Sequential Observation of Alkali-halide Gas Phase Clusters in High Resolution TOF-MS and Prediction of Their Structures

Alkali halide clusters are interesting model systems that can provide information about how crystal properties evolve. To study these properties, a high-resolution atmospheric pressure inlet time-of-flight mass spectrometry （APi-TOF-MS） study of the sequential sodium halides series, C1-（NaC1）n and Br-（NaBr）m, has been reported, and the viability of the APi-TOF- MS equipped with an electrospray ionization source in determining cluster compositions has been demonstrated. The isotopic patterns were well resolved, as n=4 and 7 were determined to be the magic numbers for C1-（NaC1）n clusters, which were particularly abundant in the mass spectra. A global minimum search based on density functional theory enabled basin hopping yield the most stable structures for the mentioned series. The structures exhibit several distinct motifs which can be roughly categorized as linear chain, rock salt, and hexag- onal ring. This work provides an effective way to discover and elucidate the nonstoichiometry sodium halide clusters. These clusters possess very high vertical detachment energies and are generally called as superhalogens, which play important roles in chemistry because they are widely used in the synthesis of new classes of charge-transfer salts.

A Study on Stoichiometry of Complexes of Tributyl Phosphate and Methyl Isobutyl Ketone with Lithium in the Presence of FeCl_3

To study the characteristic of liquid-liquid extraction equilibrium of lithium from brine sources, the complexes formed from tributyl phosphate （TBP） and methyl isobutyl ketone （MIBK） with lithium were investi- gated using FeCl3 as coextracting agent. Liquid-liquid extraction reaction mechanisms were proposed and the stoichiometry of tetrachloroferrate（III） complex with lithium was obtained by regressing the experimental data. It is found that the stoichiometry of tetrachloroferrate（III） to lithium in the complex is 1 ： 1 with either TBP or MIBK as extractant in kerosene. The stoichiometry of the complex of TBP with Li was 1 ： 1 and that of MIBK with Li was 2 ： 1. The formed complexes of TBP and MIBK with lithium are determined to be LiFeCla-TBP and LiFeC14.2MIBK, respectively, according to the rule of neutralization.

Ecological stoichiometry of nitrogen, phosphorous, and sulfur in China's forests

Much attention has been paid to the stoichiometry of carbon(C), nitrogen(N), and phosphorus(P) because of their significance for plant growth and climate change. However, other nutrients, such as sulfur(S), are often ignored. In this study, we analyzed the stoichiometry of N, P, and S in leaves of 348 plant species in China's forests. The results show higher N content and higher molar ratios of N/P and P/S in Angiospermae than in Gymnospermae. At the family level, Ulmaceae absorbed more N and P from soils than other families, and Cupressaceae absorbed more S than other families. In addition,except for bamboo and other tropical forests, leaf N and P content of China's forests generally increased from low to middle latitudes and then slightly decreased or plateaued at high latitudes. Plant ecotypes, taxonomic groups, environmental conditions, atmospheric S precipitation, and soil-available N and P significantly affected the distribution and stoichiometry of leaf N, P, and S in China's forests.Our study indicates that China's forests are likely limited by P and S deficiencies which may increase in the future.

Structural Evolution and Electronic Properties of Au2Gen-/0（n=1-8） Clusters: Anion Photoelectron Spectroscopy and Theoretical Calculations

Investigating the structures and properties of Au-Ge mixed clusters can give insight into the microscopic mechanisms in gold-catalyzed Ge films and can also provide valuable information for the production of germanium-based functional materials. In this work, size-selected anion photoelectron spectroscopy and theoretical calculations were used to explore the structural evolution and electronic properties of Au2Gen^-/0 (n=1-8) clusters. It is found that the two Au atoms in Au2Gen^-/0 (n=1-8) showed high coordination numbers and weak aurophilic interactions. The global minima of Au2Gen- anions and Au2Gen neutrals are in spin doublet and singlet states, respectively. Au2Gen- anions and Au2Gen neutrals showed similar structural features, except for Au2Ge4^-/0 and Au2Ge5^-/0. The C2v symmetric V-shaped structure is observed for Au2Ge1^-/0, while Au2Ge2^-/0 has a C2v symmetric dibridged structure. Au2Ge3^-/0 can be viewed as the two Au atoms attached to different Ge-Ge bonds of Ge3 triangle. Au2Ge4- has two Au atoms edge-capping Ge4 tetrahedron, while Au2Ge4 neutral adopts a C2v symmetric double Au atoms face-capping Ge4 rhombus. Au2Ge5-8^-/0 show triangular, tetragonal, and pentagonal prism-based geometries. Au2Ge6 adopts a C2v symmetric tetragonal prism structure and exhibits σ plus π double bonding characters.

Infrared Spectroscopy of CO2 Transformation by Group Ⅲ Metal Monoxide Cations

Infrared photodissociation spectroscopy of mass-selected[MO(CO2)n]^+(M=Sc,Y,La)complexes indicates that the conversion from the solvated structure into carbonate one can be achieved by the ScO^+ cation at n=5 and by the YO^+ cation at n=4,while only the solvated structures are observed for the LaO^+ cation.These findings suggest that both the ScO^+ and YO^+cations are able to fix CO2 into carbonate.Quantum chemical calculations are performed on[MO(CO2)n]^+ to identify the structures of the low-lying isomers and to assign the observed spectral features.Theoretical analyses show that the[YO(CO2)n]^+ complex has the smallest barrier for the conversion from the solvated structure into carbonate one,while[LaO(CO2)n]^+ exhibits the largest conversion barrier among the three metal oxide cations.The present system affords a model in clarifying the effect of different metals in catalytic CO2 transformation at the molecular level.

Office Furniture Design for Wheelchair User

There are an estimated 1.19 million wheelchair users in Spain. People use wheelchairs for a variety of reasons, the most common one is paralysis from spinal cord injuries. Current estimates indicate there are around 504,000 people alive in Spain with spinal cord injuries. Among other reasons for using wheelchairs are： fatigue from multiple sclerosis, muscle weakness from muscular dystrophy, lower limb spasticity from cerebral palsy, and missing limbs due to amputation. People who use wheelchairs may encounter a variety of obstacles at their workstations depending on their limitations. Some possible accommodations could be adjustable height desk or table for a person who cannot work comfortably at an existing desk, accessible filing system or office supplies, and frequently used materials on most accessible shelves or drawers for a person who cannot reach upper and lower shelves and drawers. This paper presents the graphical design of a workstation for wheelchair users, in this case, technical, anthropometric, ergonomic, aesthetics and scientists aspects have been analyzed. The design of composite structure conduct to explicit safety constraints applied to office furniture requirements kept continuously current and updated as part of innovation. Finally, results are showed in a three-dimensional model.

Improvement of electrocatalytic alcohol oxidation by tuning the phase structure of atomically ordered intermetallic Pd-Sn nanowire networks

Atomically ordered intermetallic compounds(OICs)have aroused remarkable interests for wide applications and are considered as very promising materials for electrocatalysis owing to the strict stoichiometry,well-defined atom binding environment,and the specific crystalline phase.However,the tunable synthesis of the intermetallics remains a giant challenge.Herein,this study reports the preparation of the Pd-Sn OICs composed of an interconnected nanowire network structure with adjustable molar ratios of elements Pd and Sn.The co-reduction of Pd(acac)_(2) and SnCl_(2)·2H_(2)O in ethylene glycol(EG)in the presence of sodium hypophosphite(NaH_(2)PO_(2))as the reducing agent affords OICs of three phases:hexagonal Pd_(3)Sn_(2-)P6_(3)/mmc,orthorhombic PdSn-Pnmb,and orthorhombic PdSn_(2)-Aba_(2).Also,the pure phase can convert to two mixed phases(Pd_(3)Sn_(2)/PdSn and PdSn/PdSn_(2))by just altering the feed ratio.It is found that orthorhombic PdSn-Pnmb OIC has a large electrochemically active surface area(ECSA),excellent electrocatalytic performance(4857 mA mg_(Pd)^(−1)),and outstanding stability toward ethanol oxidation reaction(EOR),which could be attributed to its optimal electronic structure.These results demonstrate that the phase engineering of OICs with desired components is an excellent way for catalysts design.

The impacts of stress on the chemical structure of coals:a mini-review based on the recent development of mechanochemistry

The chemical structure evolution of coal,which is important for understanding coalification and the accompanying volatile and possible oil generation,is generally thought to be influenced by temperature,time and confining pressure.Though evidence concerning the impacts of stress on the chemical structure has accumulated for many years and some hypotheses have been proposed,the mechanism remains controversial.Recent years have seen a breakthrough in mechanochemistry,which proves that stress can act on the molecule directly to initiate or accelerate reactions by deforming the chemical bonds.The progress in mechanochemistry gives researchers incentive to consider how stress works on the chemical structure of coals.Preliminary quantum chemical calculations have been performed on the macromolecule of anthracite to explain the mechanism of gas generation during the deformation experiments at low temperatures.This paper briefly reviews the evidence regarding the impacts of stress on the chemical structure of coals and introduces the recent achievements in the mechanism research.To further investigate this problem,more work should be undertaken by researchers from both geology and quantum chemistry fields.