二硫化钼基复合材料的合成及光催化降解与产氢特性

随着环境污染和能源短缺的加剧,无污染环境修复技术及清洁能源替代工程已成为一项重要而紧迫的任务。作为层状结构的过渡金属硫化物,二硫化钼带隙较窄,边缘具有高的反应活性,容易与其他物质形成复合结构,是近年来光催化环境修复及清洁能源领域的研究热点。本文详细介绍了半导体二硫化钼及其复合物的合成方法和光催化降解与产氢行为,重点阐述了二硫化钼及其复合物的具体复合方式、光催化降解污染物活性、光催化产氢活性以及具体的降解与产氢机理等方面的内容,并举例说明。二硫化钼及其复合物在光催化降解污染物和光催化产氢方面具有绿色、廉价、高效等优点,在环境修复及清洁能源领域具有巨大的潜力和应用发展前景。     

反相流动注射催化光度法测定痕量锰

本文基于在邻菲罗啉活化下，锰（Ⅱ）对高碘酸钾氧化罗丹明Ｂ褪色的催化作用，建立了痕量锰的反相流动注射分析方法。方法的线性范围为０－５０μｇ／Ｌ，检测下限为０．７μｇ／Ｌ锰（Ⅱ）。对２０μｇ／Ｌ锰（Ⅱ）测定九次的相对标准偏差为１．８％，进样频率不少于６０次／ｈ。方法应用于水样和标准镁合金样品分析，结果满意。     

Ordre chimique dans les alliages metalliques liquides

Due to improvements of high temperature calorimetry, the quantity of liquid alloys showing large negative departures from ideality increased strongly during the last decades. Such a behaviour is now explained by the occurence of chemical short-range order (CSRO), the stoichiometry of which is often elucidated from direct structural determinations as well as from modelization of the thermodynamic functions. In some extreme cases, the destruction of CSRO by increasing temperature lead to a genuine second order transition. The short rewiev of experimental results concerning the variation of physical properties of some liquid alloysvs. temperature and concentration agrees well with CSRO. Some examples of structural determination of CSRO in metallic melts are given. Finally, links between CSRO and phase diagrams and between CSRO and glass-forming ability are also examined.     

Synthesis and Crystal Structur of (4,4''-H2bipy)[CdBr4]·H2O

The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms.     

添加剂铜和银离子对MnO2催化燃烧CH4的影响

催化燃烧法，由于起燃温度低、去除率高、适用氧浓度范围大、无二次污染、燃烧缓和等，是国内外治理有机废气时，回收利用能量最有效的方法之一［１］．但目前用于该过程的催化剂中均含有来源有限、价格昂贵的贵金属铂或钯［２］．因此，寻找来源丰富、价格低廉、性能相当...     

Electrosorption of hydrogen into palladium-gold alloys

Hydrogen electrosorption into Pd-Au alloys has been studied in acidic solutions (1 M H₂SO₄) using cyclic voltammetry. Pd-Au electrodes with limited volume were prepared by electrochemical co-deposition. It was found that the maximum H/(Pd+Au) ratios decrease monotonically with increasing gold content and reach zero at ca. 70 at% Au. Similarly to the case of Pd limited volume electrodes, two peaks in the hydrogen region, corresponding to two types of sorbed hydrogen, are observed on voltammograms for Pd-rich alloys. The hydrogen capacity, H/(Pd+Au), measured electrochemically, depends on the sweep rate in the cyclic voltammetry experiments, which suggests that two different mechanisms for hydrogen desorption from the Pd-Au alloy are possible. After a strong decrease of Pd concentration at the electrode surface, caused by long cyclic polarization to sufficiently anodic potentials, the amount of absorbed hydrogen is still significant for alloys initially rich in Pd. The results obtained from CO adsorption experiments suggest that only Pd atoms are active in the hydrogen absorption/desorption process. Electronic Publication     

A model for short alpha-neurotoxin bound to nicotinic acetylcholine receptor from Torpedo californica: comparison with long-chain alpha-neurotoxins and alpha-conotoxins

Short-chain alpha-neurotoxins from snakes are highly selective antagonists of the muscle-type nicotinic acetylcholine receptors (nAChR). Although their spatial structures are known and abundant information on topology of binding to nAChR is obtained by labeling and mutagenesis studies, the accurate structure of the complex is not yet known. Here, we present a model for a short alpha-neurotoxin, neurotoxin II from Naja oxiana (NTII), bound to Torpedo californica nAChR. It was built by comparative modeling, docking and molecular dynamics using 1H NMR structure of NTII, cross-linking and mutagenesis data, cryoelectron microscopy structure of Torpedo marmorata nAChR [Unwin, N., 2005. Refined structure of the nicotinic acetylcholine receptor at 4A resolution. J. Mol. Biol. 346, 967-989] and X-ray structures of acetylcholine-binding protein (AChBP) with agonists [Celie, P.H., van Rossum-Fikkert, S.E., van Dijk, W.J., Brejc, K., Smit, A.B., Sixma, T.K., 2004. Nicotine and carbamylcholine binding to nicotinic acetylcholine receptors as studied in AChBP crystal structures. Neuron 41 (6), 907-914] and antagonists: alpha-cobratoxin, a long-chain alpha-neurotoxin [Bourne, Y., Talley, T.T., Hansen, S.B., Taylor, P., Marchot, P., 2005. Crystal structure of Cbtx-AChBP complex reveals essential interactions between snake alpha-neurotoxins and nicotinic receptors. EMBO J. 24 (8), 1512-1522] and alpha-conotoxin [Celie, P.H., Kasheverov, I.E., Mordvintsev, D.Y., Hogg, R.C., van Nierop, P., van Elk, R., van Rossum-Fikkert, S.E., Zhmak, M.N., Bertrand, D., Tsetlin, V., Sixma, T.K., Smit, A.B., 2005. Crystal structure of nicotinic acetylcholine receptor homolog AChBP in complex with an alpha-conotoxin PnIA variant. Nat. Struct. Mol. Biol. 12 (7), 582-588]. In complex with the receptor, NTII was located at about 30 A from the membrane surface, the tip of its loop II plunges into the ligand-binding pocket between the alpha/gamma or alpha/delta nAChR subunits, while the loops I and III contact nAChR by their tips only in a 'surface-touch' manner. The toxin structure undergoes some changes during the final complex formation (for 1.45 rmsd in 15-25 ps according to AMBER'99 molecular dynamics simulation), which correlates with NMR data. The data on the mobility and accessibility of spin- and fluorescence labels in free and bound NTII were used in MD simulations. The binding process is dependent on spontaneous outward movement of the C-loop earlier found in the AChBP complexes with alpha-cobratoxin and alpha-conotoxin. Among common features in binding of short- and long alpha-neurotoxins is the rearrangement of aromatic residues in the binding pocket not observed for alpha-conotoxin binding. Being in general very similar, the binding modes of short- and long alpha-neurotoxins differ in the ways of loop II entry into nAChR.     

In Situ Study of the Surface Oxidation of FeCr Alloys Using Grazing Incidence X‐ray Absorption Spectroscopy (GIXAS)

The surface oxidation of FeCr alloys with 18, 28, and 43 mass‐% Cr was investigated in situ using grazing‐incidence X‐ray absorption spectroscopy (GIXAS) at the chromium and iron K‐edges. Oxidation in air was monitored in situ in the temperature range from 290 K to 680 K. The standard GIXAS data analysis is extended for the treatment of a single layer model in order to estimate the chromium concentrations of the oxide layer and of the near‐interface substrate as well as the oxide layer thickness. XANES analysis shows transitions from b.c.c. Fe to corundum type Fe₂O₃ and from b.c.c. Cr to corundum type Cr₂O₃. The initial oxide layers are 1.1‐1.4 nm thick and contain 60‐90 mass‐% chromium, while the near‐interface substrate is depleted in Cr. During heating, iron oxide growth dominates up to 560‐600 K. Then the chromium oxide layer loses its passivation effect and Cr oxidation sets in.     

α-Al2O3纳米粒子对Co-Ni合金异常共沉积电化学行为的影响

为了研究在电化学复合共沉积过程中,惰性纳米粒子和金属离子、电极表面的相互作用,以及由此产生的对合金电化学共沉积行为的影响.本文从两个吸附过程出发: 电解液中的金属离子和H＋在纳米粒子表面的吸附；纳米粒子迁移到阴极表面,在电极表面的吸附.采用Zeta电势和稳态极化以及电化学交流阻抗（EIS）研究了纳米Al2O3粒子和电解液中的金属离子，和电极表面的相互作用,进而分析了纳米粒子对Co2＋和Ni2＋还原沉积的影响规律.通过对阻抗数据的拟合,讨论了Al2O3纳米粒子对等效电路中各物理参数的影响.在H＋和不同金属离子在纳米粒子上发生竞争吸附的基础上,提出了纳米粒子和合金共沉积的可能反应历程.     

Static ultrasonic oscillations induced degradation and its effect on the linear rheological behavior of novel propylene based plastomer melts

The ultrasonic degradation of novel propylene based plastomer (DP) melts with different melt viscosities was conducted in a “static” ultrasonic device where the samples were taken from various distances from the tip of an ultrasonic probe. The effects of ultrasonic time, oscillation temperature, ultrasonic intensity and the distance from the ultrasonic probe tip on the degradation behavior of DP melts as well as the ultrasonic degradation effect on the linear rheological behavior of DP melts were studied. The results show that the increase of initial melt viscosity of DP (higher molecular weight) has greater impact on the ultrasonic degradation of DP melt. The molecular weight and intrinsic viscosity of DP decrease with the increase of ultrasonic oscillation time and they approach to a limiting value. The molecular weight distribution of DP increases after ultrasonic degradation. Decreasing oscillation temperature and distance from probe tip and increasing ultrasonic intensity lead to an increase in the degradation of DP melt. The linear rheological behavior measurements of the samples obtained near the ultrasonic probe tip show that ultrasonic oscillations decrease the complex viscosity, zero shear viscosity, viscoelastic moduli, cross modulus, relaxation time and the slope of log G′ − log G″ for DP melts.