强脉冲磁场致金属铝电离化研究进展

研究了脉冲兆高斯磁场致金属铝表面热电离的物理现象。所采用厚铝棒的初始半径范围为0．25～1．00mm，大于磁场的趋肤深度。加载的脉冲电流在100ns时间内从0上升到1．0MA。铝表面磁感应强度Bs的上升速率为3×10^9～8×10^9 T／S，不同铝棒表面的磁感应强度峰值的范围为150～400T。对于这种范围的参数，等离子体形成的阈值是Bthreshold=220T。当半径R0=0．5mm的铝棒达到峰值电流时，Bs=300T，铝棒表面的电子能量为20eV；相应地，半径为R0=1．0mm的铝棒表面电子能量为0．7eV，Bs（t）〈220T，意味着没有等离子体产生。

Improvement of ionic conductivity of solid polymer electrolyte based on Cu-Al bimetallic metal-organic framework fabricated through molecular grafting

A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.

Effect of metallic ions on dispersibility of fine diaspore

Dispersion experiments were conducted to study the influence of metallic cations on the dispersibility of diaspore. The reaction mechanisms were investigated based on the analysis of zeta （ξ） potential and calculations of solution chemistry and DLVO theory. The results show that the valence of cations, instead of the cation type, plays an important role in the dispersibility of diaspore The impact of multivalent metallic cations is greater than that of monovalent cations. In the presence of Ca^2＋ and Mg^2＋, the dispersion of diaspore doesn＇t change in the range of pH value below 10. However, Ca^2＋ and Mg^2＋ may induce strong coagulation of particles when pH value is higher than 10. The adsorption of species of calcium and magnesium ions on diaspore can cause the compression of electric double layer, the decrease of the absolute value of zeta potential and the repulsion force between diaspore particles. The new IEP （isoelectric point） appeared at pH value of 11 may attribute to the adsorption of Mg（OH）2（s）.

Treatment of Organic Wastewater Containing Cr^(3+) by a Novel Complex Process of Electrodeposition and Biofilm

A novel complex process of electrodeposition and biofilm is utilized to treat organic wastewater containing Cr 3+, and its purifying mechanism is also described in this article. In details, organic materials in wastewater are consumed as nutritious source by biofilm composed of microorganism and EPS (extracellular polysaccharide substance). While one part of heavy metal ions, such as Cr 3+, is removed by electrodeposition, the other part is adsorbed on biofilm. In contrast, experimental data of single electrodeposition or biofilm process are listed. Further, the kinetic curves of microbes cultivated or microbes acclimated by Cr 3+ to degrade glucose are provided,too. In conclusion, the experimental results indicate that initial wastewater consists of C 6H 12O 6 (500 mg·L -1), Cr 3+ (10 mg·L -1), after treated with the complex process, concentrations of C 6H 12O 6 and Cr 3+ are on the scale of 15-20 mg·L -1, and less than 1 mg·L -1, respectively. Purified water can meet the standards of industrial reused water.

Treatment of Organic Wastewater Containing Cr3+ by a Novel Complex Process of Electrodeposition and Biofilm

A novel complex process of electrodeposition and biofilm is utilized to treat organic wastewater containing Cr 3+, and its purifying mechanism is also described in this article. In details, organic materials in wastewater are consumed as nutritious source by biofilm composed of microorganism and EPS (extracellular polysaccharide substance). While one part of heavy metal ions, such as Cr 3+, is removed by electrodeposition, the other part is adsorbed on biofilm. In contrast, experimental data of single electrodeposition or biofilm process are listed. Further, the kinetic curves of microbes cultivated or microbes acclimated by Cr 3+ to degrade glucose are provided,too. In conclusion, the experimental results indicate that initial wastewater consists of C 6H 12O 6 (500 mg·L -1), Cr 3+ (10 mg·L -1), after treated with the complex process, concentrations of C 6H 12O 6 and Cr 3+ are on the scale of 15-20 mg·L -1, and less than 1 mg·L -1, respectively. Purified water can meet the standards of industrial reused water.

Purification technology of molten aluminum

Various purification methods were explored to eliminate the dissolved hydrogen and nonmetallic inclusions from molten aluminum alloys. A novel rotating impeller head with self-oscillation nozzles or an electromagnetic valve in the gas circuit was used to produce pulse gas currents for the rotary impeller degassing method. Water simulation results show that the size of gas bubbles can be decreased by 10%20% as compared with the constant gas current mode. By coating ceramic filters or particles with active flux or enamels, composite filters were used to filter the scrap A356 alloy and pure aluminum. Experimental results demonstrate that better filtration efficiency and operation performance can be obtained. Based on numerical calculations, the separation efficiency of inclusions by high frequency magnetic field can be significantly improved by using a hollow cylinder-like separator or utilizing the effects of secondary flow of the melt in a square separator. A multi-stage and multi-media purification platform based on these methods was designed and applied in on-line processing of molten aluminum alloys. Mechanical properties of the processed scrap A356 alloy are greatly improved by the composite purification.

Decorating non-noble metal plasmonic Al on a TiO2/Cu2O photoanode to boost performance in photoelectrochemical water splitting

Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.

Development of a bismuth-based metal-organic framework for photocatalytic hydrogen production

A novel 3 D bismuth-organic framework(called Bi-TBAPy) single crystal was synthesized by employing 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H4TBAPy) as an organic linker. The study demonstrates that the Bi-TBAPy not only possesses good chemical stability and suitable band edge positions for promising photocatalytic H2 evolution, but it also exhibits a typical ligand-to-metal charge transfer for favorable charge separation. The photocatalytic H2 evolution rates on the as-obtained Bi-TBAPy with different cocatalysts modified were examined with triethanolamine as the sacrificial reagent. Based on this, the hydrogen evolution rate of 140 μmol h-1 g-1 was obtained on the optimized sample with a loading of 2 wt% Pt as a cocatalyst. To the best of our knowledge, this is the first bismuth-based metal-organic framework(MOF) that functions as an effective photocatalyst for photocatalytic water reduction. Our study not only adds a new member to the family of photocatalyst materials, but also reveals the importance of cocatalyst modification in improving photocatalytic activity of MOFs.

Trace Metals in Water Samples Taken from Azerbaijan Sector of Caspian Sea

The present study was conducted to investigate the heavy metal contents （As, Ba, Cd, Co, Cr, Cu, Ga, Mo, Mn, Rb, Pb, Cu, Ni, V, U and Zn） in seawater samples, which were collected at two c （5 and 100 m）, from 9 different sites of Azerbaijan sector of the Caspian Sea. The Agitent 7700x Series ICP-MS （inductively coupled plasma mass spectrometry） with HMI （high matrix introduction） system applied to analysis seawater. It was shown, the average concentrations of elements as Cr, Co, Cu, Mn, Pb and Zn in surface water slightly higher than their concentrations in depth water at 100 m. Practically it is not deference of the Mo, Rb and U average concentrations in surface and 100 m depth column water. There was little variation observed for nickel and vanadium. In contrast the concentrations of As, Ga and Ba in samples taken from 100 m, were significantly higher than the concentration in surface samples. Dependence concentration of elements from water columns depth can be explained in accordance with the geochemical system of classification of dissolved forms of elements in the sea water.

Alkali metal cation effects on electrocatalytic CO_(2)reduction with iron porphyrins

The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.

Photodetachment of H^- Near a Dielectric Surface

Using the closed orbit theory, the photodetachment cross section of H- near a dielectric surface has been derived and calculated. The results show that the dielectric surface has great influence on the photodetachment process of negative ion near the ionization threshold. Above the ionization threshold, the photodetachment cross section starts to oscillate. With the increase of the energy, the oscillating amplitude decreases and the oscillating frequency increases. The oscillation in the photodetachment cross section of H- in the presence of a dielectric surface is either larger or smaller than the photodetachment of H- without the surface. As the photon energy is larger than the critical value Epc, the oscillatory structure disappeared and the cross section approaches to the case of the photodetachment of H- without any external fields. For a given detached-electron energy, the photodetachment cross section becomes decreased with the increase of the ion-surface distance. Besides, the dielectric constant has great influence on the photodetachment of H-. With the increase of the dielectric constant, the oscillation in the cross section becomes increased. As the dielectric constant increases to infinity, the cross section is the same as the photodetachment of H- near a metal surface. This study provides a new understanding on the photodetachment process of H- in the presence of a dielectric surface.

The effect of transition metal ions (M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.

Synthesis and physico-chemical properties of new green electrolyte 1-butyl-3-methylimidazolium perchlorate

1-butyl-3-methylimidazolium perchlorate([BMIM]ClO4) was synthesized by two steps with N-methylimidazolium.Some physico-chemical properties,such as density,surface tension,viscosity,electrical conductivity as well as electrochemical window,were investigated and solvent performance was also studied.The results show that this kind of ionic liquid is an excellent electrolyte with low viscosity,high electrical conductivity and wide electrochemical window.In addition,[BMIM]ClO4 is soluble in most conventional solvents and some metal oxides have high solubility in it,which lays the foundation of direct electrolysis of metal oxides in this ionic liquid.

Highly Dispersed Pt Species with Excellent Stability and Catalytic Performance by Reducing a Perovskite-Type Oxide Precursor for CO Oxidation

A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 （x = 0.03, 0.05, 0.07, 0.09, and 0.10） were prepared through a simple method of citrate acid complexa-tion combined with impregnation. In a nanocrystallite of LaCOl-xPtxO3, ions of lanthanum, cobalt, and platinum are evenly mixed at the atomic level and confined within the nanocrystallite. In the reduction process, platinum ions were reduced and migrated onto the surface of the nanocrystallite, and the platinum should be highly dispersed owing to the even mixing of the platinum ions in the precursor. When x = 0.05 or lower, the highest dispersion of Pt could be achieved. The highly dispersed Pt is stable, because of the strong interaction between Pt atoms and the support. The catalysts were characterized by BET surface area, temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, CO temperature-programmed desorption, and turnover frequency. Compared with general precious metal Pt catalysts, the LaCo0.95Pt0.05O3/ SiO2 catalyst exhibited better activity for CO oxidation, and it maintained stability at a high temperature of 400 ℃ for 250 h with complete CO conversion.

Recovering metals from printed circuit board scrap by a mechanical separation process

A mechanical separation process was developed for recovering metals from printed circuit board(PCB) scrap;it included three steps:impact crushing,sieving and fluidization separation.The mechanism of the technique was based on the difference in the crushabilities of metallic and nonmetallic materials in the PCBs that led to the concentrated distribution of metals in particles of larger sizes and nonmetals mostly in particles of smaller sizes.It was found that crushed PCB particles from 0.125 mm to 1.000 mm contained about 80% of metals in the PCBs.Metals acquired satisfactory liberation in particles smaller than 0.800 mm.The crushed PCB particles were sieved into fractions of different size ranges.Each fraction separately went through a gas-solid fluidized bed operating at a selected optimal gas velocity for the specific size range.Approximately 95% of metals in printed circuit board particles from 0.125 mm to 0.800 mm was recovered by the gas-fluidized bed separator at the selected optimal gas velocity.However,separation of metals from particles smaller than 0.125 mm was not satisfactory.Further study is needed on metal recovery from fine particles.

Electric Conductivity Study of o-Substituted Phenoxo Iron （Ⅲ） Complexes

The coordination nature of a number of substituted sodiumphenoxides to iron （Ⅲ） ion has been studied. The o-nitrosodiumphenoxide was found to have different coordination behaviour from that the sodium salts of salicylic acid and methylsalicylate showed. The structure of the complexes, the number of the ligands being coordinated to the metal ion, has also been determined by titration, uv-vis spectroscopy, atomic absorption and the flame test. In addition, other sodium phenoxides were also involved in this study for comparison. An electric conductivity study on the resulting complexes was carried out and all complexes were found to be semiconductors.

Hydrogen ion beam assisted preparation of metal halide electrodes for batteries

A new method of preparing thin film metal-hydride electrodes for metal-hydride batteries is described. The method consists of simultaneous deposition of multi-component metallic species onto a substrate while bombarding the growing, deposited thin film electrode with a low energy hydrogen ion beam An amorphous LaNi4 hydride thin film electrode has been prepared by this Hydrogen Ion Beam Assisted Deposition （HIBAD） technique. The electrochemical discharge capacity and cycle life of this electrode in a 6 M KOH solution surpass previously reported values for La-Ni thin film electrodes prepared by other deposition methods.

Synthesis of Porphyrin-Appended Pyridine as a Fluorescent Chemosensor for Cd（Ⅱ） and Hg（Ⅱ）

In this research, specific molecular sensors are classified according to the type of receptor-cation interaction, that is ligand-metal interactions. Receptors are based on a multidentate protoporphyrin-appended pyridine platform, which leaves at least a vacant coordination site for the incoming metal ions. A protoporphyrin-appended pyridine, 2,5-pyridine dicarboxyamidyl-8,13-bis（vinyl）-3,7,18,17-tetramethyl-21 H, 23 H-porphyrin（P-PTP）, was designed and synthesized. Its application as potential fluoroionophore for recognition of cadmium and mercury ions is reported. P-PTP shows chelation-enhanced fluorescence effect with Cd（Ⅱ） and Hg（Ⅱ） via the interruption of photoinduced electron transfer （PET） process, which has been utilized as the basis of the fabrication of the metal ions-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd（Ⅱ）- and Hg（Ⅱ）- sensitive chemosensors were investigated. It shows a linear response toward Cd（Ⅱ） and Hg（Ⅱ） in the concentration range of 1.0×10-3 to 1.0×10-7 M with a limit of detection of 1.0×10-7 M and 0.5×10-7M for Cd（Ⅱ） and Hg（Ⅱ）, respectively. The chemosensor shows good selectivity for Cd（Ⅱ） over a large number of other transition metal ions, i.e., Cu（Ⅱ）, Zn（Ⅱ） and mixed metal ions.

Synthesis, characterization and electrochemical recognition of metal ions of three new ferrocenyl derivatives containing pyridyl moiety

Three new ferrocene （Fc） based receptors with pyridyl moiety, named methyl-6- ferrocenoylacetyl-2-pyridine carboxylate （FcLl）, 1,1＇-（2,6-bispyridyl）bis-3-ferrocenyl-l,3-propanedione （FcL2）, ferrocenecarboxaldehyde-2,6-dipicolinoyhydrazone （FcL3） were synthesized, and further characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H and 13C NMR. The electrochemical properties and ion sensing properties of FcL1, FcL2 and FcL3 were also investigated by means of cyclic voltammetry in ethanol solution with 0.1 mol/L LiC104 as the supporting electrolyte. The E~ values of the receptors increase with the scanning rate increasing at high scanning rate, and Ipa/Ipo approaches unity, indicating that the redox reaction is basically reversible. Their recognition performances to different metal cations such as Cd（II）, Co（II）, Cu（II）, Hg（II）, Mn（II）, Ni（II）, Zn（II） show that the FcL1 is responsive to Cu（II） with the maximum electrochemical shift of the FcL1 for Cu（II）of about 72.0 mV, whereas the FcL2 is responsive to Cu（II） and Mn（II） with shift of 102 mV and 109 mV, respectively, and the FcL3 is responsive to Hg（II） and Mn（II） with the shift of 53.0 mV and 54.0 mV, respectively. All the results show that these receptors may have potential applications in electrochemical sensor technology, material science, and molecular devices.

Numerical model and experimental observation for distribution of SiC_p in electromagnetic-centrifugally cast composites

A two-phase numerical model coupled with heat transfer was presented to describe the radial distribution of SiC particles on centrifugally-cast metal matrix composite,and a transverse static magnetic field was concurrently imposed to induce electromagnetic stirring of the melt as it revolved with the mold.Meanwhile,experimental observations were also carried out to examine the radial distribution of SiC particles in pure aluminum.The effects of the imposed magnetic field,particle size and the matrix metals were discussed.The computational results show that the particles tend to be congregated by the centrifugal force,and both increasing the imposed magnetic field and decreasing the particle size tend to result in even distribution of the particles.With the magnetic field varying from 0 to 1 T and the particle size from 550 to 180 μm,a uniform distribution of the particles in the aluminum matrix can be obtained among the computational results.The matrix metal can also influence the particle distributions due to the difference in physical properties of metals.Experimental observation shows similar tendency of particle distributions in aluminum matrix influenced by magnetic field and particle size.However,the chilling effect from the mold wall results in an outer particle-free zone,which is not involved in the numerical model.