PO-Cu-BDC材料的合成及其对铀的吸附性能研究

以N,N-二甲基甲酰胺、对苯二甲酸和四丁基溴化铵为原料采用电化学法合成Cu-BDC金属有机骨架材料,对其进行氧磷基修饰,得到PO-Cu-BDC材料,将其用于对含铀废水的吸附研究。结果表明:该材料在吸附底液的p H处于5. 0~7. 0间,吸附时间50 min以上时对UO2^2+的吸附率在90%以上;吸附铀饱和后的材料用1. 5 mol/L Na NO3洗脱时,洗脱体积4倍以上,洗脱时间30 min以上时对UO2^2+的洗脱率达95%以上;材料重复吸附三次后对UO2^2+吸附率降为原来的66. 8%,该材料具有一定稳定性,可作吸附剂重复利用。

Incorporation of Reactive Corrosion Inhibitor in Waterborne Acrylic Polyurethane Coatings and Evaluation of its Corrosion Performance

Hydroxyl-epoxy phosphate （HEP） as a reactive corrosion inhibitor was innovatively synthe- sized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite （HEP-APU） coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.

Surface modification of biomedical magnesium alloy wires by micro-arc oxidation

Magnesium alloy wires were processed by micro-arc oxidation （MAO） in a modified silicate-phosphate composite electrolyte containing hydroxyapatite （HA） nanopowders and NaOH. Effects of NaOH content in the composite electrolyte on the microstructure and properties of the MAO ceramic coatings on magnesium alloy wires were studied. It is found that the arc voltage of magnesium alloy wires in the micro-arc oxidation process is significantly reduced while the oxidation rate is accelerated. Addition of 2 g/L NaOH in the composite electrolyte is a better choice for improving corrosion resistance of magnesium alloy wires. During early simulated body fluids （SBF） immersion, the micro-arc oxidized magnesium alloy wires undergo a slow and stable degradation. After soaking for 28 d, the protective ceramic coating still shows no damage but significant degradation is observed for magnesium alloy wires after immersion for more than 60 d.

Reactive Extraction of o-Aminophenol Using Trialkylphosphine Oxide

Extraction of o-aminophenol (OAP) using trialkylphosphine oxide (TRPO) was studied with different diluents. The neutral OAP was extracted using TRPO under an equilibrium pH in the range of 6—7.5, and a maximum distribution coefficient occurred. It was confirmed that the pH value and the TRPO concentration are the key factors that affect dis-tribution coefficient. Nonpolar diluents could provide better extraction distribution coefficient for the extraction of OAP and the order is: kerosene >n-octanol >chloroform.

Effects of phosphate precursors on morphology and oxygen evolution reaction activity of NiFe(oxy)hydroxide on nickel foams

NiFe(oxy)hydroxides nanosheets were synthesized on nickel foams via co-precipitation and electrochemical activation. It is found that the phosphate precursors(Na_(3)PO_(4), Na_(2)HPO_(4)and NaH_(2)PO_(4)) have diverse effects on the morphology and thus the oxygen evolution reaction activity of the formed final catalysts. The resulting NiFe(oxy)hydroxides nanosheets prepared with Na_(2)HPO_(4)demonstrate a low overpotential of 205 m V to achieve a current density of 50 mA/cm^(2) with a Tafel slope down to 30 mV/dec in 1 mol/L KOH, and remain stable for 20 h during stability test.

Mechanical properties of hydroxyapatite-zirconia coatings prepared by magnetron sputtering

Hydroxyapatite （HA）-zirconium （ZrO2） composite coating was produced by magnetic sputtering on Ti6Al4V titanium alloy substrate, the coatings of 50HA-50ZrO2 and 75HA-25ZrO2 （mass fraction, %） were characterized by scanning electron microscopy, energy disperse spectroscopy, X-ray diffraction and scratch test, respectively, and the effects of HA contents in the coating on residual stress were analyzed. The experimental results show that the phases of HA-ZrO2 composite coatings are HA, ZrO2 and Y2O3, and the HA has a certain decomposition in the combination process, producing TCP and CaO impurity phases. The porous surface of coating is conducive to the growth of bone tissue, and the surface roughness values of 50HA-50ZrO2 and 75HA-25ZrO2 are 1.61 μm and 2.92 μm, respectively. The coating interface is of mechanical integration, the bonding strength values of 50HA-50ZrO2 and 75HA-25ZrO2 are 30 N and 17.5 N, respectively, showing a downward trend with the HA contents increasing. The residual stress values in the coating of 50HA-50ZrO2 and 75HA-25ZrO2 are （-399.1±3.0） MPa, （-343.2±20.3） MPa, respectively, as a result, the appropriate increase of HA contents in the coating will reduce its residual stress.

Effect of Diluents on the Extraction of Oxalic Acid by Trialkylphosphine Oxide

In liquid-liquid solvent extraction processes, diluents have a strong influence on the extraction mechanism and efficiency. In this study, benzene, cyclohexane, trichloromethane, carbon tetrachloride, methyl isobutyl ketone (MIBK), butyl acetate, and 1-octanol were used as diluents in the extraction of oxalic acid by trialkylphos-phine oxide (TRPO). The effects of extractant concentration, initial concentration of oxalic acid and diluent type on the extraction equilibrium partition coefficient are analyzed. The sequence of the extraction ability by different diluents is MIBK > butyl acetate > cyclohexane=benzene > carbon tetrachloride > 1-octanol > trichloromethane. Extraction mechanism was analyzed and extraction model parameters were evaluated.

Effect of hydroxyapatite:zirconia volume fraction ratio on mechanical and corrosive properties of Ti-matrix composite scaffolds

Ti-based scaffolds reinforced with zirconia and hydroxyapatite were produced successfully by a hybrid method with an eco-friendliness and low cost to obtain low elastic modulus(E) with sufficient physical, electrochemical and biological properties. The effect of simultaneous modification of the volume fraction of hydroxyapatite(HA) and zirconia(ZrO_(2)) on scaffolds was investigated in terms of mechanical, corrosive, and antibacterial properties. Scanning electron microscopy with attached electron dispersive spectroscopy and X-ray diffraction were used for the characterization of scaffolds. Compression and electrochemical tests were performed to determine mechanical properties with detailed fracture mechanism and in-vitro corrosion susceptibility to simulated body fluid at 37 ℃,respectively. Antibacterial tests were carried out by comparing the inhibition areas of E.coli and S.aureus bacteria. It was observed that the mechanical strength of the scaffolds decreased with increasing HA:ZrO_(2)volume fraction ratio.The lowest E was achieved(6.61 GPa) in 6:4 HA:ZrO_(2)composite scaffolds. Corrosion current density(J_(corr)) values were calculated to be 21, 337, and 504 μ A/cm^(2) for unreinforced Ti, 3:2 and 6:4 HA:ZrO_(2)reinforced scaffolds,respectively. The inhibition capacity of the 6:4 reinforced composite scaffold was found to be more effective against S.aureus bacteria than other scaffolds.

Mathematical model and reaction mechanism of molybdenum and tungsten extraction with TRPO from peroxide solution

To understand the behavior of molybdenum and tungsten extracted by tri-alkyl phosphine oxide(TRPO)from peroxide solution,the extraction mechanism was studied by slope method and Raman and FTIR spectroscopy.The empirical formulas of molybdenum and tungsten extraction distribution ratio(D_(Mo)and D_(W))as functions of equilibrium pH,TRPO concentration and temperature were obtained by establishing mathematical models.Furthermore,the reliability of the empirical formula was verified in the H^(+)-W-Mo-H_(2)O_(2) solution.The results indicate that the calculated values of D_(Mo)or D_(W)were consistent with the experimental values.The apparent extraction equilibrium constants of molybdenum and tungsten wereK_(Mo)^(app)=8.51×10^(3)(0.74≤pH_(e)≤1.7),K_(Mo)^(app)=99.89×10^(3)(1.7<pH_(e)≤4.62)andK_(W)^(app)=2.65×10^(3)(0.92<pH_(e)<2.16)at 20°C,respectively.The main extraction complex of molybdenum or tungsten was[H_(2)(Mo or W)_(2)O_(3)(O_(2))_(4)(H_(2)O)_(2)]·2TRPO.These empirical formulas can be used to analyze and estimate the extraction and separation of Mo and W from low molybdenum and tungsten concentration solutions.

THE EFFECTS OF SHORT CHAIN FATTY ACID ON BIOLOGICAL PHOSPHATE RELEASE AND PHB SYNTHESIS UNDER ANAEROBIC CONDITION

The basic objective of this research is to determine the effects of acetate, propionate and butyrate on the biological phosphate(bio p) release and poly β hydroxybutyrate(PHB) synthesis and to test the effects of different acetate concentrations on the bio p release as well as the effect of butyrate on the bio p release and PHB synthesis in the presence of nitrates. Oxidation reduction potential probes are used to monitor the relative anaerobic and anoxic states of the sewage. The author quantified PHB, PHV in activated sludge by gas liquid chromatography. It has been demonstrated through a series of batch experiments that phosphorus release and PHB synthesis both take place in anaerobic zone of the bio p removal process, and the key factors to the maximization of PHB synthesis are that simple carbon substrates should be added to the anaerobic zone and that the addition of electron acceptors should be avoided.

Synthesis and Crystal Structure of Mixed Mo-W Cubane-type Cluster Compound [Mo_2W_2S_4 (μ-OAc)_2 (dtp)_3(dtpH)]·CH_2Cl_2

The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc and Ac2O solution in the presence of dtp-ligand. Crystallographic data: Mr=1632. 71,monoclinic, space group P2/n, a=13. 146 (8), b=11. 961 (5),c=17. 157 (9) β =105. 99(8)°, V=2593(8), Z=2, Dc=2. 09 /cm￣3 ,λ(MoKa) =0.71073 ,F (000)=1578, final R=0. 029, Rw = 0. 041 for 3765 unique intensity data [I≥4σ (I)]. The result of X-ray study and elemental analysis indicated that, in the crystal lattice, molybdenum and tungsten are statistically distributed in the metal positions each with 0. 5 fractional occupation.

Research on Reactivities of Mo Cluster. A Selective Substitution Reaction of the Bridging (dtp) Ligand and Structure of Tetranuclear Molybdenum Cluster Compound [Mo_4S_4(μ-O_2CC_6H_5)_2(dtp)_4]

The cluster compound [Mo4S4 (μ-O2CC6H5)2(dtp)4] (dtp = S2P (OEt)2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo4S4(μ-dtp)2(dtp)4] in the mixed solvent of acetone, ethanol and water in the presence of C6H5CO2Na. It is monoclinic and crystallizesin space group C2/c, Mr =1495. 09, a=12. 175 (5) , b=22. 01 (1) , c=20.875(9) ,β=99. 04(4)°; V=5570(5) ; Z=4; Dc= 1. 78g/cm3;μ(MoKα) = 14. 52 cm-1; F(000) =2984. Final R factor is 0. 066. The result reveals that the [Mo4S4] cluster core and t-(dtp)1ligands are retained and onlyμ-bridged (dtp)1- ligands are substituted by (C6H5CO2)1in the substitution reaction, thus producing the title cluster compound,the structure of which contains two species of bidentate ligand.

Preparation of a halogen-free P/N/Si flame retardant monomer with reactive siloxy groups and its application in cotton fabrics

A novel halogen-free phosphorus–nitrogen–silicon flame retardant monomer with reactive siloxy groups,N-(diphenylphosphino)-1,1-diphenyl-N-(3-(triethoxysilyl)propyl) phosphinamine(DPTA) has been synthesized and was applied to the fire-resistant finishing of cotton fabrics. The molecular structure of DPTA has been well characterized by elemental analysis, FTIR,1H NMR, and ^(31)P NMR spectroscopies. The chemically-grafted cotton fabrics, which were treated with 25 wt% DPTA, were obtained and confirmed by attenuated total reflectance Fourier infrared spectroscopy(ATR-FTIR). The flame retardancy and thermal property of the treated samples were investigated by limited oxygen index(LOI), vertical flammability test(VFT), thermogravimetric analysis(TGA) and microscale combustion calorimeter(MCC). It is noted that in vertical flammability test, the treated samples extinguished immediately upon removing the ignition source, whereas the untreated one was completely burned out. Furthermore, TGA and MCC tests revealed that the treated samples produced a high char formation and a low heated release during combustion. The surface morphology of the untreated and treated samples and the char residues after LOI tests were observed by scanning electron microscopy(SEM). Therefore, all the results showed that the treated cotton fabrics with 25 wt% DPTA apparently improved the fireresistant and thermal performances.

Ammoxidation of 3-Picoline over V-Mo-P Oxide Catalyst Prepared from 11-Molybdo-l-Vanado Phosphoric Acid

V-Mo-P oxide catalyst system was directly prepared from ll-molybdo-l-vanado phosphoric acid by thermal decomposition. Supported V-Mo-P oxide catalysts were prepared by wet impregnation method. Catalysts were characterized by FTIR （Fourier transform infrared）, XRD （X-ray diffraction） and TPD （temperature programmed desorption）. The catalytic activity of V-Mo-P oxide catalysts were investigated for vapour phase ammoxidation of 3-picoline. The unsupported catalyst showed 92.1% yield where as V-Mo-P oxide/HZSM-5 showed the highest yield （80.4%） amongst the supported catalysts.

Syntheses, Structures and Reactivity of Incomplete Cubane-like Compound[{ W_3S_4} {S_2P(OEt)_2}_4(H_2O)]and Its Derivates

The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the 'loose' ligands are determined. The crystallographic data of the cluster compounds with [W_3S_4]￣(4+) and [W_3CuS_4]￣(5+) cores are compared and their UV-Vis spectra are firstly reported. Thus, the 'quasi-aromaticity' of the [W_3S_4]￣(4+) core of these cluster compounds is discussed.

Zic1 negatively regulates brown adipogenesis in C_3H_(10)T_(1/2) cells

Zinc finger in the cerebellum 1 （Zicl） is known to regulate neurogenesis and myogenesis in the develop- mental stage and widely used as one of the brown adipocyte-specific markers. In this study, we examined the effect of Zicl on brown adipogenesis. Overexpression of Zicl attenuated the lipid accumulation and the expressions of PPAR72 and C/EBPα in C3H10T1/2 mesenchymal stem cells. The mRNA levels of BAT-specific thermogenic genes （PRDM16, PGC-1α and UCP1） and fatty acid oxidation regulatory genes （PPARα, CPT1α, CPT1β and COX7α1） were suppressed in Zicl-overexpressed cells. Moreover, overexpression of Zicl reduced the mitochondrial oxidative phosphorylation （OXPHOS） regulatory proteins including ATP5α, UQCRC2, SDHB and NDUFB5. These results indicate a potential role of Zicl in the regulation of brown adipogenesis via inhibiting adipogenesis, fatty acid oxidation and mitochondrial OXPHOS.

Recoverable Mn~Ⅲ (salen) supported on diamine modified zirconium poly(styrene-isopropenyl phosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

Chiral Mn Ⅲ (salen) (Jacobsen's catalyst) was axially immobilized onto a new type of organic polymer-inorganic hybrid materialzirconium poly(styrene-isopropenyl phosphonate)-phosphate(ZPS-IPPA) with different linkage lengths and evaluated as catalysts for the epoxidation of unfunctionalized olefins. The results demonstrated that the prepared catalysts exhibited moderate to good activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the immobilized catalysts were relatively stable and could be conveniently separated from the reaction system by simple precipitation in hexane. Moreover, higher enantioselectivity was obtained with catalyst 2c than that of homogeneous counterpart catalyzed even after eight times. The excellent recycling of the catalyst was attributed to its structure feature of ZPS-IPPA which is different from either pure polystyrene or pure zirconium phosphates.