碳酸肼对乏燃料后处理模拟污溶剂中磷酸二丁酯和Zr(Ⅳ)的洗涤行为研究

碳酸肼作为碱性无盐试剂对钚铀氧化还原萃取(PUREX)流程的污溶剂的洗涤有广泛的应用前景。本文使用碳酸肼溶液对30%磷酸三丁酯-正十二烷有机溶液中的磷酸二丁酯和Zr(IV)进行洗涤,利用单一变量原则,考察了振荡时间、温度、水相与有机相体积比、碳酸肼质量分数以及磷酸二丁酯质量浓度等因素对去除有机溶液中磷酸二丁酯和Zr(IV)的影响。结果表明:在25℃下振荡洗涤15 min,5%碳酸肼洗涤3次同体积的有机溶液后对0.1 g/L和0.5 g/L的磷酸二丁酯的去除率分别约为98.7%和88.1%。此外,磷酸二丁酯的存在可以促进有机相对Zr(IV)的萃取和保留,当磷酸二丁酯的质量浓度为0时,碳酸肼对Zr(IV)的去除率为98.5%。

复杂多组元Cu-Cr-Zr-Ni-Si-Co-Zn合金时效析出动力学研究

Cu-Cr-Zr及Cu-Ni-Si合金均为性能优异的引线框架材料,但二者性能均存在局限性。Cu-Cr-Zr合金具有优异的导电性能,但其强度偏低;Cu-Ni-Si合金具有极高的强度,但其导电性能一般。如果结合二者的优点,并通过后续工艺对其组织进行调控,则是制备高强高导铜合金的一条新路径。实验通过真空感应熔炼的方法制备了复杂多组元Cu-0.746Cr-0.217Zr-0.605Ni-0.109Si-0.177Co-0.085Zn(质量分数)合金,对其进行了不同工艺条件的固溶处理,并研究了不同固溶工艺条件下,合金时效过程中电导率及硬度的演化规律。结果表明:合金经1010℃×1.5 h固溶处理后,时效过程在500℃×3 h时,可获得较优异的综合性能,此时合金的硬度为HV 142.83,电导率为60.00%IACS。此外,根据Avrami经验方程描述了合金的时效析出过程,发现不同固溶工艺的合金在时效过程中,析出速率均随时效温度的提高而提高。

CRYSTAL STRUCTURE OF FIVE-COORDINATE ZIRCONOCENE COMPLEX CP_2ZrCl(S_2CNBz_2) (Bz=C_6H_5CH_2)

Cp;ZrCl（S;CNBz;） is a five-coordinate bent zirconocene in which the dibenzyldithiocarbamate is a bidentate ligand (Zr-Cl 2.549（1）A; Zr-C 2.489-2.533; Zr-S 2.667（1）, 2.734（1）; Zr-Cl-S1 137.6（1）;; Zr-Cl-S2 73.3（1）;).

皮胶原纤维固载Zr(IV)对水体中苯羧酸的吸附特性

制备皮胶原纤维固载Zr(IV)吸附剂(ZLCF),并考察ZLCF对水体中苯甲酸(BA)、邻苯二甲酸(o-PA)、对苯二甲酸(p-PA)和间苯二甲酸(m-PA)的吸附特性。研究表明:这4种苯羧酸的吸附平衡同时符合Langmuir和Freundlich方程,但随着它们的羧基数量和位置的不同,其吸附容量也随之变化。总体看,ZLCF对所研究的苯羧酸均具有较大的吸附容量。当苯羧酸溶液(10ml)的初始浓度为6mmol/L、吸附温度为293K时,ZLCF(0.05g)对BA、o-PA、m-PA和p-PA的吸附容量分别达0.4616、0.5892、0.4912和0.3138mmol/g。吸附动力学研究表明:BA的吸附符合拟一级速率方程,边界层扩散为主控步骤;而o-PA、m-PA和p-PA的吸附符合拟二级速率方程,化学吸附为主控步骤。

L-吡咯烷功能化Zr(IV)金属有机骨架配合物的合成和催化不对称Aldol反应研究

设计合成了L-脯氨甲胺三联苯-4,4’-二甲酸配体(H2L)及其Zr(IV)-金属有机骨架配合物Zr6O4(OH)4(L)6(I),并研究了配合物I催化对硝基苯甲醛和环己酮的不对称羟醛缩合反应,催化反应具有适中的产率(60%)和较低的对映选择性(1.5%),催化产物的dr值为26∶74(anti/syn),以顺式异构体为主.

活化柠檬酸结合Zr(Ⅳ)改善胶原蛋白膜性能的研究

为提高胶原膜的机械性能,分别以活化柠檬酸、硫酸锆和复合改性法交联胶原膜,测定胶原膜的表面粗糙度、抗张强度和断裂伸长率等指标变化情况。结果表明,复合改性明显降低胶原蛋白膜的表面粗糙度,使薄膜表面光滑;干态拉伸强度和断裂伸长率分别提高46.40%和52.05%,湿态拉伸强度提高373.63%,水蒸气透过系数降低23.65%,明显优于单一改性方法。复合改性的胶原蛋白膜机械性能优越,有利于实际应用,在食品包装领域具有潜在应用价值。

Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes

A new complexes of Cp2Ti[S2P(OR)2]2 (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp2Ti[S2POGO]2 (where G = -CH2CMe2CH2-, -CH2CEt2CH2- and -CMe2CMe2-) were prepared by the dropwise addition of the appropriate O,O’-dialkyl or -alkylenedithiophosphoric acid to biscyclopentadienyl titanium dichloride in 1:2 molar ratio and refluxed in benzene solution. These novel deep red colored complexes were characterized by elemental analyses, molecular weight measurements and spectroscopic techniques (IR., NMR 1H, 13C and 31P NMR). These titanium (IV) dithio complexes have also been screened for their antibacterial activities.

Efficient preparation of Zr(Ⅳ)-salen grafted mesoporous MCM-41catalyst for chemoselective oxidation of sulfides to sulfoxides and Knoevenagel condensation reactions

Zr（IV）-salen-MCM-41 was prepared by reaction of NH2-MCM-41 with salicylaldehyde to afford Schiff base ligands. Thereafter, ZrOCh.SH2O was reacted with the Schiff base ligands for complex formation. The structural properties of the synthesized materials were investigated by a number of analytical techniques including X-ray diffraction, N2 sorption-desorption, thermogravimetric analysis, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscpopy, and energy dispersive X-ray spectroscopy. Catalytic studies of the mesoporous materials functionalized with Zr（IV）-Schiff base complexes were investigated and extended to selective oxida- tion of sulfides to sulfoxides and the Knoevenagel condensation reactions of aldehydes with malo- nonitriles and ethyl cyanoacetate. Additionally, catalyst recycling of the Zr-salen-MCM-41 materials was also studied.

Synthesis, spectral characterization and biological activities of Organotin(IV) complexes with <i>ortho</i>-vanillin-2-hydrazinopyridine (VHP)

Five new organotin(IV) complexes of ortho-vanillin-2-hydrazinopyridine hydrazone with formula [RnSnCl4–n(VHP)] [R = Me2, n = 2 (2);R = Ph2, n = 2 (3);R= nBu2, n = 2 (4);R = nBu, n = 2 (5) and R = 1, n = 0 (6)] have been synthesized by direct reaction of ortho-vanillin-2-hydrazinopyridine hydrazone [(VHP), (1)], base and organotin(IV) chloride(s) in absolute methanol. The hydrazone ligand [(VHP), (1)] and its organotin(IV) complexes (2-6) have been characterized by UV-Visible, FT-IR and 1H NMR spectral studies. Spectroscopic data suggested that in the complexes (2-4), the ligand (1) acted as a neutral bidentate ligand and is coordinated to the tin(IV) atom via the azomethine nitrogen and pyridyl nitrogen atoms, whereas the ligand (1) acted as a uninegative tridentate ligand and coordinated to the tin(IV) atom through phenolic-O, azomethine-N and pyridyl-N atoms in complexes (5-6). The toxicity of the ligand (1) and its organotin (IV) complexes (2-6) were determined against Artemia salina. Organotin(IV) complexes showed moderate activity against Artemia salina. The ligand (1) and its organotin(IV) complexes (2-6) were also tested against four types of bacteria namely Bacillus cereus, Staphylococcus aureus, Escherichia coli and Enterobacter aerogenes. All organotin(IV) complexes and the free ligand (1) showed better antibacterial activities against bacteria. Among the organotin(IV) complexes (2-6), diphenyltin(IV) complex (3) showed higher activity against the four types of bacteria.

Synthesis, spectral, 3D molecular modeling and antibacterial studies of dibutyltin (IV) Schiff base complexes derived from substituted isatin and amino acids

New dibutyltin(IV) complexes of Schiff base derived from 5-chloroindoline-2,3-dione, indoline- 2,3-dione with amino acids (tryptophan, alanine and valine) were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, and biological activity. The analytical data showed that the Schiff base ligand acts as bidentate towards metal ions via the azomethine nitrogen and carboxylate oxygen by a stoichiometric reaction of M:L (1:2) to form metal complexes. NMR (1H, 13C and 119Sn) spectral data of the ligands and metal complex agree with proposed structures. The conductivity values between 14 - 27 ohm-1cm2mol-1 in DMF imply the presence of non-electrolyte species. 3D molecular modeling and analysis of bond lengths and bond angles have also been conducted for a representative compound, [Bu2Sn(L2)2], to substantiate the proposed structures. Antibacterial results indicate that the metal complexes are more active than the free ligands.

Adsorption and reduction of platinum(Ⅳ) chloride complex ions on activated carbon

The adsorption kinetics of platinum（IV） chloride complex ions on the activated carbon Norit GF40 was investigated. Experiments were carried out at different initial concentrations of Pt（IV） chloride complex ions, temperature, rate of mixing and pH. It was found that the value of activation energy of the studied process is equal to 19.7 kJ/mol. From the ICP MS analysis it was confirmed that platinum ions （Pt（IV） and Pt（II）） are removed from the solution due to the adsorption and are further reduced to the metallic state. Such mechanism was confirmed by XPS analysis which showed that on the carbon surface three forms of platinum species, i.e. Pt（0）, Pt（II） and Pt（IV）, exist. The presence of platinum in the solution at different oxidation states was also confirmed spectrophotometrically by identification of their characteristic absorption bands. The metallic form of Pt present on the surface of activated carbon was observed in the form of small spherical islands with the diameter not exceeding 500 nm. Those islands consist of smaller, flake-shape particles with a thickness of about 35 nm.

Spectrophotometric Investigation of Complex Formation of Ge（IV） with Bis（2,3,4-Trigidroksifenilazo） Benzidine in the Presence of Cationic Surfactants Active Substances

It is investigated the interaction of Ge（IV） with bis（2,3,4-trigodroksifenolazo） benzidine （R） in the presence of KSAS （cationic surface active substances）-CPCl （cetylpyridinium chloride）, CPBr （cetylpyridinium bromide） and CTMABr （cetyltrimethylammonium bromide）. It is studied the effect pH, time on the formation of ternary complexes. It is determinated of molar absorption coefficients and stability constants of germanium. Binary （Ge-R） and triple （Ge-R-CPCI, Ge-R-CPBr, Ge-R-CTMaBr） complex form at pH 4 and pH 1, respectively. The composition proportion of binar system is 1：2 and the composition proportion triple complex is 1：1：2. The concentration interval of germanium which obeying beer low in the Ge-R 0.12-2.92 mkq/mL, in the Ge-R-CPCI is 0.04-1.46 mkq/mL, in the Ge-R-CPBr is 0.00-1.00 mkq/mL and in the Ge-R-CTMaBr is 0.00-1.00 mkq/mL. Molar absorbtivities of complexes are 45,000, 57,000, 59,000 and 60,000, respectively. The effect of interfering ions and masking agents has been learned. Stability constants of complexes have been determined： lgKl = 7.21 ＋ 0.06 （Ge-R）,＇ lgK1 = 12.08 _＋ 0.05 （Ge-R-CPCI）, lgK1 = 12.12 ＋ 0.07 （Ge-R-CPBr） and lgK1 = 12.85 ＋ 0.06 （Ge-R-CTMaBr）. It is developed highly selective method of photometric determination of trace amounts of Ge（IV） in petroleum coke.

New Square-Pyramidal Oxovanadium (IV) Complexes Derived from Polydentate Ligand (L1)

New series of oxovanadium (IV) complexes isolated from 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (L1) are incorporated and portrayed using spectroscopic (IR, UV-Vis, ESR, mass spectrometric), magnetic moment, thermal and cyclic voltammetry measurements. The results demonstrate that L1 acts in various styles of chelation with [V3O3(L1)(SO4)3(EtOH)1/2(H2O)3/2] 1), [VO(L1)(2,4-pentadionate)]·Cl·4HCl 2), [V2O2(L1)(SO4)2(EtOH)5/2] 3), [V2O2(L1)(SO4)2(EtOH)3/2(H2O)1/2] 4), [VO(L1)SO4 (H2O)3/2]·2.5H2O 5) and [V2O2(L1)(SO4)2(H2O)]·H2O 6). The values of magnetic moments and spectral studies suggest a square-pyramidal geometry around the V (IV) ion for all complexes. The molar conductance values suggest that the complexes are non-electrolyte, except the [VO(L1) (2,4-pentadionate)] Cl·4HCl. Molecular modeling calculates the bond length, bond angle, chemical reactivity, energy components (Kcal/mol) and binding energy (Kcal/mol) for the isolated complexes. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria prove them as growth inhibiting agents. Antitumor activity is carried out in vitro on human mammary gland (breast) MCF-7 and cervical cancer cell-HeLa has shown that [VO(L1)SO4(H2O)3/2]·2.5 H2O and [VO(L1)(2,4-pentadionate)] Cl·4HCl complexes display the highest powerful activity between all of the investigated complexes.

Study on the Tin （IV） Complex of 4,5-benzo-1,2-dithiole-3-thione with IR, Analysis Centesimal, and Theatrically

A tin （IV） complex with 4,5-benzo-1,2-dithiol-3-thione （C7H4S3） （A）, [SnCI4 （C7H4S3）2] （B） was synthesized. The structure of the obtained complex （B） was characterized by Infrared Spectroscopy （IR）, analysis centesimal composition, and theoretical study. The complex （B） has an octahedral structure, where a tin in the center takes an octahedral geometry and is coordinated by four atoms of chlorine and two thiocarbonyl sulfur atom （C=S） of the ligand.

CRYSTAL STRUCTURE OF SEVEN-COORDINATE ZIRCONOCENE COMPLEX (CH_3C_5H_4) Zr(S_2CNBz_2)_3 (Bz=CH_2C_6H_5)

(CH_3C_5H_4)Zr(S_2CNBz_2)_3, Mr=987.55, space group P1, a=13.002(4), b=13.659(3), c=29.685(8); α=100.72(2)~o,β=97.23(2)~o, γ=105.36(2)~o; V=4909(2)~3, Z=4, Dc=1.34gcm^(-3), Mo-K(λ=0.71073A) radiation, μ=5.0cm^(-1), R=0.069, Rw=0.078 for 6100 reflections. The title complex has pentagonal bipyramid configuration in which the zirconium atom is coordinated by one CH_3C_5H_4 group and three bidentate dibenzyldithiocarbamate ligands.

Se(IV)在北山花岗岩上的吸附

采用批式法研究了粉碎的甘肃北山花岗岩样品(BS03, 600 m)对Se(IV)的吸附作用. 实验结果表明: 在pH 3-7范围内, Se(IV)的吸附分配比(Kd)基本不随pH变化; 当pH > 7时, Se(IV)在北山花岗岩上的Kd随pH的增大而减小. Se(IV)在北山花岗岩上的吸附不随离子强度变化. 北山地下水条件下的Ca2+(4.10×10-3 mo·lL-1)和SO42- (3.17×10-3 mo·lL-1)对Se(IV)的吸附没有影响. 此外, Se(IV)/Eu(III)/北山花岗岩三元吸附体系的实验结果表明, Se(IV) (1.46×10-5 mo·lL-1)和Eu(III) (3.33×10-6 mo·lL-1)在北山花岗岩上的吸附作用相互之间没有表观影响. 通过假定HSeO3-在广义的吸附位点≡SOH上发生了生成≡SHSeO3和≡SSeO3-的两个表面配位反应, 定量解释了Se(IV)的吸附实验结果.

壳聚糖-Zr(Ⅳ)配合物的制备及催化氧化降解的研究

对壳聚糖进行液态均相配合反应制得壳聚糖-Zr(Ⅳ)配合物,通过AMF,IR,XRD及XPS等检测证实了壳聚糖与锆离子之间配位键的存在,且显示壳聚糖在形成配位结构后存在有利于降解的优势构象。以H2O2对壳聚糖-Zr(Ⅳ)配合物及壳聚糖进行氧化降解,探讨相同条件下粘度的变化及降解产物的分子量分布。结果表明,壳聚糖-Zr(Ⅳ)配合物的降解速度明显高于壳聚糖,降解产物分子量分布较壳聚糖直接降解窄,进一步证明壳聚糖-Zr(Ⅳ)配合物中存在有利于降解的优势结构。

Zr掺杂K2La2Ti3O10制备及光催化性能研究

以钛酸四丁酯、碳酸钾、硝酸镧、氧氯化锆为原料,采用聚合-络合法制备出了新型的Zr掺杂改性的纳米复合物K2La2Ti3-xZrxO10,通过X射线衍射(XRD)、紫外可见漫反射(DRS)、比表面(BET)以及光致发光(PL)测试对其晶体结构和光学性质进行了表征。以乙醇为电子给体,比较了Zr掺杂量对催化剂光解水活性的影响。结果表明,通过低浓度Zr的掺杂,载Pt后光催化活性得到了大大地提高。Zr掺杂量x=0.2时获得比表面为18.72m2/g的纳米颗粒具有最好的光催化活性,测得其5h内在乙醇溶液中的产氢量子效率为2.69%。

乙异羟肟酸与Zr(Ⅳ),UO_2^(2+)配合物稳定常数的测定

对乙异羟肟酸(AHA)与Zr(Ⅳ),UO22+的配位行为进行了初步研究,测定了AHA与Zr(Ⅳ),UO22+配合物的稳定常数。结果表明,在HCl O4体系中,AHA与Zr(Ⅳ),UO22+分别发生三、二级配位,其稳定常数分别为:β1(Zr(Ⅳ))=(6.7±0.1)×1013,β2(Zr(Ⅳ))=(1.8±0.1)×1025,β3(Zr(Ⅳ))=(3.8±0.3)×1035;β(UO2+)=(8.6±0.4)×107,β(UO2+)=(3.8±0.1)×1014。

大别造山带宿松杂岩中石榴斜长角闪岩变质演化过程、原岩时限及其构造涵义

大别造山带是由扬子板块向华北板块俯冲碰撞而形成的,出露了世界上规模最大的、种类最齐全的各类超高压岩石,全面深刻地记录了大陆深俯冲过程。然而,对于该造山带“浅层”(地壳层次)俯冲折返过程的研究则较少涉及,这制约了对大别造山带形成全过程的整体理解。为此,本次研究以大别造山带最南缘经历绿帘-角闪岩变质的宿松杂岩为研究靶区,针对该杂岩别河地区的石榴斜长角闪岩展开了精细的岩相学、矿物化学、温压评价和年代学研究。研究表明,该岩石记录了三个变质阶段,其中第二阶段可进一步分为a和b两个亚阶段,具体的变质温压条件分别为:①阶段Ⅰ:T=562±12℃、P=1.03±0.05GPa;②阶段Ⅱ-a:T=663±8℃、P=1.09±0.04GPa;③阶段Ⅱ-b:T=508~584℃、P_(-设定)=0.5~0.7GPa;④阶段Ⅲ:T=396~472℃、P_(-设定)=0.1~0.3GPa。其中,①→②表现为近等压增温型式,反映了一个俯冲迟滞过程,暗示了“浅层”俯冲止于莫霍面附近,并受下伏岩石地幔热源供给导致其持续增温,而②→③→④则显示降温降压样式,表现为缓慢抬升的过程。显然,大别造山带“浅”地壳层次的俯冲属于“暖”俯冲类型,并表现为一个缓慢变质演化过程,明显不同于大别造山带“冷”俯冲类型的大陆深俯冲的快速演化过程。锆石U-Pb年代学研究显示,石榴斜长角闪岩的锆石均为具振荡环带结构,测定的37个谐和年龄范围数据范围为1470±80Ma~1258±101Ma,Th/U比值均大于0.4,加权平均年龄为1381±25Ma,该年龄应为其原岩结晶年龄,代表了哥伦比亚超大陆最终裂解时限。此外,侵入于石榴斜长角闪岩中的富石英花岗岩的加权平均年龄为129±5Ma,反映了中国东部中生代伸展事件。结合前人的年龄资料,可以推测1.38~1.30Ga为哥伦比亚超大陆向罗迪尼亚超大陆转换的时间节点。同时,可以明确宿松杂岩则是由不同时代、不同岩石类型构成的单元,是探究扬子板块自新太古代至中生代漫长复杂的演化过程最佳的场所变质单元。