三种不同碳桥联双核茂钛配合物的合成及催化乙烯聚合研究

合成了3种不同结构的CnH₂n桥联双核茂钛配合物(CH₃)₂C[(C₅H₄)TiCl₂(C₅H₅)]₂(3),(CH₂)_n[(C₅H₄)TiCl₂(C₅H₅)]₂(6,n=3;7,n=4),并用1HNMR进行了表征.发现以甲苯为溶剂时,不仅提高了产率,而且有效地避免了副产物Cp₂TiCl₂的生成.研究了化合物7/MAO(甲基铝氧烷)催化乙烯聚合的反应,考察了反应条件对催化体系的影响.结果表明,催化活性随着n(Al)/n(Cat.)比的增大而提高,聚乙烯的分子量在n(Al)/n(Cat.)=500和50℃时达到最高值9.0102×10⁴;随着聚合时间的延长,催化活性下降,而产物分子量不断升高;随着温度的上升,50℃时催化活性和聚乙烯的分子量最高,分别为2.4074×10⁵gPE/(molTi·h)和6.8679×10⁴.随着桥联双核茂钛配合物碳桥的增长,催化活性增加,所得聚乙烯的分子量降低.     

碳热还原辅助溶胶-凝胶法制备氟代聚阴离子型嵌/脱锂材料LiVPO4F/C

采用碳热还原辅助溶胶-凝胶法合成了锂二次电池正极材料LiVPO₄F/C, 探讨煅烧温度和煅烧时间对所制备材料纯度、结构和电化学性能的影响. 采用X射线衍射(XRD), 扫描电子显微镜(SEM), 恒流充放电, 电化学阻抗谱(EIS)和循环伏安(CV)等手段对不同煅烧温度和时间所得的材料进行结构表征和电化学性能测试. 当煅烧时间为4 h 时, 温度为450 ℃时, 能够得到纯相LiVPO₄F/C, 在0.1C、0.5C和1.0C倍率下, 电池放电比容量分别为193.2、175.6 和173.7 mAh·g^-1. 随着煅烧温度升高, Li₃V₂(PO₄)₃杂相逐渐增多, 650 ℃煅烧后的材料Li₃V₂(PO₄)₃ 成为主相. 优化煅烧时间也能够有效控制Li₃V₂(PO₄)₃ 杂相的生成, 能得到电化学性能良好的LiVPO₄F/C. 当煅烧温度为550 ℃时, 反应3 h后得到的产物综合电化学性能最优.     

HA/CuO/SrCO3梯度复合涂层的制备及体外生物活性

在羟基磷灰石(HA)悬浮液中, 以正丁醇为分散介质, 三乙醇胺为乳化剂, 成骨微量元素化合物CuO 和SrCO₃作为添加剂, Ti片为基材, 壳聚糖(CS)为造孔剂, 依次通过区带电泳分布并在反向电场作用下电 泳沉积, 得到HA/CS/CuO/SrCO₃复合涂层, 经700 ℃高温煅烧2 h后, 制得HA/CuO/SrCO₃复合涂层. 通过X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 场发射扫描电子显微镜(FESEM)、 能量色散光谱仪(EDS)、 劳埃德万能材料试验机、 电化学工作站、 模拟体液培养和抑菌实验等手段对复合涂层进行测试与表征. 结果表明, Ca, Cu和Sr 元素含量在HA/CuO/SrCO₃复合涂层的径向上均呈现梯度分布; 复合涂层与钛基材的结合强度达33.0 MPa; 循环伏安(CV)曲线和Tafel极化曲线测试表明, 复合涂层在N-2-羟乙基哌嗪-N′-2-乙磺酸(HEPES)模拟体液(H-SBF)中电化学性能稳定, 耐腐蚀性较强; 在H-SBF中培养24 d后, 复合涂层表面完全碳磷灰石化; 抑菌实验发现, 复合涂层粉末对大肠杆菌和金黄色葡萄球菌的抑菌率分别为81.82%和71.86%.     

电化学合成系列锡配合物及纳米SnO2的制备

采用锡金属为"牺牲"阳极,首次在无隔膜电解槽中,电化学一步法制备了纳米SnO₂前驱体锡配合物Sn(OEt)₄, Sn(OBu)₄, Sn(OCH₂CH₂OCH₃)₄, Sn(OEt)₂(acac)₂, Sn(OBu)₂(acac)₂, Sn(OCH₂CH₂OCH₃)₂(acac)₂[acac为乙酰丙酮基],产物通过红外光谱(FT-IR)、拉曼光谱和核磁共振进行表征.同时采用含Sn(OR)₂(acac)₂>的电解液直接水解制备纳米SnO₂粉体,纳米SnO₂通过X射线粉末衍射(XRD)和透射电子显微镜(TEM)进行表征.实验表明,电解时防止阳极钝化,控制温度在40～60℃之间,采用有机胺溴化物为导电盐,可以提高电合成效率;电解合成Sn(OCH2CH₂OCH₃)₄, Sn(OEt)₂(acac)₂, Sn(OBu)₂(acac)₂, Sn(OCH₂CH₂OCH₃)₂(acac)₂的电流效率比Sn(OEt)₄, Sn(OBu)₄高,适宜作为溶胶-凝胶(Sol-gel)法制备纳米SnO₂的原料,制备得到的纳米SnO₂经600℃煅烧后呈球形单分散结构,晶型为四方锡石型,平均粒径在(10±0.4) nm左右.     

Li2SO4-MgSO4及LiNO3-Mg(NO3)2熔盐体系的研究

用目测变温法和差热分析法研究了Li₂SO₄-MgSO₄、LiNO₃-Mg(NO₃)₂熔盐体系。在前一体系中有固液异组成化合物Li₂SO₄·2MgSO₄生成,它在832°熔化分解。化合物与Li₂SO₄间形成低共熔点,温度为647℃,组成含MgSO₄23.6Wt%。Li₂SO₄多晶转变点575℃,在加入MgSO₄后形成类低共熔点,温度552℃,组成含MgSO₄4.2%。LiNO₃-Mg(NO₃)₂为一简单低共熔体系,共晶点含Mg(NO₃)₂47.3%,温度200℃。     

纳米晶(CeO2)1-x(BiO1.5)x固溶体的水热合成与离子输运性质研究

在240℃水热体系中首次合成出系列纳米晶固溶体(CeO₂)_1-x(BiO_1.5)_x(x=0.0～0.50).产物采用X射线衍射,扫描电子显微镜和X射线光电子能谱仪进行表征.Bi₂O₃在CeO₂中的固溶限约为50%.所有固溶体结晶属立方萤石结构,粒度范围为10～18nm.当Bi₂O₃掺杂量小于固溶限时,于800℃烧结不会导致结构转变.而对于(CeO₂)_0.5(BiO_1.5)_0.5,于800℃在空气中烧结将导致固溶限降低.Bi₂O₃含量低于固溶限时,固溶体只具有体电导,而(CeO₂)_0.6(BiO_1.5)_0.4的总电导可分为体电导和晶界电导.体电导为氧离子,而晶界为来自电极的银离子.     

化合物Al2Mo3-xWxO12的合成与结构

合成并表征了一系列化合物Al₂Mo_3-xW_xO₁₂ x=0,0.5,1.0,1.5和2.0的化合物是以单斜晶系Al₂(MoO₄)₃为基质的化合物和固溶体,空间群为P2₁/a;x=2.5和3.0的标题化合物是以正交晶系Al₂(WO₄)₃为基质的固溶体和化合物,空间群为Pbcn.利用粉末X射线衍射图谱全谱拟合的方法精修了x=0,0.5,1.0,1.5,2.0的标题化合物的结构,讨论其相变机理.     

BeSO4-Al2(SO4)3-Na2SO4三元熔盐体系相图的研究

热分析法研究了BeSO₄-Al₂(SO₄)3-Na₂SO₄三元熔盐体系的状态图。体系中存在三元转熔(包晶)点P,温度490℃,组成为BeSO₄18.8Wt%,Al₂(SO₄)₃15.0%,Na₂SO₄66.2%;三元低共熔(共晶)点E₁,温度为476℃,组成为BeSO₄20.0%,Al₂(SO₄)₃11.2,%,Na₂SO₄68.8%。另一低共熔点E₂温度为595℃,组成未能确定。体系中无三元化合物生成。     

Fe3O4/HA复合吸附剂对Ni(Ⅱ)的吸附性能研究

采用碱溶酸析法提取腐植酸(HA),通过CaCl₂对其改性后与Fe₃O₄进行复合,制备出不同配比的Fe₃O₄/HA复合吸附剂。利用SEM、BET、FT-IR、XRD分析方法对HA、钙改性HA、Fe₃O₄/HA复合吸附剂进行了表征,考察了物料配比及吸附时间、pH值、温度、投加量和初始浓度对Ni(Ⅱ)吸附率的影响。结果表明:质量复合比mHA:mFe₃O₄:mCaCl₂为3∶2∶2的Fe₃O₄/HA复合吸附剂(HA2)对Ni(Ⅱ)吸附效果最佳。当加入0.8 g吸附剂,Ni(Ⅱ)初始浓度为0.1 g·L^-1,吸附5 h,pH=5,温度40℃,吸附剂对Ni(Ⅱ)的吸附率为92.57%。复合吸附剂在4次吸附脱附后,对Ni(Ⅱ)的吸附率仍达到52%。吸附过程符合准二级动力学方程和Freundlich吸附等温式。在20℃~40℃条件下,热力学参数ΔG<0、ΔS=37.57 J/(mol·K)、ΔH=11.07 kJ·mol^-1,表明该吸附是自发、熵增、吸热的过程。     

铽激活的镧、钇、钆硫氧化物二元体系的发光性质

为了寻找新的发光体基质材料,本文研究了(Y_1-xLa_x)₂O₂S:Tb、(Y_1-xGd_x)₂O₂S:Tb和(Gd_1-xLa_x)₂O₂S:Tb三个二元稀土硫氧化物固溶体的发光。用稀土氧化物高温硫化法合成了试样。研究了这三个二元体系的发光亮度、发射光谱、发光颜色和余辉时间等发光特性随组成的变化规律。     

羟基磷灰石粉末的水热合成及动力学研究

以CaHPO_4·2H_2O(DCPD)为前驱物,在0.1mol·L~(-1)NaOH溶液中,100～200℃,2～12h条件下水热合成羟基磷灰石(HA)粉末。结果表明:HA晶粒尺寸和结晶程度随反应温度的提高和时间的延长而增大。提高反应温度,有利于晶粒沿c轴方向生长;延长反应时间,有利于晶粒沿a轴方向生长。在120～160℃、2～10h条件下可以得到HA纳米棒。水热合成过程中有缺钙磷灰石(DAP,Ca_(10)～(HPO_4)_x(PO_4)_(6-x)(OH)_(2-x),0≤x≤1)形成,并经历β-TCP→DAP→HA这一转化过程。转化反应为二级反应,活化能为72.91kJ·mol~(-1),推测反应为表面控制反应。     

电化学沉积羟基磷灰石过程晶体生长行为

采用恒电流电化学沉积方法从含钙与磷盐水溶液中直接在纯金属钛电极表面沉积纳米羟基磷灰石涂层,运用EDS、SEM、XRD、FTIR等方法对其进行表征. 重点考察了一种典型制备条件下钙磷沉积层的形貌、结构及组分随沉积时间的变化,进而探讨相应条件下电化学沉积羟基磷灰石涂层晶体生长过程的基本规律. 研究表明电化学沉积法可用于在医用金属表面直接涂覆含钙离子缺陷的纳米羟基磷灰石涂层,典型条件下涂层的生长规律为: (1)沉积过程中羟基磷灰石晶粒以c轴方向沿沉积面法线方向择优生长,且这一趋势延续整个沉积过程; (2)内层晶粒的生长受到外层晶粒生长的抑制, 对于同层的晶粒,当晶粒分布密集时,晶粒生长可能发生相互制约; (3)随沉积时间的延长,沉积量增加,而膜层的化学组成基本不发生变化.     

Colloidal and monocrystalline Ln3+ doped apatite calcium phosphate as biocompatible fluorescent probes

Ultrafine individualised mono crystalline Ca(10-x)(PO4)(6-x)(HPO4)x(OH)(2-x) deficient calcium hydroxyapatite nanocrystals displaying fluorescence under visible excitation are proposed for utilisation as biocompatible biological probes.     

Apparent solubility of hydroxyapatite in aqueous medium and its influence on the morphology of nanocrystallites with precipitation temperature

Two differing wet-chemical synthesis routes, Ca(OH)2 + H3PO4 and CaCl2 + Na3PO4/NaOH, were used to prepare hydroxyapatite (HA) at various temperatures ranging from 30 to 95 degrees C. The electrical conductivity of the solution was measured at regular intervals of time during H3PO4 and Na3PO4 addition to the suspension/solution containing Ca2+ ions. The rate of change of conductivity is used to note the end point of the reaction. X-ray diffraction of the dried, precipitated particles revealed HA as the predominant phase, and the FTIR spectroscopy studies indicated the presence of CO3(2-) groups which substituted PO4(3-) groups in the HA lattice (B-type). FESEM observations revealed that the aspect ratio of the particles decreased with increasing precipitation reaction temperature in one system [Ca(OH)2 + H3PO4] and in the other system it increased with increasing temperature. The changes in the morphology with temperature were analyzed through conductivity measurements and the thermochemical properties of the reaction systems. Conductivity measurements showed that the concentration of dissolved ions at the end point of the reaction between Ca(OH)2 and H3PO4 increased, indicating an increased apparent solubility of HA with increasing temperature, whereas the end-point conductivity did not increase noticeably in the other reaction system.     

两步电化学沉积技术制备功能陶瓷/金属复合镀层

通过两步电化学沉积技术,在医用金属表面得到羟基磷灰石生物活性陶瓷/金属复合镀层.从含有硝酸钙和磷酸二氢氨的溶液中,首先通过恒流模式电化学沉积钙磷生物陶瓷;然后采用恒压模式,在多孔的生物陶瓷沉积层中嵌入金属骨架,从而得到具有良好结合力的羟基磷灰石/金属复合镀层.实验结果表明在复合镀层中作为骨架的金属镍含量约为31%时,复合镀层与基底合金之间的结合力达到21.2MPa.     

Solid-state synthesis of monazite-type compounds containing tetravalent elements

On the basis of optimized grinding/heating cycles developed for several phosphate-based ceramics, the preparation of brabantite and then monazite/brabantite solid solutions loaded with tetravalent thorium, uranium, and cerium (as a plutonium surrogate) was examined versus the heating temperature. The chemical reactions and transformations occurring when heating the initial mixtures of AnO2/CeO2, CaHPO(4).2H2O (or CaO), and NH4H2PO4 were identified through X-ray diffraction (XRD) and thermogravimetric/differential thermal analysis experiments. The incorporation of thorium, which presents only one stabilized oxidation state, occurs at 1100 degrees C. At this temperature, all the thorium-brabantite samples appear to be pure and single phase as suggested by XRD, electron probe microanalyses, and micro-Raman spectroscopy. By the same method, tetravalent uranium can be also stabilized in uranium-brabantite, i.e., Ca0.5U0.5PO4, after heating at 1200 degrees C. Both brabantites, Ca0.5Th0.5PO4 and Ca0.5U0.5PO4, begin to decompose when increasing the temperature to 1400 and 1300 degrees C, respectively, leading to a mixture of CaO and AnO2 by the volatilization of P4O10. In contrast to the cases of thorium and uranium, cerium(IV) is not stabilized during the heating treatment at high temperature. Indeed, the formation of Ca0.5Ce0.5PO4 appears impossible, due to the partial reduction of cerium(IV) into cerium(III) above 840 degrees C. Consequently, the systems always appear polyphase, with compositions of CeIII1-2xCeIVxCaxPO4 and Ca2P2O7. The same conclusion can be also given when discussing the incorporation of cerium(IV) into La1-2xCeIIIx-yCeIVyCay(PO4)1-x+y. This incomplete incorporation of cerium(IV) confirms the results obtained when trying to stabilize tetravalent plutonium in Ca0.5PuIV0.5PO4 samples.     

Supercapacitor Performance of Hollow Carbon Spheres by Direct Pyrolysis of Melamine-formaldehyde Resin Spheres

The nitrogen and oxygen co-doped hollow carbon spheres(HCSs) were prepared via a simple pyrolysis of solid melamine-formaldhyde resin spheres. The carbonization temperature has an important influence on the specific surface area, pore-size distribution and heteroatom contents of HCSs. The synergistic effects of those physical and chemical properties on supercapacitor performance were systematically investigated. Among the HCSs obtained at different temperatures, HCSs-800(co-doped HCSs at 800 ℃) exhibits the best reversible specific capacitance in 2 mol/L H₂SO₄ electrolyte and meanwhile maintains a high-class capacitance retention capability. The nitrogen heteroatoms were confirmed to play a crucial role in improving capacitance in an acid medium. This kind of nitrogen doped HCSs is a potential candidate for an efficient electrode material for supercapacitors.     

Electrophoretic separations of twelve phenothiazines and N-demethyl derivatives by using capillary zone electrophoresis and micellar electrokinetic chromatography with non ionic surfactant

We focused our work on the separation of phenothiazines that are important drugs used for the treatment of psychic diseases. For a better understanding of the metabolism of these solutes, we wanted to separate not only a mixture of 12 phenothiazines but also a mixture containing phenothiazines and their N-demethyl metabolites by capillary electrophoresis. Separations in capillary zone electrophoresis were performed using 3 x 10(-2) mol/L H3PO4 (pH 2.5) but the obtained resolutions were not entirely satisfactory especially with regard to phenothiazine -N-demethyl derivative pairs. To improve the obtained results, we have performed separations by using micellar electrokinetic chromatography. In this approach, we used a running electrolyte containing 3 x 10(-2) mol/L H3PO4 electrolyte (pH 2.5) and octaethylene glycol monododecyl ether (C12E8) as neutral surfactant. By introducing 2 x 10(-3) mol/L C12E8 in the electrolyte, 11 out of 12 phenothiazines have been baseline separated. With respect to the separation of a mixture containing 3 phenothiazines and their 3 demethyl derivatives, we obtained an excellent separation by using a running electrolyte prepared with 7.5 x 10(-4) mol/L C12E8 and 3 x 10(-2) mol/L H3PO4.     

钛基多孔HA/SiO2复合涂层的制备及性能研究

为了制得表面多孔且与基材结合强度高的羟基磷灰石(HA)涂层,实验中以正丁醇为分散介质,以SiO2粉末为添加剂,纯钛片为基材,电泳沉积制备羟基磷灰石/二氧化硅/壳聚糖/(HA/SiO2/CS)复合涂层,经后续热处理得到多孔HA/SiO2复合涂层,采用扫描电镜(SEM)、傅立叶红外光谱仪(FT-IR)、X射线衍射仪(XRD)、万能材料试验机对涂层的表面形貌、组成、结构和结合强度进行测试和表征,并通过模拟体液(SBF)浸泡法对复合涂层的生物活性进行评价.结果表明:当悬浮液中的HA/SiO2/CS质量比为1∶1∶1时,制得的HA/SiO2/CS涂层经700℃热处理后获得的HA/SiO2复合涂层孔洞分布均匀,大孔孔径在10～15μm,小孔孔径在1～5μm;涂层与基材的结合强度达到25.5 MPa;多孔HA/SiO2复合涂层在SBF中浸泡7 d后,涂层表面碳磷灰石化;说明实验中添加SiO2所制得的多孔HA/SiO2复合涂层与钛基材结合强度高,且具有良好的生物活性.     

Theoretical and experimental studies of substitution of cadmium into hydroxyapatite

Substitution of cadmium into bulk hydroxyapatite Ca((10-x))Cd(x)(PO(4))(6)(OH)(2) (CdHA: x = 0.12, 1.3, 2.5) is studied by combining X-ray diffraction data from synchrotron radiation, Fourier transform infra-red spectroscopy (FTIR) and density functional theory (DFT) calculations. Energetic and electronic analyses are carried out for several configurations of Cd substitution for Ca at both cationic sites. Rietveld analysis shows preferential occupation of the Ca2 site by cadmium. FTIR data suggest a non-negligible covalent character of Cd-OH. The much-discussed cation site preference for substitution is determined on the basis of relaxed-lattice energetics, and interpreted in terms of chemical concepts; theory indicates that the Ca2 site is clearly favored and this preference is related to the more covalent character of this site compared to that of site 1.