聚N-异丙基丙烯酰胺与Eu(Ⅲ)相互作用的研究

利用X射线光电子能谱、红外光谱、紫外光谱和荧光光谱对Eu（Ⅲ）与聚N-异丙基丙烯酰胺（PNIPAM）的相互作用进行了研究。结果表明，Eu-（Ⅲ）和PNIPAM有相互作用：①Eu（Ⅲ）可与PNIPAM中酰胺基团配位形成配合物PNIPAM—Eu（Ⅲ）；②PNIPAM—Eu（Ⅲ）配合物兼具热敏性；③Eu（HI）与PNIPAM之间存在能量传递，当Eu（Ⅲ）含量为0．8w％时荧光强度最大。     

微凝胶-铕-α-噻吩甲酰三氟丙酿三元配合物的合成与表征

合成了聚N-异丙基丙烯酰胺-丙烯酸P（NIPAM-co-AAc）共聚微凝胶与Eu（Ⅲ）离子、α-噻吩甲酰三氟丙酮（HTTA）的三元配合物。用透射电镜、激光光散射、Zeta电位、紫外光谱、红外光谱、荧光光谱进行了表征。结果表明,微凝胶粒径为400nm;Eu（Ⅲ）与微凝胶、HTTA之间以配位作用为主;微凝胶、HTTA和Eu（Ⅲ）之间能进行有效的能量传递。其配合物的最佳激发波长为317nm,在此激发波长下Eu（Ⅲ）有较强的荧光特征发射。     

微凝胶-铕-α-噻吩甲酰三氟丙酮三元配合物的合成与表征

合成了聚N-异丙基丙烯酰胺-丙烯酸P(NlPAM-co-AAc)共聚微凝胶与Eu(Ⅲ)离子、α-噻吩甲酰三氟丙酮(HTTA)的三元配合物.用透射电镜、激光光散射、Zeta电位、紫外光谱、红外光谱、荧光光谱进行了表征.结果表明,微凝胶粒径为400 nm;Eu(Ⅲ)与微凝胶、HTTA之间以配位作用为主;微凝胶、HTTA和Eu(Ⅲ)之间能进行有效的能量传递.其配合物的最佳激发波长为317 nm,在此激发波长下Eu(Ⅲ)有较强的荧光特征发射.     

三(乙酰丙酮)合铱(Ⅲ)的谱学性质研究

对三(乙酰丙酮)合铱(Ⅲ)的质谱、红外吸收光谱、核磁共振氢谱以及紫外．可见吸收光谱进行了理论解析,从中得知：三(乙酰丙酮)合铱(Ⅲ)的质谱中,基峰是准分子离子峰,即质子化的分子[193Ir(C5H7O2)3]H^ ;红外光谱中许多基团的吸收峰与乙酰丙酮钠相比都发生了明显的位移,尤其是羰基(C=O)吸收峰更向低波数方向移动了超过100cm^-1;在核磁共振氢谱中,配体乙酰丙酮基的1个γ-H和6个甲基氢原子的化学位移分别为5．46ppm和1．98ppm,与乙酰丙酮钠中对应的2类氢核相比均移向低场;它的紫外．可见吸收光谱有4个吸收峰,分别是由π→π跃迁、电荷迁移跃迁、n→π^*跃迁和配位场跃迁中的d-d跃迁引起的。这些结果进一步论证了三(乙酰丙酮)合铱(Ⅲ)的结构特征。     

磁性核壳结构Ce掺杂氧化锆的制备及其As(Ⅲ)吸附性能（英文）

采用溶剂热法和溶胶–凝胶法制备磁性介孔As(Ⅲ)吸附剂Fe₃O₄@SiO₂@Ce-ZrO₂。该核壳结构材料具有高比表面积(168.2 m²/g)和快速磁分离性能(5.37 A·m2/kg)。与Fe₃O₄@SiO₂@ZrO₂相比,Ce掺杂样品的As(Ⅲ)平衡吸附量提高12%-23%(pH3-11),这主要归因于双金属M—O—As配合物的形成。共存的SO₄^2-和PO₄^3-会削弱As(Ⅲ)的吸附,Ca²⁺对除As(Ⅲ)有积极作用,而Cl^-和NO₃^-的影响很小。在初始As(Ⅲ)浓度5mg/L、313K和pH中性条件下,As(Ⅲ)最大吸附容量可达24.52 mg/g。准二级模型对As(Ⅲ)吸附动力学数据的拟合效果良好。此外,吸附...     

聚甲基丙烯酸甲酯微球表面镀银的研究

用分散聚合法制备聚甲基丙烯酸甲酯(PMMA)微球,以聚乙烯吡咯烷酮(PVP)为分散剂,依次用葡萄糖和硼氢化钠还原银氨溶液,在微球表面化学镀银,得到表面覆银的PMMA-Ag微球,对其进行了表征和分析。结果表明,微球分散性好,银层光滑致密,粒径较均匀,直径约2μm;XRD图谱显示无银以外的其它物相存在;红外光谱显示银与PMMA微球的表面可能存在相互作用,是银还原沉积的影响因素;热重分析表明,PMMA-Ag耐热性有所提高(26℃);制备使用的硝酸银占PMMA微球质量分数为55%时,样品的导电率最大(330 S/cm)。     

001×14.5强酸性树脂对铬(Ⅲ)的吸附性能

采用离子交换树脂法吸附铬(Ⅲ),通过树脂选型确定强酸性阳离子交换树脂001×14.5对铬(Ⅲ)吸附容量最大,用所选的001×14.5树脂研究铬(Ⅲ)的吸附性能。静态吸附实验表明:转速大于120 r/min时,对树脂吸附的影响可忽略,即外扩散基本消除,pH=7.0时,吸附最佳,铬(Ⅲ)吸附率随树脂用量的增加而增大;001×14.5树脂吸附铬(Ⅲ)的过程符合Langmuir等温曲线,且为优惠吸附;吸附过程符合拟二级动力学方程,吸附过程的表观活化能Ea=23.4 kJ/mol,颗粒内扩散为吸附速率的主要控制步骤;用1 mol/L的硫酸对吸附后的饱和树脂进行脱附再生,脱附率可达99%。     

巯基树脂对金(Ⅲ)的吸附性能及其机理

研究了Au(Ⅲ)在巯基树脂上的吸附行为。结果表明:在298 K时静态饱和吸附容量为1106.9 mg/g树脂,用15%硫脲与1 mol.L-1盐酸的1∶1混合溶液作解吸剂解吸率可达92.60%。等温吸附遵循Freundlich经验式;测得在298 K时,吸附速率常数k298=5.23×10-5s-1;吸附活化能Ea=16.23 kJ.mol-1;吸附反应热效应ΔH=27.8 kJ.mol-1。用饱和容量法测定巯基树脂吸附Au(Ⅲ)的配位比均接近1∶1。红外光谱测定表明:树脂功能基-SH中硫原子与Au(Ⅲ)形成了配位键。     

利用循环伏安法对铱(Ⅲ)、铱(Ⅳ)氯水配合物的电化学行为研究

利用循环伏安法对Ir(Ⅲ)、Ir(Ⅳ)氯水配合物的电化学行为进行探索性研究.结果表明:随着配合物中水分子的增加,Ir(Ⅲ)、Ir(Ⅳ)氯水配合物电对的式电位增大;Ir(Ⅲ)、Ir(Ⅳ)氯水配合物的氧化还原反应属于可逆反应或准可逆反应;峰电流ip与各物种浓度c之间存在较好的线性关系.     

两种新型铱(Ⅲ)配合物的合成与性质研究

分别以2-苯基吡啶(ppy)为第一配体,以1-苯基-1,3-丁二酮(phbd),1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5(pmbp)为第二配体合成了两个新的铱配合物Ir(ppy)2(pmbp)、Ir(ppy)2(phbd),通过红外光谱、元素分析和核磁共振对其化学组成进行了结构表征,表征结果与理论吻合良好;配合物在紫外吸收光谱图上的290~310 nm处出现了强的配体自旋允许的单重态π-π*跃迁吸收峰,在400~460 nm处出现了配合物分子内金属铱到配体的单重态和三重态电荷跃迁吸收峰(1MLCT和3MLCT);同时配合物Ir(ppy)2(pmbp)、Ir(ppy)2(phbd)在荧光光谱上522、518 nm处出现了强的绿光发射。     

A Study of Interaction of Cobalt Sulphide Coatings with Cu(II) Ions

Cobalt sulphide coatings formed by two cycles (one cycle includes the treatment of the surface with the solution of Co(II) ammoniate complex; hydrolysis of the adsorbed Co(II) compounds; and sulphidation (in Na₂S solution) of the products of the hydrolysis) contain ～15% CoS, which in 0.1 M KClO₄ solution is reduced in the region of potentials of hydrogen evolution, and Co hydroxosulphide. Reduction of the latter occurs at the potentials from -0.4 to -0.8 V in 0.1 M KClO₄ solution and in the potential region 0.2-0.3 V in 0.05 M H₂SO₄, The reduction occurs in the solid phase and is reversible. After treating such a coating with a solution of Cu(II) ions, only CoS interacts with Cu(II), giving, as a result of redox and exchange processes, Cu_2–xS.     

Zn对锂电池材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2结构和电化学性能的影响

采用共沉淀法掺入少量Zn得到Li(Ni1/3Co1/3Mn1/3)1-xZnxO2材料。通过X射线衍射、光电子能谱(XPS)和电化学测试研究掺杂对其晶体结构、元素价态和电化学行为的影响。结果表明:掺入Zn增大晶格常数;在粉末颗粒表面的Zn含量是颗粒内部的数十倍;掺杂后Co、Mn依然保持+3、+4价,但是Ni由+2、+3混合价态组成;掺入少量Zn阻止电极在4.5V电位下的不可逆氧化反应;掺入Zn有效改善高截止电压下的循环容量保持能力,其作用与改变材料表面状态有关。     

铑(Ⅲ)氯水配合物的制备及紫外可见光谱的研究

采用封管氯化的方法[1 ] ,制得铑的标准溶液。在一定条件下处理H3[RhCl6]溶液 ,获得K2 [Rh(H2 O)Cl5]、K3[RhCl6]和 [Rh(H2 O) 6]·(ClO4) 3种态。以K2 [Rh(H2 O)Cl5]和K3[RhCl6]为起始物 ,利用国产 71 7阴离子树脂 ,分别得到trans - [Rh(H2 O) 4 Cl2 ]+、cis- [Rh(H2 O) 4 Cl2 ]+、mer- [Rh(H2 O) 3Cl3]、fac- [Rh(H2 O) 3Cl3]和cis- [Rh(H2 O) 4 Cl4]- 种态。研究它们的紫外 -可见吸收光谱发现 ,随着配位内界水分子数的增加 ,其特征吸收峰表现为紫移。通过分析和研究它们的极性及特性吸收峰 ,提出了铑 (Ⅲ )氯水配合物新的鉴别方法。     

Voltammetry and fluorescence studies on the interaction between Eu(phen)_3~(+3)and DNA

The binding mode of Eu(phen) 3+3 with DNA is studied by fluorescence and voltammetric methods. From the Scatchard graph and the fluorescence quenching phenomenon, it is concluded that the mode of interaction between Eu(phen)3+3 and DNA is intercalation bind by inserting the phen ?-? conjugate surface between the base pairs of the DNA duplex. Voltammetry was used to confirm the results obtained from the fluorescence method, the result from both methods agrees with each other. The binding constant (K) and the binding site size (ns) were calculated from voltammetric data such as the shifts in potential and limiting currents in the process of adding DNA, according to the positive shifts of peak potential. It was considered that the complex of the +2 ion interacted more favorably with the nucleotide bases than that of the +3 ion by hydrophobic interaction.     

不锈钢柠檬酸钝化工艺研究

研究了不锈钢柠檬酸钝化的工艺,用柠檬酸对不锈钢进行钝化处理,通过电化学技术、浸泡试验对改性后的试样进行耐蚀性测试,并运用XPS技术对表面改性后的不锈钢表面进行了微区成分分析.结果表明:钝化后,不锈钢试样表面由金属氧化物、金属氢氧化物以及少量的金属单质和结晶水组成钝化膜,其耐蚀性大大提高,点蚀电位达到1 100mV左右,在6?Cl3溶液中浸泡的腐蚀速率显著低于未钝化试样的腐蚀速率.综合考虑,不锈钢柠檬酸钝化的最佳工艺为:柠檬酸质量分数4%,温度65℃,钝化时间15min,浓硝酸后处理11min.     

Synthesis and photoluminescence properties of Eu(pzc)3(phen) and Eu(mpzc)3(phen)

Novel europium(III) complexes, (2-pyrazinecarboxylato)(phenanthroline) europium(III) [Eu(pzc)₃(phen)] and (5-methyl-2-pyrazinecarboxylato) (phenanthroline)europium(III) [Eu(mpzc)₃(phen)] have been designed and synthesized. These complexes were characterized by FT-IR, UV-Vis, and X-ray photoelectron spectroscopy. Photoluminescence (PL) studies showed that the two complexes emitted remarkably red luminescence. When powder samples of Eu(pzc)₃(phen) and Eu(mpzc)₃(phen) were examined using time-resolved spectroscopic analysis, the luminescence lifetimes were found to be 1.05 and 2.36 ms, respectively. Thermogravimetric analysis showed that the europium complexes possessed good thermal stability up to 345–350 °C.     

Investigation of the Interaction Between Cu2-x S +So Coatings and Pd(II) Ions by Cyclic Voltammetry and X-ray Photoelectron Spectroscopy

The interaction between Pd²⁺ ions and Cu_2-xS coating formed by three cycles and containing ~30 at.% of elementary S has been investigated by the methods of cyclic voltammetry and photoelectron spectroscopy (one cycle of coating formation includes treatment of the surface with Cu(I)+Cu(II) ammoniate solution, hydrolysis of the adsorbed copper compounds and sulphidation of copper oxygen compounds in Na₂S_n solution). After exposure of such a coating to Pd²⁺ ions (1.7 mM PdCl_2’ pH-2), an exchange as well as a redox interaction between the coating components and Pd²⁺ ions has been shown to occur. Due to this the amount of copper in the coating decreases from 2 to 4 times and that of sulphur from 1.5 to 5 times. The coating modified in such a way has been found to contain up to 75 at.% of palladium, ~90% of it being in a metallic state.

It has been determined that at the beginning S^o is bound into a soluble compound:

2Pd²⁺ + S^o + 3H₂O → 2Pd^o + H₂SO₃ + 4H⁺.

The Cu₂S present in the coating is considered to interact with Pd²⁺, with the formation of Pd⁰ and CuPdS_2’, while CuS reacts most likely according to the reaction:

CuS + 3Pd²⁺ + 3H₂O → 3Pd^o; + H₂SO₃ + Cu²⁺ + 4H⁺.

The Cu_2-xS +S^o coating formed on a dielectric and modified with Pd²⁺, contrary to the initial Cu_2-xS +S^o coating, can be plated with copper from any electrolyte for copper deposition.     

Eu掺杂ZnO薄膜与Si(100)衬底间扩散过程分析

利用雾化热解工艺,在Si(100)衬底上制备了Eu掺杂的ZnO薄膜,通过N2的作用,将前驱体溶液输送到衬底表面,同时为实现ZnO的晶化,衬底温度保持在350℃.通过RBS分析了薄膜和衬底之间的原子分布,结果显示了ZnO薄膜与Si衬底之间存在过渡层.对RBS数据的分析表明该过渡层的形成是由于Si向ZnO层中的扩散,表明Si向氧化物中的扩散是不能忽略的,即使在350℃的低温下.同时,作者利用Fick扩散方程对Si向Eu3 掺杂ZnO薄膜的扩散行为进行了分析,结果表明掺杂离子Eu3 具有阻止Si扩散的能力,其原因可能与Eu3 离子在晶界上的偏析有关.     

Spectroscopic investigation of the interactions between emeraldine base polyaniline and Eu(III) ions

The interactions of emeraldine base form of polyaniline (EB-PANI) and Eu(III) ions in 1-methyl-2-pyrrolidinone (NMP) solution and in films have been investigated by UV–vis–NIR, resonance Raman, luminescence and electron paramagnetic resonance (EPR) spectroscopies. These spectroscopic techniques allowed to characterize quinone and semiquinone segments in the polymeric chains, and the oxidation state of europium ions in Eu-PANI samples. For high values of Eu(III)/N molar ratio (24/1) the presence of a weak polaronic absorption band at 980 nm in UV–vis–NIR spectrum and the observation of bands at 1330 and 1378 (ν_C–N+) cm^?1 due to emeraldine salt in the Raman spectrum at 1064 nm indicate a low doping degree. Oxidation of EB-PANI to pernigraniline base (PB-PANI) occurs in diluted solutions. The experimental data showed that the solvent plays an important role on the nature of formed species. The narrow EPR signal at g = 2.006 (line width 8G) confirms the presence of PANI radical cations in Eu-PANI film. The absence of broad signal characteristic of Eu(II) in EPR spectrum suggested that europium ions are primarily at Eu(III) oxidation state. The luminescence spectra of Eu-PANI film presented emission bands at 405 and 418 nm assigned to PANI moieties and bands at 594, 615 and 701 nm assigned to ⁵D₀ → ⁷F_J (J = 1, 2 and 4, respectively) transitions of Eu(III). EPR and photoluminescence data confirm that europium ions are mainly in Eu(III) oxidation state in Eu(III)/PANI films.