四苯基卟啉夹层石墨烯复合物的光电子特性研究

以四苯基卟啉和石墨烯为原料,用溶剂-非溶剂共沉淀法制备得到四苯基卟啉夹层石墨烯复合物,通过扫描电镜（SEM）、透射电镜（TEM）、荧光光谱和电化学循环伏安对所得复合物进行表征。分析结果表明,共沉淀过程使得四苯基卟啉成功包裹了石墨烯,它们之间存在电子转移,且四苯基卟啉在654nm和717nm处的荧光淬灭;四苯基卟啉-石墨烯复合物是一个很好的电子给体-受体体系,在新型显示器、光伏电池等方面有潜在的应用价值。     

新型四苯基卟啉衍生物及其锌(Ⅱ)配合物的合成与性质研究

以四苯基卟啉(TPP)为原料,经过硝化、还原、酰胺化等反应合成了一种新型四苯基卟啉衍生物及其锌(Ⅱ)配合物,通过FAB-MS、IR、1 H-NMR和元素分析等方法鉴定了目标产物的结构,并对其发光性质进行了研究。结果表明,四苯基卟啉衍生物及其锌(Ⅱ)配合物的紫外-可见光谱和荧光光谱均发生了明显红移。     

利用紫外光电子谱和第一性原理确定四苯基卟啉的结构与电子态

利用第一性原理确定了四苯基卟啉分子的结构模型,结果表明分子中的苯环与卟吩骨架的夹角为55°,且苯环的自由旋转导致卟吩骨架略微偏离平面形状。再利用紫外光电子谱（UPS）研究了四苯基卟啉在Ru（0001）面的沉积过程,饱和沉积后出现了分子的4个特征峰。对UPS的DV-Xα分析解释了上述光电子谱中四个特征峰的物理起源。     

meso-四-(4-甲氧基-3-磺酸苯基)卟啉在测定痕量金属的应用—锌的分光光度法测定

本文研究了在咪唑存在下 meso—四—(4—甲氧基—3—磺酸苯基)卟啉(TMPPS_4)与锌显色反应的最佳条件,建立了测定锌的新方法,灵敏度高,锌量在0—1.2μg/10mL 范围内遵守比耳定律,用于测定粮食中的锌时结果满意     

四苯并卟啉锌及其衍生物敏化的TiO_2光催化降解曙红B的研究

为提高TiO2纳米晶在光催化过程中对可见光的利用效率,采用化学吸附的方法分别制备了四苯并卟啉锌、中位-四(酰氯基亚甲基)苯并卟啉锌和中位-四(羧基亚甲基)苯并卟啉锌修饰的TiO2纳米晶,并将其用于氙灯辐照下曙红B的降解。由于卟啉吸收可见光后,激发态电子能转移到TiO2的导带,敏化后TiO2的光降解效率均有所提高,其中中位-四(羧基亚甲基)苯并卟啉锌因其与TiO2有效地结合,降解效率最高。     

瓜环与四苯基卟啉锌的功能组装

采用紫外-可见吸收光谱(UV-Vis)、红外光谱(IR)、扫描电镜(SEM)技术探讨了瓜环Q[7,8]与具有光动力疗效的光敏剂四苯基卟啉锌(Zn TPP)分子之间的组装作用。结果表明,Q[7,8]与Zn TPP均形成以1∶1为主的组装物;溶液p H值在5.0~11.0范围内,组装体较稳定;主-客体间的相互作用都能够自发进行,组装过程是放热反应,以熵驱动为主;与Zn TPP相比,组装体的荧光量子产率并没有明显下降;Zn TPP与Q[7,8]组装后,溶解度得到极大的提高。     

中位-四(羧基亚甲基)苯并卟啉锌的合成及其在染料敏化太阳能电池中的应用研究

利用热凝聚法合成四苯并卟啉锌的经典反应,加入过量的丁二酸钠代替原反应物乙酸钠,控制合成了中位-四(羧基亚甲基)苯并卟啉锌.由于羧基的引入,使卟啉分子能够锚定在二氧化钛表面.为转移卟啉激发态电子到二氧化钛的导带提供了通道,并改善了其在二氧化钛表面的分散性,从而使苯并卟啉锌敏化太阳能电池的效率明显提高.     

四-(对酰氧基苯基)卟啉的合成及液晶性能研究

合成了4个系列的中位－四（对酰氧基苯基）卟啉化合物，通过元素分析，紫外－可见光谱，红外光声光谱和核磁共振氢谱等分析手段表征了4种卟啉自由碱化合物，并肜DSC和偏光显微镜研究这些化合物的液晶行为，探讨了碳链长度对卟啉自由碱液晶性能的影响。     

原卟啉IX锌-聚乳酸的合成及表征

血红素用硫酸亚铁-氯化氢的氯仿-甲醇溶液处理,制得原卟啉IX二甲酯。原卟啉IX二甲酯水解得到原卟啉IX,再与乙酸锌反应制得原卟啉IX锌。然后,利用原卟啉IX锌上的羧基,在脱水剂DCC和催化剂HOBt的作用下,与聚乳酸端基的氨基发生酰胺化反应,制备得到了原卟啉IX锌-聚乳酸。UV-Vis光谱、IR和1 H-NMR分析表明,卟啉环脱除铁离子和络合锌离子过程中乙烯基保持稳定。采用GPC测试分子量及分子量分布。结果表明,酰胺化反应近似按照投料比进行反应。     

原卟啉Ⅸ锌-聚乳酸的合成及表征

血红素用硫酸亚铁-氯化氢的氯仿-甲醇溶液处理,制得原卟啉Ⅸ二甲酯.原卟啉Ⅸ二甲酯水解得到原卟啉Ⅸ,再与乙酸锌反应制得原卟啉Ⅸ锌.然后,利用原卟啉Ⅸ锌上的羧基,在脱水剂DCC和催化剂HOBt的作用下,与聚乳酸端基的氨基发生酰胺化反应,制备得到了原卟啉Ⅸ锌-聚乳酸.UV-Vis光谱、IR和1 H-NMR分析表明,卟啉环脱除铁离子和络合锌离子过程中乙烯基保持稳定.采用GPC测试分子量及分子量分布.结果表明,酰胺化反应近似按照投料比进行反应.     

Preparation of zinc oxide-montmorillonite hybrids

The new hybrid materials of zinc oxide with montmorillonite were synthesized by a reaction between the aqueous solutions of the reactants of zinc oxide (zinc chloride and sodium hydroxide solutions) and montmorillonite or hexadecyltrimetylammonium-montmorillonite. The hybrids were characterized by powder X-ray diffraction, Fourier transform-infrared, UV-visible and photoluminescence spectroscopies. The diffuse reflectance absorption spectra of the hybrids exhibited the absorption onsets at 375 nm for zinc oxide-montmorillonite and at 378 nm for zinc oxide-hexadecyltrimetylammonium-montmorillonite, respectively, confirming the formation of zinc oxide in the hybrid materials. The photoluminescence bands of both hybrids, which can be attributed to singly ionized oxygen vacancy in zinc oxide, were observed at 548 nm. The enhancement in emission intensity of the zinc oxide hybrids may be probably due to increase in oxygen vacancies defect arose by the surrounding environment of montmorillonite.     

Nanostructured zinc oxide film for urea sensor

Nanostructured zinc oxide (Nano-ZnO) film has been electrochemically deposited onto indium-tin-oxide (ITO) coated glass plate to co-immobilized urease (Urs) and glutamate dehydrogenase (GLDH) for urea detection. The observed reflection planes corresponding to wurtzite ZnO nanoparticles (~25 nm) in XRD diffraction pattern and UV-visible absorption band at 338 nm reveal the formation of Nano-ZnO. Urs-GLDH/Nano-ZnO/ITO bioelectrode shows high sensitivity for urea detection within 10-80 mg/dL and limit of detection as 13.5 mg/dL with regression coefficient as 0.994 and Michaelis-Menten constant (K_m, 6.1 mg/dL) indicating good affinity of Urs-GLDH to urea.     

Synthesis of different architectures like stars, multipods, ellipsoids and spikes of zinc oxide by surfactantless precipitation

Zinc oxide with different morphologies like stars, multipods, ellipsoids and spikes was synthesized using zinc nitrate and sodium hydroxide in the absence of surfactants. Seed mediation was found to be essential for the formation of ZnO nanospikes. Synthesized ZnO samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), UV-visible diffuse reflectance spectroscopy (UV-vis-DRS) and energy dispersive analysis by X-rays (EDAX) techniques. The predominant c-axis growth of hexagonal lattice was observed in ZnO anisotropic particles. TEM analysis revealed the formation of two types of ZnO ellipsoid particles. Concentration of the reactants was found to have a role in controlling the morphology of the resulting ZnO. Mechanism of formation of varying morphologies of ZnO particles has been proposed.     

Neodymium conversion layers formed on zinc powder for improving electrochemical properties of zinc electrodes

Zinc powder, as active material of secondary alkaline zinc electrode, can greatly limit the performance of zinc electrode due to corrosion and dendritic growth of zinc resulting in great capacity-loss and short cycle life of the electrode. This work is devoted to modification study of zinc powder with neodymium conversion films coated directly onto it using ultrasonic immersion method for properties improvement of zinc electrodes. Scanning electron microscopy and other characterization techniques are applied to prove that neodymium conversion layers are distributing on the surface of modified zinc powder. The electrochemical performance of zinc electrodes made of such modified zinc powder is investigated through potentiodynamic polarization, potentiostatic polarization and cyclic voltammetry. The neodymium conversion films are found to have a significant effect on inhibition corrosion capability of zinc electrode in a beneficial way. It is also confirmed that the neodymium conversion coatings can obviously suppress dendritic growth of zinc electrode, which is attributed to the amelioration of deposition state of zinc. Moreover, the results of cyclic voltammetry reveal that surface modification of zinc powder enhances the cycle performance of the electrode mainly because the neodymium conversion films decrease the amounts of ZnO or Zn(OH)₂ dissolved in the electrolyte.     

Fluorescence-based zinc ion sensor for zinc ion release from pancreatic cells

In this paper, we describe the synthesis and characterization of analytical properties of fluorescence-based zinc ion-sensing glass slides and their application in monitoring zinc ion release from beta pancreatic cells in cell cultures. To fabricate the sensors, the zinc ion indicator ZnAF-2 {6-[N-[N',N'-bis(2-pyridinylmethyl)-2-aminoethyl]amino-3',6'-dihydroxyspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one} was modified to include a sufficiently long linking aliphatic chain with a terminal carboxyl functional group. The recently synthesized ZnAF-2 zinc ion indicator provided high zinc ion selectivity in physiological solutions containing millimolar levels of calcium and other possible interfering cations. The carboxyl-modified ZnAF-2 was conjugated to the activated surface of glass slides, which then served as zinc ion sensors. It was possible to grow pancreatic cells directly on the zinc-sensing glass slide or on a membrane placed on these glass slides. The sensors were used to monitor zinc ion release events from glucose-stimulated pancreatic cells. The study showed that the zinc ion sensors responded effectively to the release of zinc ions from pancreatic cells at the nanomolar level with high selectivity and rapid subsecond response time.     

Zinc nanoparticles in solution by laser ablation technique

Colloidal zinc metallic nanoparticles are synthesized using pulsed laser ablation of metal plate in an aqueous solution of suitable surfactant to prevent aggregation. UV-visible absorption, TEM, small angle X-ray diffraction and wide-angle X-ray diffraction are used for the characterization of colloidal zinc metallic nanoparticles. Colloidal nanoparticles are found highly stable for a long time.     

Sulfidation of zinc plating sludge with Na2S for zinc resource recovery

A high amount of zinc disposed in the landfill sites as a mixed-metal plating sludge represents a valuable zinc source. To recover zinc from the plating sludge, a sulfidation treatment is proposed in this study, while it is assumed that ZnS formed could be separated by flotation. The sulfidation treatment was conducted by contacting simulated zinc plating sludge with Na(2)S solution at S(2-) to Zn(2+) molar ratio of 1.5 for a period of 1-48 h, while changing the solid to liquid (S:L) ratio from 0.25:50 to 1.00:50. The conversion of zinc compounds to ZnS was determined based on the consumption of sulfide ions. The reaction products formed by the sulfidation of zinc were identified by X-ray diffraction (XRD). As a result, it was found that the conversion of zinc compounds to ZnS increased with an increase in S:L ratio. A maximum conversion of 0.809 was obtained at an S:L ratio of 1.00:50 after 48 h. However, when the zinc sludge treated at S:L ratio of 1.00:50 for 48 h was subjected to XRD analyses, only ZnS was identified in the treated zinc sludge. The result suggested that the rest of zinc sludge remained unreacted inside the agglomerates of ZnS. The formation behavior of ZnS was predicted by Elovich equation, which was found to describe the system satisfactorily indicating the heterogeneous nature of the sludge.     

氨法浸出氧化锌烟尘制取活性氧化锌

为实现冶锌废渣中锌资源的再利用,以商洛炼锌厂冶锌过程中产生的氧化锌烟尘为原料,采用氨法浸出-微波蒸氨-火法焙解工艺制得粒度分布均匀的球状活性氧化锌.对锌的浸出工艺及氧化锌前驱体的热解工艺进行研究,并利用TG/DTA、XRD、SEM等测试手段对产品进行结构及物相表征.研究表明,氨法浸出过程中总氨浓度为8 mol/L、pH为10.0、液固比为4∶1、浸出温度为40℃时,锌的浸出率最高可达92.05%.浸出液经两段净化除杂后,80℃下蒸氨25 min时,制得前驱体碱式碳酸锌.在400℃焙解120 min制得平均粒径约为3μm,六方晶系的球状活性氧化锌.此法对设备要求不高,生产成本低,工艺流程短,具有较强的实用性.     

Studies on nanocrystalline zinc coating

Nano zinc coatings were deposited on mild steel by electrodeposition. The effect of additive on the morphology of crystal size on zinc deposit surface and corrosion properties were investigated. Corrosion tests were performed for dull zinc deposits and bright zinc deposits in aqueous NaCl solution (3·5 wt.%) using electrochemical measurements. The results showed that addition of additive in the deposition process of zinc significantly increased the corrosion resistance. The surface morphology of the zinc deposits was studied by scanning electron microscopy (SEM). The preferred orientation and average size of the zinc electrodeposited particles were obtained by X-ray diffraction analysis. The particles size was also characterized by TEM analysis.     

Preparation of extrapure zinc oxide and zinc acetate from diethylzinc

We have developed a process for the preparation of extrapure zinc oxide and zinc acetate from diethylzinc, which includes ultrapurification of this compound through low-pressure fractional distillation, oxygen oxidation of the purified diethylzinc in combustion mode, and heat treatment of the resultant zinc oxide. Zinc acetate was obtained by dissolving the zinc oxide in acetic acid. The content of regulated metallic impurities (iron, copper, aluminum, silicon, cadmium, nickel, cobalt, tin, lead, chromium, molybdenum, and magnesium) in the zinc oxide and zinc acetate was 10^?5 to 10^?6 wt %, and their net content was <5 × 10^?4 wt %.