氧化锌薄膜的制备及掺Co2+对结构和性能的影响

采用溶胶-凝胶方法在Si(111)衬底上制备了ZnO:Co氧化锌薄膜,利用X射线衍射(XRD)仪和振动样品磁强计(VSM)分别测试了样品的结构和磁性.实验表明,采用溶胶-凝胶方法制备的掺Co2+氧化锌薄膜具有(002)峰的择优取向,同时ZnO:Co薄膜在室温情况下呈现出铁磁性.     

生物淋滤溶出废旧锂离子电池中钴的研究

考察不同培养条件对生物淋滤溶出钴的影响,研究提高钴生物溶出效率的方法和工艺条件. 研究表明:在硫磺质量浓度为4 g/L,起始pH为2.0,培养温度为27 ℃时,当电极混合材料的质量浓度为1%的条件下,淋滤12 d后钴的溶出质量浓度可达306 mg/L. 降低淋滤体系起始酸度(pH为1.0)和改变淋滤液硫源组合(2 g/L硫磺和2 g/L黄铁矿)可以有效提高钴的生物溶出效率,淋滤12 d后钴的溶出质量浓度高达1 682 mg/L,溶出率超过90%.     

Fabrication of Sensitive Potentiometric Cholesterol Biosensor Based on Co3O4 Interconnected Nanowires

Highly sensitive, selective, reliable and inexpensive cholesterol biosensors are highly demanded for the routine monitoring of cholesterol molecules in order to prevent heart failure incidents. In this study, Co₃O₄ nanostructures are synthesized using polyvinyl pyrrolidone surfactant as growth template by a low temperature aqueous chemical growth method. The morphology of nanostructures was investigated by scanning electron microscopy and X‐ray diffraction techniques. The nanostructures exhibit interconnected nanowires like morphology with interconnected network of nanowires. The nanostructures of Co₃O₄ are polycrystalline. The cholesterol oxidase was physically adsorbed on the interconnected nanowires of Co₃O₄ for the chemical sensing of cholesterol molecules. The sensor device detected a wide range of cholesterol from 1×10^?7 M to 1×10^?3 M concentrations with sensitivity of ?94.031 mV/decade. A detection limit of 0.035×10^?7 M cholesterol concentration was observed and a fast response time of 10 s was also noticed. The fabricated device is highly stable, selective, sensitive, reproducible and repeatable. All the collected information about presented cholesterol biosensor indicates its potential application for the monitoring of cholesterol concentrations from human blood serum and real‐life samples.     

Uncatalyzed Hydroamination of Electrophilic Organometallic Alkynes: Fundamental,Theoretical, and Applied Aspects

Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among the crucial tools of molecular chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide synthesis and “click” chemistry. We are concerned with redox organometallic compounds that can potentially be used as biosensors and redox catalysts and report an uncatalyzed reaction between primary and secondary amines with organometallic electrophilic alkynes that is free of side products and fully “green”. A strategy is first proposed to synthesize alkynyl organometallic precursors upon addition of electrophilic aromatic ligands of cationic complexes followed by endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene ligands of Fe, Ru, and Co complexes subsequently react with amines to yield trans‐enamines that are conjugated with the organometallic group. The difference in reactivities of the various complexes is rationalized from the two‐step reaction mechanism that was elucidated through DFT calculations. Applications are illustrated by the facile reaction of ethynylcobalticenium hexafluorophosphate with aminated silica nanoparticles. Spectroscopic, nonlinear‐optical and electrochemical data, as well as DFT and TDDFT calculations, indicate a strong push–pull conjugation in these cobalticenium– and Fe– and Ru–arene–enamine complexes due to planarity or near‐planarity between the organometallic and trans‐enamine groups involving fulvalene iminium and cyclohexadienylidene iminium mesomeric forms.     

氨蒸发诱导法制备纳米结构LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2及其作为高功率型锂离子电池正极材料的性能

采用氨蒸发诱导法成功制备出纳米结构LiNi1/3Co1/3Mn1/3O2正极材料,借助X射线衍射(XRD)分析、扫描电镜(SEM)、透射电镜(TEM)、高分辨率透射电镜(HRTEM)、能量分散谱(EDS)和比表面测试等表征手段及恒电流充放电测试研究了其晶体结构、微观形貌和电化学性能.研究表明该方法制备出的材料具有良好的α-NaFeO2层状结构,阳离子混排程度低.纳米片交错堆积而成核桃仁状形貌,片与片之间形成许多纳米孔,而且纳米片的侧面属于{010}活性面,能够提供较多的锂离子的脱嵌通道.在室温下及3.0-4.6 V充放电范围内,该材料在电流密度为0.5C、1C、3C、5C和10C时放电比容量分别为172.90、153.95、147.09、142.16和131.23mAh?g-1.说明其具有优异的电化学性能,非常有潜力用于动力汽车等高功率密度锂离子电池中.     

Synthesis and electrochemical performance of LiNi0.6Co0.2Mn0.2O2 as a concentration-gradient cathode material for lithium batteries

A well-ordered and spherical LiNi0.6Co0.2Mn0.2O2 cathode material was successfully synthesized from Ni and Mn concentration-gradient precursors via co-precipitation. The crystal structure, morphology and electrochemical properties of LiNi0.6Co0.2Mn0.2O2 were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and charge-discharge tests. The material delivered an initial discharge capacity of 174.3 mAh/g at 180 mA/g （1 C rate） between 2.8 and 4.3 V and more than 93.1% of that was retained after 100 cycles. In addition, it also exhibited excellent rate capability, high cut-off voltage and temperature performance.     

微波法制备还原氧化石墨烯负载Pt_3Co纳米合金(英文)

微波辐射法可以在数分钟内将高度分散的Pt3Co合金颗粒负载于还原氧化石墨烯表面上.表征结果发现,与传统的溶剂热法和浸渍法相比,微波法制备的催化剂中贵金属的利用率高,合金颗粒的分布均匀,组成可控,同时氧化石墨烯的再石墨化现象也得到有效地抑制.采用微波法制备的Pt3Co/RGO-MW催化剂在肉桂醛加氢反应中具有较高的活性和和产物选择性.Pt3Co/RGO-MW中每一个Pt原子在70℃的转化频率高达23.8 min-1.     

烯醇-酮互变异构型亚胺衍生物对Co2+的高选择性识别

设计合成了新型烯醇-酮互变异构型亚胺衍生物R, 考察了受体R对18种阳离子的紫外光谱及裸眼识别性能. 结果表明, 该受体对Co²⁺, Fe²⁺和Ni²⁺表现出良好的紫外光谱识别能力, 且可实现对Co²⁺相对明显的裸眼单一识别. Job曲线表明, 受体R与Co²⁺形成了1:1型金属配合物, 且检出限可达4.14×10^-7 mol/L. 制备了受体R裸眼比色识别试纸; 根据理论计算及核磁滴定实验结果阐述了Co²⁺离子识别过程中烯醇-酮互变异构机理.     

Structural,thermal, optical and conductivity studies of Co/ZnO nanoparticles doped CMC polymer for solid state battery applications

In this study, a simple chemical precipitation method was used to synthesize ZnO: Co²⁺ as nanoparticles. The solution casting technique was used for the preparation of polymer films of Carboxymethyl cellulose (CMC) doped with different contents (0.5, 1.5, 3, and 5 wt%) of ZnO/Co NPs. As shown by the X-ray diffraction, the average size of ZnO/Co crystallite of the NPs is 25.6 nm. Meanwhile, the addition of ZnO/Co reduced the semi-crystallinity of CMC. The Fourier transform infrared (FTIR) confirmed the interaction between the ZnO/Co NPs and the polymer CMC. The direct and indirect band gap (Eg) was reduced from (5.32–5.01 eV and 5.20 to 4.99 eV respectively) with the increase in ZnO/Co NPs content up to 3 wt% after this content the Eg is increased as shown by the UV–Vis spectra. In addition, the results of TGA displayed the decomposition of the nanocomposite to be little compared to that of the pure CMC indicating the success of fabrication of products. The improvement of the ionic conductivity was noticed upon the addition of ZnO/Co NPs into the polymer CMC system which can be explained in terms of an increase in amorphicity as shown by the impedance spectroscopic study. It was found that the optimum ionic conductivity (3.209 × 10⁻⁶ Scm⁻¹) at ambient temperature was higher for the sample containing 1.5 wt% ZnO/Co NPs with highest of amorphicity and the lowest total loss of weight. Therefore, the improvements in optical properties, thermal stability, and AC conductivity which were observed represent a strong support for the use of the nanocomposite films in the solid state battery applications.     

基于钴离子介导信号转换的抗坏血酸比色分析

抗坏血酸是许多生化过程所必需的一种生物小分子。借助于羟基氧化钴纳米片的氧化性和钴离子与硫氰酸根离子之间强的螯合作用,本研究首次报道了一种基于钴离子信号转换的新方法用于抗坏血酸的比色分析。在抗坏血酸存在时,羟基氧化钴纳米片被还原降解产生二价钴离子,钴离子与硫氰酸根离子之间通过螯合作用生成蓝色的[Co(NCS)₄]^_2-阴离子络合物,在625 nm处产生可见吸收信号。实验首先对羟基氧化钴纳米片与抗坏血酸的反应时间、硫氰酸铵和吐温-80的加入量等实验参数进行了优化,当反应时间为5 min,硫氰酸铵(3 mol/L)和吐温-80(10%, w%)的加入体积分别为30 μL和80 μL时,检测体产生最强的吸收信号。在优化的条件下,随着抗坏血酸浓度的增加,检测体系在625 nm处的吸收值线性增强,在0.03～0.45 mmol/L浓度范围内,检测体系在625 nm处的吸收值与AA浓度呈良好的线性关系,线性方程为A₆₂₅=0.638C (mmol/L)+0.042,相关系数R=0.993,检测限(3S/N)为1.5 μmol/L。