Synthesis and Properties of Copper Tetra-4-lauryloxyphthalocyanine

Copper tetra-4-lauryloxyphthalocyanine was synthesized. Its electronic absorption spectra show that the complex is associated in organic solvents. The shape of the spectrum and the positions of the absorption bands are virtually independent of the solvent. The compound exhibits thermotropic and lyotropic mesomorphism.     

铜卟啉-TiO2复合光催化剂制备及降解4-NP的研究

合成了取代基数目不同的3种铜卟啉配合物,并与纯锐钛矿型TiO2作用,得到相应的铜卟啉敏化TiO2复合光催化剂.采用扫描电子显微镜(SEM)考察了铜卟啉-TiO2复合光催化剂的形貌特征,紫外-可见光谱和X射线衍射(XRD)分析结果表明,铜卟啉负载于TiO2表面,未改变TiO2的晶型.可见光降解4-硝基苯酚(4-NP)实验结果表明,复合催化剂性质稳定,可多次重复使用,卟啉环外围极性取代基数目越多,铜卟啉光敏化效果越好.     

Association of Copper Tetra-4-(n-alkoxycarbonyl)phthalocyanines in Solvents with Low Dielectric Permittivity

Association of copper tetra-4-(n-butoxycarbonyl)- and copper tetra-4-(n-nonoxycarbonyl)phthalocyanines in benzene and chloroform was studied. It was found that the length of the alkyl chain has no noticeable effect on the association; the solvent effect is somewhat stronger. The thermodynamic parameters of dimerization were calculated.     

Structure of Copper Chelate of 2-Hydroxy-4-methylthiobutanoic Acid as Trace Mineral Additive in Animal Feeding

The chelate complex of Cu2+ with 2-hydroxy-(4-methylthio)butanoate(MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA) is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure(C10H18Cu O6S2, 1, monoclinic, space group P21/c, Z = 2, a = 16.158(4), b = 4.9733(12), c = 9.159(2) ?, β = 104.786(4)°) exhibits that two MHA-H ligands coordinate with a CuII ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.     

碳纳米管的化学修饰以及作为润滑油添加剂的摩擦学性能研究

采用硫酸和硝酸混合酸对催化裂解法(CVD法)制备的多壁碳纳米管(MWNNTs)进行纯化,然后运用硬脂酸对碳纳米管进行表面修饰,并研究了硬脂酸修饰后的碳纳米管的表面状况以及作为润滑油添加剂的摩擦学行为．实验结果表明,在硫酸催化剂作用下,通过酯化反应碳纳米管能够被硬脂酸包覆,并且硬脂酸修饰的碳纳米管作为润滑油添加剂能够显著提高基础油的减摩抗磨性能,当添加量为0．15％左右时,润滑油的减摩抗磨性能最佳,与基础油相比可以使摩擦系数下降10％左右,磨损量下降30％～60％．     

4-溴苯甲醚用作锂离子电池过充保护添加剂的研究

通过在锂离子电池电解液中添加4-溴苯甲醚(4-Bromoanisole, 简称4BA)来提高锂离子电池的过充保护能力. 对电池分别进行了过充实验、循环伏安扫描、红外光谱分析、交流阻抗和容量特性测试, 实验结果表明, 在1 mol•L－1 LiPF6/EC＋DEC＋DMC(质量比1/1/1)中添加5% 的4BA(质量分数)时, 当外加电压为4.4 V(相对于Li/Li＋)时, 4BA开始发生电聚合反应且生成高分子聚合物膜, 使电池内阻增大而阻止电压的升高, 从而使电池处于比较安全的状态. 该体系正常充放电过程中, 添加5%的4BA对电池容量特性基本没有影响, 4BA 的防过充机理为阻断机理.     

Synthesis and Physico-Chemical Properties of Homoleptic Copper(I) Complexes with Asymmetric Ligands as a DSSC Dye

To develop low-cost and efficient dye-sensitized solar cells (DSSCs), we designed and prepared three homoleptic Cu(I) complexes with asymmetric ligands, M1, M2, and Y3, which have the advantages of heteroleptic-type complexes and compensate for their synthetic challenges. The three copper(I) complexes were characterized by elemental analysis, UV-vis absorption spectroscopy, and electrochemical measurements. Their absorption spectra and orbital energies were evaluated and are discussed in the context of TD-DFT calculations. The complexes have high V_OC values (0.48, 0.60, and 0.66 V for M1, M2, and Y3, respectively) which are similar to previously reported copper(I) dyes with symmetric ligands, although their energy conversion efficiencies are relatively low (0.17, 0.64, and 2.66%, respectively).     

Host-Guest Interactions and Laser Activity in AlPO4-5/Laser Dye Composites

In situ inclusion of the laser dyes coumarin 466, coumarin 7, pyridine 2 and DCM has been conducted successfully in AlPO₄-5 crystals. The charged molecule pyridine 2 interacts with the framework and leads to bundle-like morphologies with increasing dye content. Uncharged molecules (DCM, coumarin 7, coumarin 466) are included, although corresponding molecular dimensions are exceeding pore size. These dyes probably induce local defects in the pore walls of AlPO₄-5 which are healed during crystal growth leading to well-developed hexagonal prisms. Spectroscopic studies show interactions of the dyes with the solid-state matrix which are reflected by shifts of absorption and emission maxima of the dyes. For the first time, laser activity is demonstrated on a perfect hexagonal single AlPO₄-5/DCM crystal.     

3, 4-乙烯二氧噻吩单体用作锂离子电池安全性改善添加剂的研究

安全性是制约锂离子电池向电动汽车领域应用拓展的主要障碍. 本工作提出了一种能够有效改善锂离子电池安全性的电解液添加剂-3,4-乙烯二氧噻吩单体（EDOT）,研究了其在有机电解液中的电氧化聚合行为,以及对LiCoO₂电极高温热行为和电池安全性、电化学性能的影响. 循环伏安（CV）和透射电镜（TEM）表征结果表明,单体添加剂能够在电池充电过程发生电氧化聚合,在正极表面形成一层聚（3,4-乙烯二氧噻吩）（PEDOT）导电聚合物膜;差示扫描量热（DSC）分析结果显示,PEDOT隔离了电解液与正极表面的直接接触,减少了过热条件下电解液在正极表面的分解放热. 安全性测试结果表明,在电解液中仅添加0.1%的EDOT单体,即可将电池在150 ^oC高温热冲击下发生热失控的时间推迟13.8分钟. 电化学性能测试结果表明,聚合产物良好的电子导电性能有效改善正极的电子传导能力,在一定程度上提高电池的倍率性能和循环稳定性,而容量、低温性能等基本不受影响,展示出良好的应用前景.     

镍铁氧体/碳纳米管复合材料的制备及其对染料废水的吸附性能

用浸渍法制备了镍铁氧体/碳纳米管(NF/MWNTs)复合材料。用XRD、SEM、TEM、VSM、UV-Vis等表征了样品的组成、结构、形貌、磁性能和吸附性能。结果表明,制备的NF/MWNTs复合材料保留了碳纳米管优良的吸附性能,且具有良好的镍铁氧体负载率和优异的磁性能。质量比(mNF/mMWNTs)为1的NF/MWNTs复合物对亚甲基蓝溶液的最大吸附容量为18.87mg·g^-1,其吸附行为符合Langmuir和Freundlich模型。NF/MWNTs复合材料对亚甲基蓝溶液的脱色率与溶液温度和pH值呈正相关性。此外,NF/MWNTs复合材料回收容易,活化处理简便,可重复使用。     

Probing CO2 Reduction Pathways for Copper Catalysis Using an Ionic Liquid as a Chemical Trapping Agent

The key to fully leveraging the potential of the electrochemical CO₂ reduction reaction (CO2RR) to achieve a sustainable solar‐power‐based economy is the development of high‐performance electrocatalysts. The development process relies heavily on trial and error methods due to poor mechanistic understanding of the reaction. Demonstrated here is that ionic liquids (ILs) can be employed as a chemical trapping agent to probe CO2RR mechanistic pathways. This method is implemented by introducing a small amount of an IL ([BMIm][NTf₂]) to a copper foam catalyst, on which a wide range of CO2RR products, including formate, CO, alcohols, and hydrocarbons, can be produced. The IL can selectively suppress the formation of ethylene, ethanol and n‐propanol while having little impact on others. Thus, reaction networks leading to various products can be disentangled. The results shed new light on the mechanistic understanding of the CO2RR, and provide guidelines for modulating the CO2RR properties. Chemical trapping using an IL adds to the toolbox to deduce the mechanistic understanding of electrocatalysis and could be applied to other reactions as well.     

Synthesis of a Starchy Photosensitive Material for Additive Manufacturing of Composites Using Digital Light Processing

In this study, digital light processing (DLP) was used to achieve 3D-printed composite materials containing photosensitive resin blended with starch and hemp fibers. The synthesis of 3D-printed composites was performed without heating, according to various material combinations ranging from pure photosensitive resin to a mixture of three phases, including resin, starch, and hemp fibers, with the weight content for each reinforcing phase reaching up to a third of the formulation. The morphology, composition, and structure of the 3D-printed composites were assessed using infrared spectroscopy, laser granulometry, X-ray diffraction, and optical and scanning electron microscopy. In addition, thermal behavior and mechanical performance were studied using calorimetry, differential scanning calorimetry, and tensile testing combined with high-speed optical imaging. The results showed that the post-curing step is a leading factor for improving the mechanical performance of the 3D-printed composites. In addition, hemp fiber or starch did not alter the tensile strength. However, the largest reinforcing effect in terms of stiffness improvement was obtained with starch. Additionally, starchy composites demonstrated the strongest dependence of heat capacity on operating temperature.     

Photorefractive Composites Based on Nanocrystalline Carbocyanine Dye J-Aggregates with a Fast Response Time

The use of carbocyanine dye J-aggregates as sensitizers of photoelectric sensitivity and chromophores with the third-order nonlinear optical polarizability made it possible, by the action of two intersecting He–Ne laser (633 nm) beams and an applied electric field, to obtain photorefractive spatial modulation of the refractive index in a nonplasticized polymer layer having the glass transition temperature of about 230°C with a short (20 ms) time of response to this action. A fairly high two-beam-coupling gain coefficient was obtained, which reached a value of = 218 cm^–1 at an applied field of E ₀ = 50 V/m. The net internal gain (difference between the beam-coupling gain coefficient and the absorption coefficient ) was – = 143 cm^–1 under these conditions.     

Chemical Modifications on Linen for Unsaturated Polyester Composites

Linen was chemically modified by oleoyl chloride(OC) and stearoyl chloride(SC) to graft fatty moieties onto fiber via ester connections. Pyridine was used as solvent. The reaction was simplified by reacting the compounds in air at 60℃ for 6 h. Fourier transform infrared spectroscopy(FTIR) and thermal gravimetric analysis were conducted to characterize the treated fiber. The FTIR result confirms that the fatty portions have been successfully grafted onto the fiber after the chemical modification. The thermal stability of the SC-modified linen(SCL) was similar to that of the flax modified by oleoyl chloride(OCL). SCL and OCL demonstrated a temperature of 5% mass loss, which was above 200℃ and could meet the requirements of the processing conditions for most composites. Thereafter, the SCL-reinforced unsaturated polyester(UPE) composites were prepared and characterized. The composite presented a much better impact strength of 61.1 J/m and tensile modulus of 1.69 GPa than those of UPE with applicable thermal stability. SCL has been shown to be a promising choice as reinforcing material for composites.     

2-Sulfanylhydroquinone Dimer as a Switchable Fluorescent Dye

A new dye was developed, the photoluminescence properties of which are controlled by a chemical reaction. The fluorescence properties of 2-sulfanylhydroquinone dimers depend on the number of hydroxyl groups that are acylated. Unprotected or monoacylated 2-sulfanylhydroquinone dimers displayed good fluorescence properties, whereas diacylated and tetraacylated 2-sulfanylhydroquinone dimers showed dramatically decreased fluorescence. A monomesylated derivative was devised, which shows good fluorescence characteristics as a switching fluorescence dye through a chemical reaction.     

Copper as a Robust and Transparent Electrocatalyst for Water Oxidation

Copper metal is in theory a viable oxidative electrocatalyst based on surface oxidation to Cu^III and/or Cu^IV, but its use in water oxidation has been impeded by anodic corrosion. The in situ formation of an efficient interfacial oxygen‐evolving Cu catalyst from Cu^II in concentrated carbonate solutions is presented. The catalyst necessitates use of dissolved Cu^II and accesses the higher oxidation states prior to decompostion to form an active surface film, which is limited by solution conditions. This observation and restriction led to the exploration of ways to use surface‐protected Cu metal as a robust electrocatalyst for water oxidation. Formation of a compact film of CuO on Cu surface prevents anodic corrosion and results in sustained catalytic water oxidation. The Cu/CuO surface stabilization was also applied to Cu nanowire films, which are transparent and flexible electrocatalysts for water oxidation and are an attractive alternative to ITO‐supported catalysts for photoelectrochemical applications.     

Chemical Interaction between Nonionic Surfactants and an Acid Dye

Complexation of the dye Direct Red 1 with a series of laurylamine surfactants with varying number of ethylene oxide units has been studied by voltammetry. From the measurement of the cathodic current of both dye and surfactant, the stability constants of the established equilibrium between the dye D, the surfactant S, and the dye-surfactant complex D-S can be calculated. The values of the stability constant K at 25 degrees C calculated for a defined dye-surfactant stoichiometry depend on the number of ethylene oxide units incorporated by the surfactant. These constants decrease by one order of magnitude at 60 degrees C maintaining the dependence on the number of ethylene oxide units. Copyright 2001 Academic Press.     

TEMPO存在下丙二腈对苯乙烯聚合的加速作用研究

在少量丙二腈存在下,苯乙烯在稳定自由基TEMPO作用下的聚合速率显著增加,分子量分布较窄,且随转化率增大而增大,具有活性聚合特征.丙二腈与TEMPO的摩尔比在4:1时加速效果较好,在125℃下聚合1h转化率可达到70%,分子量可达到105,且反应温度降低到110℃.¹HNMR分析表明,丙二腈在反应中起催化剂作用,通过削弱碳氮键可以提高转化速度,还可明显降低聚合温度.     

一种近红外光记录与存储材料——克酮酸染料的三阶非线性光学性质

克酮酸染料是一类新型的近红外吸收染料,由于具有良好的光热稳定性和荧光性能,因而在光记录与存储等领域有着潜在的应用价值.本文利用简并四波混频技术,在近红外区不同吸收波长,在脉宽为130 fs条件下研究了一种吲哚克酮酸染料在溶液和薄膜中的三阶非线性光学性质.该克酮酸染料在773 nm,四氢呋喃溶液中的共振三阶超分子极化率γ为5.3×10^-29esu,在薄膜中的共振三阶非线性极化率χ⁽³⁾值达到10^-8esu数量级.同时,对于三阶非线性光学响应及其动力学机制也进行了研究和探讨.