Controlled synthesis of CuO nanostructures by a simple solution route

A simple solution route has been developed to prepare nanostructured CuO with Cu(NO₃)₂·3H₂O and NaOH as starting materials. CuO nanoribbons or nanorods and their assemblies into hierarchical structures have been synthesized, respectively, by controlling the molar ratio of NaOH to Cu(NO₃)₂, reaction temperature and the concentration of the starting NaOH solution. Experiments demonstrate that the molar ratio of NaOH to Cu(NO₃)₂ is an important parameter which may decide whether CuO exists in nanoribbons (nanorods) or assemblies into hierarchical structures. Whether Cu(NO₃)₂ is dissolved in ethanol or water also influences the formation of monodispersed CuO nanoribbons (nanorods). The growth mechanism of these nanostructures is discussed. The products were characterized by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy (HRTEM) and their optical absorption spectra were also studied.     

Hydrothermal synthesis and structure evolution of hierarchical cobalt sulfide nanostructures

Hierarchical and well-defined cobalt sulfide with flower-like, cube-like, ball-like, and surface hollowed-out nanostructures were successfully prepared by a facile one-pot hydrothermal synthesis approach, employing Co(NO(3))(2)·6H(2)O as a cobalt precursor and thiourea as a sulfur source. The morphologies of these structures can be easily controlled by simply adjusting the molar ratio of reactants and solvents, reaction time, reaction temperature, and ligand types. Thiourea plays two important roles in the growth process of CoS nanostructures. First, it is decomposed to produce S(2-) for the final formation of CoS. On the other hand, it serves as a structure-directing agent to control the crystalline growth of CoS. The electrochemical capacitance performances of the CoS nanostructures were studied, and the flower-like CoS nanostructures show the best charge-discharge performance among all CoS products with the highest specific capacitance values of 389 F g(-1) at current density of 5 mA cm(-2), and 277 F g(-1) at higher current density of 50 mA cm(-2).     

Influence of Microwave Synthesis Parameters on the Size and Morphology of the Resulting MgAl2O4 Nanoparticles

In the present study, Nano-sized magnesium aluminate powders were successfully synthesized via microwave process based on the reaction between Mg (NO₃)₂·6H₂O and Al (NO₃)₃·9H₂O in distilled water, at various conditions. The products were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, photoluminescence (PL) spectroscopy, and EDAX analysis. The effects of different parameters such as reaction time and microwave power on the morphology, particle size, and PL properties of the product were studied by SEM images and the PL.     

A small biomolecule-assisted synthesis of iron sulfide nanostructures and magnetic properties

In this article, a facile l-cysteine-assisted solvothermal method is described, which is about the large-scale synthesis of Fe_0.985S novel nanostructures in a mixed solution composed of ethylenediamine (EN) and distilled water. By varying process parameters, such as the molar ratio of Fe³⁺-to-l-cysteine (reactants), the volume ratio of water to ethylenediamine, and the reaction temperature, different kinds of architectural structures can be controllably synthesized in large quantities. At the same time, a reasonable mechanism for the growth of iron sulfide structures has been proposed. The as-prepared iron sulfide products were characterized using diverse techniques including X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution TEM, superconducting quantum interface device (SQUID) magnetometer (Quantum Design MPMS XL).     

Synthesis of nanostructured lanthanum fluoborate modified by oleylamine and evaluation of its tribological properties as a lubricating additive in synthetic ester

Lanthanum fluoborate modified by oleylamine [denoted as La(BF₄)₃‐OA] was synthesized as a potential lubricant additive by direct precipitation method with sodium tetrafluoroborate and lanthanum nitrate [La(NO₃)₃] as the staring materials and oleylamine (OA) as the surface‐modifying agent in distilled water‐ethanol mixed solvent. The effects of reaction temperature, OA to La(NO₃)₃ ratio, and surfactant cetyltrimethyl ammonium bromide on the size and shape of as‐synthesized La(BF₄)₃‐OA were investigated. The crystalline structure and morphology of as‐obtained La(BF₄)₃‐OA were characterized by X‐ray diffraction, transmission electron microscopy, Fourier transform infrared spectrometry, and X‐ray photoelectron spectroscopy. Moreover, the tribological properties of La(BF₄)₃‐OA as an additive in dioctyl sebacate, a synthetic ester, were evaluated with a four‐ball machine, and the worn surfaces of the steel balls were analyzed with a field emission scanning electron microscope equipped with an energy dispersive spectrometer accessory. It was found that the as‐synthesized La(BF₄)₃‐OA exhibits disk‐like nanoflake shape and have a diameter of 10–45 nm, depending on varying synthetic conditions. As‐synthesized La(BF₄)₃‐OA as an additive in DIOS possesses excellent antiwear and friction‐reduction performance for the steel–steel pair, which is because the as‐synthesized additive simultaneously contain tribologically active elements La, B, and F that facilitate the formation of a boundary lubricating and protecting film on sliding steel surfaces thereby avoiding direct contact of the steel–steel pair and significantly reducing the friction and wear. Copyright © 2016 John Wiley & Sons, Ltd.     

Photodegradation of 2-nitrophenol catalyzed by CoO, CoS and CoO/CoS nanoparticles

The nanoparticles of CoO, CoS and CoO/CoS composite are synthesized using precipitation method. The X-ray diffraction, UV–Vis absorption spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy and FT-IR spectroscopy are used to characterize the prepared nanoparticles. The EDX analysis shows the formation of CoO_0.67S_0.33 composite. The XRD pattern indicates the hexagonal structure for nanocomposite. The formation of Co–O and Co–S bonds is confirmed by FT-IR spectra. The band-gap energies of 2.97, 3.06 and 2.91 eV are obtained from UV–Vis spectra of CoO, CoS and CoO/CoS nanoparticles, respectively. The results of photodegradation of 2-nitrophenol show that the photoreactivity order of nanocatalysts is CoO/CoS > CoO > CoS. The pseudo first-order kinetic rate constants of 6.4 × 10^?3, 4.3 × 10^?3 and 12.2 × 10^?3 min^?1 are obtained for CoO, CoS and CoO/CoS nanoparticles, respectively, at photodegradation reaction conditions of pH 10, 30 mg/L of 2-NP and 1.3 g/L of the catalyst. The proposed nanocomposite shows an acceptable reusability and stability against photocorrosion in four-cycle photodegradation experiments.     

Hydrothermal synthesis of nickel hydroxide nanostructures in mixed solvents of water and alcohol

Nickel hydroxide nanosheets and flowers have been hydrothermally synthesized using Ni(CH₃COO)₂·4H₂O in mixed solvents of ethylene glycol (EG) or ethanol and deionized water at 200 °C for different time. The phase and morphology of the obtained products can be controlled by adjusting the experimental parameters, including the hydrothermal time and the volume ratio of water to EG or ethanol. The possible reaction mechanism and growth of the nanosheets and nanoflowers are discussed based on the experimental results. Porous nickel oxide nanosheets are obtained by heating nickel hydroxide nanosheets in air at 400 °C. The products were characterized by using various methods including X-ray diffraction (XRD), fourier transform infrared (FTIR), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), field emission scanning electron microscopy (FESEM). The electrochemical property of β-Ni(OH)₂ nanosheets was investigated through the cyclic voltammogram (CV) measurement.     

Glycolic acid-supported cobalt ferrite-catalyzed one-pot synthesis of pyrimido[4,5-b]quinoline and indenopyrido[2,3-d]pyrimidine derivatives

Herein, one-pot synthesis of pyrimido[4,5-b]quinoline and indenopyrido[2,3-d]pyrimidine derivatives was developed by the three-component reaction of aldehydes, 6-amino-1,3-dimethyluracil, and 1,3-dicarbonyl compounds in the presence of glycolic acid-supported cobalt ferrite CoFe₂O₄@SiO₂@Si (CH₂)₃NHCOOCH₂COOH as a novel magnetic catalyst in ethanol at reflux conditions. Glycolic acid-supported cobalt ferrite was characterized via Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and vibrating sample magnetometer (VSM). Moreover, the catalyst was easily recovered with magnetic separation and recycled at least for five times without significant loss of its catalytic activity. The products were formed in excellent yields over appropriate reaction times under environmentally friendly conditions. The high efficiency and easy isolation of catalyst from products with an external permanent magnet are some of the remarkable advantages of this method.     

负载硫化钴纳米颗粒的N、S共掺杂石墨烯氧还原电催化剂的制备及性能

采用D-氨基葡萄糖作为Co分散剂和碳源,硫脲作为氮源和硫源,以NaCl为模板制备负载硫化钴纳米颗粒的N、S共掺杂三维石墨烯氧还原电催化剂(CoS/N/S/rGO)。CoS/N/S/rGO具有良好的氧还原反应(ORR)活性,起始电位和半波电位分别为960和815 mV,性能与商业Pt/C相当。此外,CoS/N/S/rGO表现出明显的4电子转移特性和超低的过氧化氢产率。与基于Pt/C的锌-空气电池相比,基于CoS/N/S/rGO的锌-空气电池在6 mol·L~(-1) KOH和0.2 mol~(-1) Zn(CH_3COO)_2碱性电解质中显示出更高的恒电流放电性能以及更好的稳定性。     

Flowerlike MoS2 nanoparticles: solvothermal synthesis and characterization

Flowerlike MoS₂ nanoparticles have been successfully synthesized through a mild solvothermal reaction with the aid of ethanol aqueous solution, and the samples have been characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and low temperature nitrogen adsorption-desorption. The nanometer flower MoS₂ is composed of ultrathin nanosheets of approximately 10 nanometers in thickness. The influence of the reaction temperature and the reaction time on the formation of the flowerlike MoS₂ nanoparticles were evaluated. The optimal experimental conditions were determined as follows: the molar ratio of 1:1 between ethanol and water, the reaction temperature of 190°C, and the reaction time of 24 h. __________ Translated from Chinese Journal of Inorganic Chemistry, 2008, 24(6) (in Chinese)     

片状Co9S8/ZnS/C复合材料的制备及电催化产氧性能

以六水合硝酸钴[Co(NO_3)_2·6H_2O]为钴源、六水合硝酸锌[Zn(NO_3)_2·6H_2O]为锌源、2,2′-硫代二乙酸(C4H6O4S)为硫源,采用溶剂热法制备出了片状的Co_9S_8/ZnS/C复合材料。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和N_2吸附/脱附测试等手段对于片状Co_9S_8/ZnS/C复合材料结构和形貌等进行表征,同时对片状Co_9S_8/ZnS/C复合材料进行了电催化产氧性能测试。结果表明:片状Co_9S_8/ZnS/C复合材料的起始过电位为390 mV,塔菲尔斜率为144 mV·dec~(-1),具有高的电催化产氧性能。     

MOF‐Derived Hollow CoS Decorated with CeOx Nanoparticles for Boosting Oxygen Evolution Reaction Electrocatalysis

Transition‐metal sulfides (TMSs) have emerged as important candidates for oxygen evolution reaction (OER) electrocatalysts. Now a hybrid nanostructure has been decorated with CeO_x nanoparticles on the surface of ZIF‐67‐derived hollow CoS through in situ generation. Proper control of the amount of CeO_x on the surface of CoS can achieve precise tuning of Co²⁺/Co³⁺ ratio, especially for the induced defects, further boosting the OER activity. Meanwhile, the formation of protective CeO_x thin layer effectively inhibits the corrosion by losing cobalt ion species from the active surface into the solution. It is thus a rare example of a hybrid hetero‐structural electrocatalyst with CeO_x NPs to improve the performance of the hollow TMS nanocage.     

p-Aminophenylacetic acid-mediated synthesis of monodispersed titanium oxide hybrid microspheres in ethanol solution

Monodispersed TiO₂ hybrid microspheres were prepared via the hydrolysis of titanium isopropoxide (TTIP) in ethanol solution containing p-aminophenylacetic acid (APA). The effects of the APA:TTIP molar ratio, water content, reaction time and reaction temperature on the morphology of the resultant spheres were investigated. The products were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. It was demonstrated that the diameters of the resultant TiO₂ spheres could be tuned in the range of 380–800 nm by changing the APA:TTIP molar ratio (1:3 to 3:1) and water content (1–3 v/v%) in the reaction medium, and that increasing the APA:TTIP molar ratio led to larger TiO₂ hybrid spheres while increasing the water content decreased their size. The loading content of APA in the hybrid spheres could reach 20 wt.% as they were prepared with the APA:TTIP ratio of 3:1. The possible formation mechanism of the hybrid spheres was also investigated. It was found that APA slowed down the hydrolysis rate of the titanium precursor so that resulted in the formation of the TiO₂ spheres. In addition, the APA present in TiO₂ spheres acted as a reducing agent to in situ convert HAuCl₄ into metallic Au on the surface of the TiO₂ spheres. The catalytic activity of the resultant Au/APA–TiO₂ composite was examined using transfer hydrogenation of phenylacetone with 2-propanol, and it was indicated that the catalyst displayed high efficiency for this reaction.     

Activity of cobalt sulfide catalysts in the hydrogenolysis of dimethyl disulfide to methanethiol: Effects of the nature of a support and the procedure of supporting a cobalt precursor

The conversion of dimethyl disulfide to methanethiol on various catalysts containing supported cobalt sulfide in an atmosphere of hydrogen was studied at atmospheric pressure and T = 190°C. On CoS introduced into the channels of zeolite HSZM-5, the process occurred at a high rate but with a low selectivity for methanethiol because the proton centers of the support participated in a side reaction with the formation of dimethyl sulfide and hydrogen sulfide. Under the action of sulfide catalysts supported onto a carbon support, aluminum oxide, silicon dioxide, and an amorphous aluminosilicate, the decomposition of dimethyl disulfide to methanethiol occurred with 95–100% selectivity. The CoS/Al₂O₃ catalysts were found to be most efficient. The specific activity of alumina-cobalt sulfide catalysts only slightly depended on the phase composition and specific surface area of Al₂O₃. The conditions of the thermal treatment and sulfurization of catalysts and, particularly, the procedure of supporting a cobalt precursor onto the support were of key importance. Catalysts prepared through the stage of supporting nanodispersed cobalt hydroxide were much more active than the catalysts based on supported cobalt salts.     

CoS制备方法研究及在染料敏化电池中应用

通过简单的气-固反应法在氟掺杂的氧化锡导电玻璃(FTO)上成功制备了CoS对电极,并通过优化工艺,进一步确认了制备CoS的最佳浓度。通过扫面电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)、循环伏安测试(CV)、Tafel极化曲线以及光电流密度-电压特性曲线(J-V)分别研究了其表面形貌、物质结构、电催化性能和光电性能。结果表明20%浓度制备的CoS对电极具有较高的电催化活性,在一个标准太阳光照条件下(100mW.cm_-2),其光电转换效率(PCE)是7.81%,短路电流密度(J_sc)是17.3 mA.cm_?2,开路电压(V_oc)是0.74 V,填充因子(FF)是0.61,显示出与Pt对电极(7.97%)相比拟的性能。说明通过这种气-固反应法采用浓度为20%醋酸钴溶液制备的CoS薄膜具有高催化性、低成本的优点,可代替Pt作为染料敏化电池对电极。、关键词用黑体,及关键词内容用宋体。     

碳酸钡单晶微米锥阵列在方解石(104)面上的外延生长

通过液固界面上的溶解-沉淀耦合反应在Ba(NO₃)₂乙醇-水溶液中实现了毒重石晶型的碳酸钡在方解石(CaCO₃)晶体基底上的外延生长, 得到碳酸钡的单晶微米锥阵列. 碳酸钡微米锥的长轴平行于毒重石晶体的[001]方向,同时也与方解石基底[001]晶向相同, 其俯视图为六边形, 具有近似的六方对称性. 随反应时间的增加, 外延生长形成的碳酸钡微米锥的尺寸增加, 但其轴径比逐渐减小. 通过改变乙醇-水混合溶剂中的乙醇含量或者Ba(NO₃)₂浓度也能调控碳酸钡晶体的尺寸和形貌. 随着混合溶剂中乙醇含量与Ba(NO₃)₂浓度的提高, 溶液中BaCO₃的过饱和度增加, 通过外延生长在方解石的(104)表面形成的BaCO₃阵列结构的密集程度逐渐增加, 尺寸逐渐减小, 形貌从微米锥逐渐转变为微米柱状结构. 经过对晶化过程及毒重石和方解石晶体结构分析,提出了在方解石表面外延生长形成的毒重石微米锥单晶阵列结构的形成过程机理: 该过程为界面溶解-沉淀耦合反应的过程,方解石的溶解和毒重石的外延生长过程同时进行, 由于两种晶体在方解石基底的(104)晶面与(001)晶面上具有中高度错配值, 毒重石晶体在方解石的这两个晶面上发生Volmer-Weber型的外延生长, 逐渐形成在靠近基底处包覆有方解石台阶的毒重石微米锥单晶阵列结构.     

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

Urchin-like cobalt incorporated manganese oxide OMS-2 hollow spheres: Synthesis,characterization and catalytic degradation of RhB dye

Urchin-like K_xCo_yMn_8−yO₁₆ hollow spheres assembled from nanoplate building blocks were successfully fabricated via a one-pot hydrothermal route using cobalt acetate and potassium permanganate as raw material. The products were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectrometer, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) measurement. The thermal stability and surface areas of cobalt ion in the manganese sites of KMn₈O₁₆ structures were clearly evidenced by TGA and N₂ adsorption–desorption isotherms curves. Based on time depended experiment results, a possible formation mechanism for this structures was proposed. The catalytic degradation of Rhodamine B (RhB) on K_xCo_yMn_8−yO₁₆ materials has, therefore been dependent for the molar precursor ratio and specific surface area of the as-fabricated products. UV–vis, LC–MS and barium hydroxide methods were utilized to monitor the temporal course of the catalytic reaction.     

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co‐TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co‐PB‐1(6) bearing six Co‐TPP subunits connected through twenty‐four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co‐rPB‐1(6). Both Co‐PB‐1(6) and Co‐rPB‐1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co‐TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

Nicotinic acid-supported cobalt ferrite-catalyzed one-pot synthesis of substituted chromeno[3,4-b]quinolines

One-pot synthesis of substituted chromeno[3,4-b]quinoline derivatives was developed by three-component reaction of aldehydes, dimedone or 1,3-cyclohexadione, and 4-aminocoumarin in the presence of nicotinic acid-supported cobalt ferrite [CoFe₂O₄@SiO₂@Si(CH₂)₃Cl@NA] as a novel magnetic catalyst in chloroform at reflux conditions. Nicotinic acid-supported cobalt ferrite was characterized via Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and vibrating sample magnetometry. Moreover, the catalyst could be easily recovered by magnetic separation and recycled up to five times without significant loss of its catalytic activity. The products formed in excellent yields over appropriate reaction times under environmentally friendly conditions. High efficiency and easy isolation of the catalyst from products by simple magnetic attraction are some of the considerable advantages of this procedure.