Reactions of co-ordinated ligands: Kinetics and mechanisms in the charge transfer interaction between dichloro or diaquo triethylene tetramine Co(III) and ferrocyanide

The cherry red-coloured solid state product obtained by the reaction ofcis-σ diaquo Co (III) triethylene tetramine with ferrocyanide was examined by thermogravimetric, infrared and M?ssbauer techniques. Its electronic spectrum in aqueous medium was interpreted to consist of charge transfer IT transition at 440 nm and a ligand field transition around 330 nm. The kinetics of formation of this 1:1 product in solution was also studied.     

Elimination of zinc interference in the voltammetric determination of cobalt by using iminodiacetic acid

The voltammetric determination of cobalt carried out by adsorbing cobalt dimethylglyoxime onto a mercury electrode and subsequently measuring the current for the reduction of the adsorbed species is subject to interference by zinc. If this interference is neglected and the determination carried out by standard additions large errors may result. The interference can be eliminated by adding iminodiacetic acid.     

Cytotoxic and radiosensitizing effects of nano-C<Subscript>60 </Subscript>on tumor cells in vitro

There is growing evidence in recent years that the pristine fullerene may be endowed with strong pro-oxidant capacity to biological samples. In this investigation we tested the hypothesis that water-soluble fullerene-C₆₀ (nano-C₆₀) may interact with ionizing radiation enhancing its antiproliferative effects. The two tumor cell lines with different radiosensitivity B16 and SMMU-7721 were treated by a combination of pristine fullerene and ⁶⁰Co γ irradiation. We measured cell survival rates, apoptotic characteristics, reactive oxygen species (ROS) production and alteration of cell diameter with or without γ-irradiation. There was reduced survival with B16 and SMMU-7721 cells exposed to nano-C₆₀, with the inhibitory concentrations reducing the viability by 50% to 65 part per billion (ppb) and 150 ppb respectively. For cells exposed to nano-C₆₀ prior to γ-irradiation, damage to cell membranes and increased numbers of apoptotic cells were detected by morphologic Hoechst-staining analysis and Annexin V/propidium iodide double-staining. In cells exposed to nano-C₆₀, there were increased levels of ROS, as measured by fluorescence detection under laser confocal microscopy. Preincubation with non-toxic pristine C₆₀ before γ-ray caused enlargement of cells with increased diameter. The results show that nano-C₆₀ inhibits the growth of tumor cells at certain concentrations and increases the effects of ⁶⁰Co γ-irradiation, possibly through the elevated production of cellular ROS and the membrane disruption. Data in this study indicates a possible consideration of using C₆₀ as a candidate of sensitization modifier in tumor radiation biology.     

The quasicrystal-crystal interface between icosahedral Al-Pd-Mn and deposited Co: Evidence for the affinity of the quasicrystal structure to the CsCl structure

We have evaporated Co on the pentagonal surface of an icosahedral Al-Pd-Mn quasicrystal kept at room temperature. For submonolayer Co deposits, five AlCo domains are formed exposing their (1 1 0) faces parallel to the surface and rotated by 72° with respect to each other. The orientational relationship between these domains and the substrate is determined by the optimum matching of the average quasicrystal structure and the CsCl structure with a lattice constant of about 2.88 Å. For further deposition, body-centred cubic Co domains grow epitaxially on the AlCo domains.     

Magnetic properties of single crystalline Zn1−xCoxO thin films

We report on the magnetic properties of single crystalline thin films of Zn_1−xCo_xO (x=0.003–0.14) grown by plasma-assisted molecular beam epitaxy. In order to understand the role of intermediate charge carriers in the magnetic properties of this material two types of films were fabricated, with and without Ga-codoping. Magnetic measurements were made between 2 and 300 K in fields up to 5 T with a Quantum Design SQUID magnetometer. We found that all the tested films exhibit paramagnetic behavior following the Curie–Weiss law, χ=C/(T−θ), with negative Curie–Weiss temperatures and that this behavior holds even under strong n-doping. We show that the magnetization data, M(H), in function of the Co content provide additional evidence in favor of the antiferromagnetic Co–Co interaction in this material. We also observe that these data exhibit an ‘easy plane’ magnetic anisotropy for all the studied Co concentrations. Finally, we develop a simple cluster model, in order to describe the magnetic properties of ZnCoO, which is found to be in good agreement with our experiments.     

A cobalt (II) complex based on antipyrine derived schiff base as colorimetric sensor for Fe3+ ion

A novel complex [Co(NO₃)₂(APTY)₂H₂O] (1) is synthesized based on 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one) antipyrine (APTY) and the structure of complex (1) is characterized via PXRD, SEM, FTIR and X-ray single crystal diffraction technique. It is found that the complex (1) has a good response to Fe³⁺ ion with colorimetric yellow change. In addition, we demonstrate that the sensing mechanism of complex (1) could is due to the disruption of complex (1) framework and the formation of complex Fe-APTY. The stability, rapid response and low detection limit enable this complex (1) to be a good Fe³⁺ ion chemical sensor for biological and environmental sensing applications.     

The influence of P/As substitution in the melilite‐like Na2Co(P2–xAsx)O7 (x = 0.40 and 0.93) solid solutions

To investigate the influence of P/As substitution on structures and electrical properties, e.g. the effect on material densities, two new solid P/As‐doped solutions, Na₂CoP_1.60As_0.40O₇ (disodium cobalt diphosphorus arsenic heptaoxide) and Na₂CoP_1.07As_0.93O₇ (disodium cobalt phosphorus arsenic heptaoxide), with melilite‐like structures have been synthesized by solid‐state reactions. Their unit‐cell parameters are in agreement with Vegard's law. The obtained structural models were investigated by the bond valence sum (BVS) and charge distribution (CHARDI) validation tools and, for the latter, the structures are described as being built on anion‐centred polyhedra. The frameworks can be described as layered and formed by {[Co(P,As)₂O₇]²⁻}_∞ slabs, with alkali cations sandwiched between the layers and with the interlayer spaces increased due to P/As substitution. The BVS model was extended to a preliminary simulation of the sodium conduction properties in the studied structural type and suggests that the most probable sodium conduction pathways are bidimensional, at the (002) planes.     

弱磁性Co0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

氢气是一种环境友好可再生的清洁能源,电解水无疑是一种很好的制氢方法.然而,电催化分解水析氢受到其缓慢的动力学过程、较低的催化性能和较差的稳定性的限制.为了使整个过程更节能,具有高电流密度和低的过电势的高效电催化剂被广泛研究.非化学计量相硒化钴(Co0.85Se)作为一种重要的金属硫属化合物具有优异的催化性能而广受关注.但是低维的Co0.85Se活性位点少,分散性差,电子传递能力低,导致其电催化剂活性差.多壁碳纳米管(MWCNTs)具有多种电性能,包括金属导电性和电子存储能力等.因此,MWCNTs的特殊结构和高导电性可以有效地促进电子从电催化剂向碳纳米管的转移,实现高效电分解水制氢性能.本文在不使用表面活性剂和模板的情况下,通过一步水热溶剂热法合成弱磁性Co0.85Se纳米片负载碳纳米管电催化剂.采用磁滞回线研究Co0.85Se和MWCNTs/Co0.85Se的磁性能,结果表明其有弱顺磁性,Co0.85Se纳米片之间的空间距离增强导致粒子间偶极相互作用减弱,从而使MWCNTs/Co0.85Se纳米复合材料的矫顽力值增加到158 Oe.随着微晶尺寸的减小和纳米颗粒间距的增大,MWCNTs/Co0.85Se催化剂的比表面积增大,有利于提高其电催化活性.扫描电镜和透射电镜展示出Co0.85Se纳米片分散性较差,且团聚现象严重,而MWCNTs/Co0.85Se纳米复合催化剂显示Co0.85Se纳米片均匀分散在MWCNTs表面,且纳米片尺寸明显减小,有利于Co0.85Se纳米片暴露更多的活性位点.线性扫描伏安曲线测量表明,在酸性溶液中Co0.85Se纳米片在电流密度为10 mA cm?2时,其过电势为319 mV(vs.RHE),30 wt%MWCNTs/Co0.85Se的过电势为266 mV(vs.RHE).Co0.85Se和MWCNTs/Co0.85Se的Tafel斜率分别为92.6和60.5 mV dec?1.此外,MWCNTs/Co0.85Se的电流交换密度(j0)为0.07 mA cm?2.较小的Tafel斜率和高的电流交换密度表明,MWCNTs/Co0.85Se具有良好的反应动力学和快速的质子分离速率.交流阻抗谱表明MWCNTs/Co0.85Se比Co0.85Se电阻更小,电子传输速率更快.电化学活性表面积与双电层在固液界面处的电容测量值成正比.结果显示,30 wt%MWCNTs/Co0.85Se的双电层电容为0.22 mF cm^-2,高于Co0.85Se和15 wt%的rGO/Co0.85Se(0.04 mF cm^-2,0.17 mF cm^-2),这表明较大的电化学活性表面积有利于析氢反应进行.30 wt%MWCNTs/Co0.85Se的循环稳定测试表明其具有较好的稳定性.综上,本文介绍了通过一步水热法合成具有弱磁性的Co0.85Se和MWCNTs/Co0.85Se电催化剂,碳纳米管作为一种高导电性材料被引入Co0.85Se纳米片中以减少Co0.85Se的团聚,使Co0.85Se的活性位点增加,进而提高电催化制氢性能.     

Recent developments in Pt–Co catalysts for proton-exchange membrane fuel cells

Development of Pt-based oxygen reduction reaction catalysts with high efficiency and high durability is central to the application of proton-exchange membrane fuel cell systems. Pt–Co bimetallic catalysts have drawn extensive attention owing to their capability of delivering high performance and long lifetime for fuel cell applications including light-duty and heavy-duty vehicles. However, further improvements in durability and performance are needed to meet market requirements. To fully exploit the potential of Pt–Co catalysts, new insights into the relationship between catalyst properties and fuel cell performance and durability are needed, and more effective methods to tailor the features of Pt–Co catalysts need to be developed. This review provides a summary and perspective on recent efforts, including work on customizing the Pt shell and Pt:Co ratio, tailoring the crystal structure, and improving carbon support properties, with a particular emphasis on mechanisms leading to enhancement of mass activity, power density, and durability in membrane electrode assembly testing.