Elucidation of interference mechanisms caused by iron on stibine electrochemical generation by differential pulse anodic stripping voltametry. A case study

The interference effect caused by the presence of iron – both (II) and (III) oxidation states – on the electrochemical generation of SbH₃ has been characterized. Interference from Fe(III) was more severe than for Fe(II). Total signal suppression was obtained for a Fe(III) : Sb(III) concentration ratio of 5 : 1, whereas a 40% suppression was obtained for Fe(II). A mechanism is proposed based on the results obtained by differential pulse anodic stripping voltametry. The standard conditions used for the hydride electrochemical generation were simulated in the differential pulse anodic stripping voltametry measurements in order to achieve valid conclusions. The reduction of Fe(II) onto the cathode surface prevents the formation of stibine avoiding the recombination of Sb⁰ with the hydrogen atoms adsorbed on the surface. The mechanism by which the Fe(III) interferes on the stibine formation is related to the co-deposition of the iron and antimony that also avoid the further recombination of the Sb⁰. The formation of a specie of stoichiometry not determined (probably 1 : 1) on the cathode surface may justify the larger interference effect observed for the Fe(III).     

极谱法测定矿石及冶金渣中铍含量

矿石及冶金渣试样与过氧化钠在700℃熔融,用温水浸取,以一定量盐酸酸化后定容。分取部分试样溶液使其中铍(Ⅱ)与铍试剂Ⅲ在EDTA、氯化铵和氨水底液中,生成稳定的配合物,该配合物于-0.80V(vs.SCE)处产生一灵敏的吸附波,其峰电流的二阶导数与铍(Ⅱ)的质量浓度在0.004~0.20mg·L-1范围内呈线性关系,检出限(3S/N)为0.3μg·L-1。方法用于了7个矿石及冶金渣样品的分析,所得测定值与认定值一致。方法的加标回收率在96.0%~105%之间,相对标准偏差(n=6)在1.3%~9.7%之间。     

Co-MCM-41催化H2O2氧化4-甲基吡啶生成4-吡啶甲酸的反应条件及机理

研究了乙酸溶剂中无引发剂条件下,Co掺杂MCM-41催化过氧化氢（30%）氧化4-甲基吡啶的反应,催化剂表现出高底物转化率和产物吡啶甲酸选择性以及良好的再生性。 探讨了不同溶剂、反应时间、反应温度、催化剂用量等对H2O2氧化4-甲基吡啶反应的影响,确定较优反应条件为m（4-甲基吡啶)∶m（催化剂)=10∶1,V（4-甲基吡啶)∶V（冰醋酸)=1∶10,温度363 K,时间6 h。 该条件下4-甲基吡啶的转化率为96.5%,4-吡啶甲酸的选择性为91.4%。 探讨了可能的反应机理。     

Atom diffusion in furnaces — models and measurements

Experimental as well as the theoretical approach to estimate diffusion coefficients for several analyte elements with different behavior in graphite furnaces, lead, gold, indium and chromium, were investigated. ‘Close’ graphite furnaces of two designs differing in the size of end apertures and the diameter of the injection port were used. The furnaces were fast heated at rates of approximately 10 000 K s⁻¹. The peak absorbance of all studied analytes was independent of geometry, suggesting that the separation of atomization and removal was attained. Residence times of the analytes in the two different furnaces were determined from absorbance tail shapes. In the case of gold, the influence of temperature in the range between 1800 and 2200 K on the residence time in both furnaces was also found. The residence times measured in the two different furnaces under otherwise identical conditions, made possible to select the accurate model of diffusional removal from several possible models. The knowledge of the accurate model allowed the estimate of experimental diffusion coefficients. They were thus compared with those semiempirically calculated from kinetic theory of gases, extended to allow for the intermolecular forces. The accuracy of these calculations is limited since the input data (critical temperatures, boiling temperature or melting temperature, molal volumes at the critical, boiling and melting points, metallic crystallographic radii and dissociation constants of metal dimers) are not known with adequate accuracy. The comparison of ‘theoretical’ and ‘experimental’ values of diffusion coefficients makes possible to assess value of using individual sources of input data for the semiempirical calculations.     

火焰原子吸收光谱法测定工业硅中的铜

采用氢氟酸-硝酸分解试样,用高氯酸蒸发至冒烟除去硅;在硝酸介质(5%)中,采用火焰原子吸收光谱法于324.8nm波长处测定工业硅中铜含量。方法能有效地消除硅的干扰,测量结果相对标准偏差在5%以内,加标回收率在99.0%~102%。方法具有操作简便、快速、容易掌握、成本低的优点。     

Liquid-liquid extraction of iron(III) and gallium(III) with macrocyclic Schiff bases containing bisphenol A subunits

The quantitative extraction of iron(III) and gallium(III) was investigated with the recently synthesized macrocyclic Schiff base containing bisphenol A subunits. The phenol groups in the Schiff base moiety led to a large increase in the percent extraction of trivalent metal ions. The substitution of methoxy groups for phenolic OH ligands resulted in a marked decrease in the extractability of metal ions, and no iron(III) was extracted. The corresponding acyclic Schiff base was found to have a reasonable reactivity toward metal ions and a better solubility in organic solvents. The iron(III) and gallium(III) complexes with macrocyclic and acyclic Schiff bases were quantitatively extracted into nitrobenzene without the presence of bulky counter anions. A single extraction gave a good separation of iron(III) from iron(II) in the mole ratios 4:1 to 1:3. The red iron(III) complexes can be used for the extraction-spectrophotometric determination of iron(III). The apparent molar absorptivity at 518 nm is 5.43 × 10³lmol⁻¹ cm⁻¹.     

改进锂离子电池正极材料磷酸锰锂电化学性能的研究进展

磷酸锰锂(LiMnPO4)是一种非常有前途的锂离子电池正极材料,它具有理论容量高、工作电压高、成本低和对环境友好等优点。然而,该材料存在电子电导率低和锂离子扩散慢的问题,导致其电化学活性非常低。尽管可以通过碳包覆、离子掺杂或替换、晶粒纳米化等方法改进LiMnPO4的电化学性能,但是,高倍率性能低等仍然是阻碍该材料实际应用的主要问题,如何提高LiMnPO4的电化学反应动力学性能,特别同时提高其电子电导率和锂离子扩散能力仍是该领域亟待解决的关键问题,本文就国内外近年有关改进锂离子电池正极材料磷酸锰锂电化学性能的研究进展进行一个简短总结。     

La(OH)3负载锌铝水滑石的制备及其应用在锌镍二次电池中的性能

采用共沉淀法将氢氧化镧(La(OH)₃)负载在锌铝水滑石(Zn-Al LDHs)的表面,扫描电镜(SEM)、X射线衍射(XRD)表明La(OH)₃成功负载在锌铝水滑石表面,并且负载后的锌铝水滑石仍然为六边形片状晶体,且粒径均匀、分散性好。La(OH)₃质量其具有较好的可逆性、更大的正腐蚀电位及较小的电池内阻。5%La(OH)₃@Zn-Al LDHs在经过80次循环后,其循环保持率为94.84%。