Simultaneous determination of cobalt,nickel and iron by multi-wavelength spectrophotometry

A method for the simultaneous spectrophotometric determination of cobalt, nickel and iron based on the formation of their complexes with 1,5-bis(di-2-pyridylmethylene) thiocarbonohydrazide is proposed. The absorption curves of these complexes overlap severely in the scanning range 390–510 nm. The analyte concentrations are calculated by a least squares fit of the pure spectra to the mixture spectra, which therefore makes the simultaneous determination of these metallic ions possible without tedious pretreatment. The detection limits afforded by the proposed method range from 0.05 g/ml for Fe and Ni to 0.1 g/ml for Co. Root-mean-squared errors of prediction of 0.085 g/ml for Co, 0.048 g/ml for Ni and 0.1172 g/ml for Fe were obtained using the wavelength range 400–510 nm and 0.147 g/ml for Co, 0.107 g/ml for Ni and 0.127 g/ml for Fe using the wavelength range 420–434 nm. The effect of interferences is studied and the proposed method is applied to analysis for the above elements in synthetic samples and real samples, such as biological materials and alloys.     

Anodic dissolution of magnetic layers based on cobalt and nickel in conditions of electrodeposition of multilayered nanostructures by a single-bath method

Methods of quartz microgravimetry (in solutions containing no copper ions) and stripping voltammetry (in copper-containing solutions) are used to study the process of anodic dissolution of thin deposits of pure Co and Ni and deposits of these metals with inclusion of copper in the potential region of copper deposition. It is shown that, under these conditions, Ni practically does not dissolve in either the sulfate or chloride-containing electrolytes, whereas Co dissolves in sulfate electrolytes at a rate that is dependent on the potential and increases with its shift into the positive region. Stability of ternary CoNiCu deposits is examined and it is demonstrated that additionally inserting Ni in the composition of a magnetic CoCu layer facilitates suppression of selective dissolution of Co.     

Design of alkaline metal ion conducting polymer electrolytes

Polysiloxanes with covalently attached oligo ethylene oxide and di-t-butylphenol ( I ), naphthol ( II ), and hexafluoropropanol ( III ) were synthesized. The crosslinked polymers with a hexamethylene spacer were also prepared. The ion conductivities of the Li, Na, and K salts were measured as a function of temperature. The highest conductivities for K and Na of I at 30°C were 5.5 × 10^?5 and 5.0 × 10^?5 S/cm, respectively, when the ratio of the ion to ethylene oxide unit was 0.014. On the other hand, Li conductivity was 8.0 × 10^?6 S/cm when the ratio between Li and ethylene oxide unit was 0.019. The maximum conductivities of Li ions of II and III were in the order of 10^?6 and 10^?7 S/cm at 30°C, respectively. When the polymers were crosslinked by a hexamethylene residue, the ion conductivities decreased while the degree of crosslinking increased. The temperature dependence of the cation conductivities of these systems could be described by the Williams-Landel-Ferry (WLF) and the Vogel-Tammann-Fulcher (VTF) equation. The results demonstrate that ion movement in these polymers is correlated with the polymer segmental motion. The order of ionic conductivity was K⁺ > Na⁺ ? Li⁺. This suggests that steric hindrance and π-electron delocalization of the anions attached to polymer backbone have a large effect on ion-pair separation and their ionic conductivities. Thermogravimetric analysis of the polymers indicated that the degradation temperature for I and II were about 100°C higher than for poly(siloxane-g-ethylene oxide). This is due to the antioxidant properties of sterically hindered phenols and naphthols. © 1993 John Wiley & Sons, Inc.     

Peculiarities of polythermic decomposition of iron,cobalt and nickel oxalates within pores of photonic crystals based on SiO<Subscript>2</Subscript> in atmosphere with oxygen lack

Iron(II), cobalt(II) and nickel(II) oxalates were synthesized as nanofractals inside the voids of the photonic crystals based on SiO₂. Guest substances undergone polythermic decomposition within the pores of the photonic crystals in helium atmosphere containing of oxygen traces (∼1 Pa) under static conditions. Pyrolysis of Fe(COO)₂·2H₂O, Co(COO)₂·2H₂O and Ni(COO)₂·2H₂O studied by TG and DSC techniques results in the formation of the metal oxides. The nanoparticles of Fe₂O₃, CoO (Co₃O₄) and NiO populated the interspheric voids of the photonic crystals exhibited no ferromagnetic effects indicating that no metallic inclusions were formed in helium in the presence of O₂ traces. The exothermic effect was observed by the thermal decomposition of the cobalt(II) oxalate only under oxygen lack.     

Four-component relativistic computational NMR study of ferrous,cobalt and nickel bisglycinates

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Electrochemical arylation of cobalt and nickel chelates with diphenyliodonium salts

Electrochemical arylation of cobalt chelates with diphenyliodonium salts occurs at low cathodic potentials (viz., potential of the first reduction wave of the diphenyliodonium salt) and affords the phenyl derivatives of Co^III chelates containing the -Co—C(sp²) bond. Nickel complexes should be arylated at higher cathodic potentials because it is necessary to generate paramagnetic Ni^I complexes.     

An adsorptive stripping voltammetry of nickel and cobalt at a solid lead electrode

For the first time, a solid lead electrode (PbE) was exploited for adsorptive stripping voltammetric determination of Ni(II) and Co(II) in the presence of nioxime as a complexing agent. The calibration graphs for Ni(II) and Co(II) were linear from 0.059 to 0.59 µg L^?1 and from 0.029 to 0.29 µg L^?1 (accumulation time 120 s), respectively. The analytical parameters such as the detection limit and separation of analytical signals obtained at the solid lead electrode were comparable with those obtained using a lead film electrode while better in comparison to those reported before for the bismuth film or solid bismuth electrodes. Co(II) could be determined in the presence of a large excess of Ni(II) and Zn(II). The proposed electrode was applied to determine Co(II) and Ni(II) traces in certified reference material and a natural water sample with satisfactory results.     

不对称二亚胺异双核钴镍催化剂的合成及乙烯聚合研究

合成了不对称异双核钴镍催化剂MN5CoNi.该催化剂经AlEt3,MMAO,AlEt3/[PhMe2NH][B(C6F5)4](B)或MMAO/B活化后用于乙烯聚合.异双核催化剂与相应的等摩尔双组分混合单核催化剂相比,以TEA作助催化剂时,异双核催化剂的Co和Ni中心的活性都远低于双组分混合体系,且Ni中心生成的聚乙烯含量低于双组分混合体系,异双核催化剂中的Co和Ni中心同时被抑制.以MMAO作助催化剂时,异双核催化剂的活性虽低于双组分混合体系,但是异双核催化剂中的两种金属中心的活性都有了较大的提高,且Ni中心生成的聚乙烯含量高于后者.同时考察了活性随时间变化,发现异双核催化剂中活性衰减比双组分混合体系慢,说明异双核体系中Co和Ni中心在MMAO活化下比双组分混合体系的金属中心更稳定.当以TEA/B作助催化剂时,异双核催化剂中Co和Ni中心的活性有所提高,但仍远低于双组分混合体系,且Ni中心生成的聚乙烯含量低于后者,说明Ni被选择性抑制.当使用MMAO/B作助催化剂时,结果与MMAO类似.     

Principles of Water Electrolysis and Recent Progress in Cobalt-, Nickel-, and Iron-Based Oxides for the Oxygen Evolution Reaction

Water electrolysis that results in green hydrogen is the key process towards a circular economy. The supply of sustainable electricity and availability of oxygen evolution reaction (OER) electrocatalysts are the main bottlenecks of the process for large-scale production of green hydrogen. A broad range of OER electrocatalysts have been explored to decrease the overpotential and boost the kinetics of this sluggish half-reaction. Co-, Ni-, and Fe-based catalysts have been considered to be potential candidates to replace noble metals due to their tunable 3d electron configuration and spin state, versatility in terms of crystal and electronic structures, as well as abundance in nature. This Review provides some basic principles of water electrolysis, key aspects of OER, and significant criteria for the development of the catalysts. It provides also some insights on recent advances of Co-, Ni-, and Fe-based oxides and a brief perspective on green hydrogen production and the challenges of water electrolysis.     

The mechanism of pulse anodic activation of iron dissolution in acid solutions

Basing on the model of spatial separation of the dissolution and passivation of hydrophilic metals, formation of stationary surface morphology during pulse anodic activation of iron dissolution in sulfuric acid solutions is analyzed.     

Thermal decomposition of nicotinate complexes of cobalt and nickel in dynamic nitrogen atmosphere

Thermal decomposition of cobalt and nickel nicotinate was studied by TG, DTG and DSC. The mechanism of decomposition has been established from TG and DSC data. The kinetic parameters namelyE, A together with ΔH were calculated from DSC curves using mechanistic and non-mechanistic integral equations.

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Zusammenfassung Mittels TG, DTG und DSC wurde die thermische Zersetzung von Cobaltund Nickelnikotinat untersucht. Der Zersetzungsmechanismus wurde anhand der TG-und DSC-Daten entwickelt. Die kinetischen ParameterE, A wurden zusammen mit ΔH anhand der DSC-Kurven mit Hilfe von mechanistischen und nichtmechanistischen Integrationsgleichungen berechnet.

     

Sonochemical synthesis under a magnetic field: fabrication of nickel and cobalt particles and variation of their physical properties

We report on the variation of the physical properties of nickel and cobalt nanoparticles prepared by using ultrasound irradiation as energy source. First, we describe a sonochemical method for preparing aggregated particles. Second, we interpret the results on the basis of Einstein's theory (1905), which deals with a mathematical expression for the diffusivity of particles into solvents. This theory explains the stability of organosols of nickel and cobalt nanoparticles in polyethylene glycol. Finally, the effect of applying an external magnetic field during sonochemical formation of both aggregated particles and their stable colloids is investigated.     

Anodic Oxidation of Silver Alloys in Concentrated Sulfuric Acid Solutions

Anodic oxidation of Ag–Cu and Ag–Pd alloys in concentrated sulfuric acid solutions is studied by cyclic voltammetry. Influence of electronegative (Cu) and electropositive (Pd) constituents on the rate and mechanism of the silver electrooxidation in non-steady-state conditions is revealed. The maximum silver oxidation current increases with the copper content due to a decreased H₂SO₄ concentration in the near-electrode layer and increased solubility of passivating phase Ag₂SO₄. The mechanism of ionization of palladium-doped silver is complicated by two electrochemical reactions involving the formation of Ag₂SO₄ and Ag⁺ _solv.     

Synthesis of cobalt A2B triaryl corroles bearing methoxy or hydroxyl groups and their activity in electrocatalytic hydrogen evolution

Four A₂B cobalt corrole complexes 1 – 4 appending two methoxy or hydroxyl groups on the 10-meso phenyl group had been synthesized. Four cobalt corroles showed high electrocatalytic activity for hydrogen evolution reaction (HER) in the organic phase and in the aqueous phase. The hydrogen evolution pathway was EECEC when using acetic acid as proton source. When trifluoroacetic acid was used as proton source, the hydrogen evolution route via EECEC or EECC depending on the concentration of trifluoroacetic acid. Cobalt corrole 4 showed the best HER performance with the k_obs of 122.68 s⁻¹ in organic phase and the TOF of 832.2 h⁻¹ in aqueous phase respectively. The results suggested the phenyl hydroxyl group at the cobalt corrole peripheral may act as the proton relay group in HER and the o-hydroxyl of phenyl was better than m- hydroxyl for proton relay.     

双金属离子调控型镍钴氧化物纳米片用于非对称超级电容器

通过水热-煅烧两步法制备了系列镍钴氧化物（NCO）纳米片。通过改变前驱体溶液中的镍、钴离子物质的量之比,进而调控NCO纳米片中的过渡金属离子比例。NCO纳米片的晶相、形貌和结构利用X射线衍射、扫描电子显微镜和X射线光电子能谱表征。此外,对NCO纳米片的电化学性能进行测试。结果表明,NCO-2（Ni_1.95Co₁O_x）纳米片在0.5 A·g^-1电流密度下,比电容为1 096.88 F·g^-1,且经过5 000次循环后具有78.26%的循环稳定性。以NCO-2为正极、活性碳为负极构成的非对称超级电容器,在功率密度为576 W·kg^-1时,能量密度为57.70 Wh·kg^-1。     

双金属离子调控型镍钴氧化物纳米片用于非对称超级电容器

通过水热-煅烧两步法制备了系列镍钴氧化物(NCO)纳米片。通过改变前驱体溶液中的镍、钴离子物质的量之比，进而调控NCO纳米片中的过渡金属离子比例。NCO纳米片的晶相、形貌和结构利用X射线衍射、扫描电子显微镜和X射线光电子能谱表征。此外，对NCO纳米片的电化学性能进行测试。结果表明，NCO-2(Ni_1.95Co₁O_x)纳米片在0.5 A·g^-1电流密度下，比电容为1 096.88 F·g^-1，且经过5 000次循环后具有78.26%的循环稳定性。以NCO-2为正极、活性碳为负极构成的非对称超级电容器，在功率密度为576 W·kg^-1时，能量密度为57.70 Wh·kg^-1。     

Synthesis of triple-decker iron and cobalt complexes with a central tetramethylphospholyl ligand

30-Electron triple-decker complexes [(η-C₅H₅)Fe(μ-η:η-C₄Me₄P)Fe(η-C₅Me₅)]PF₆ and [(η-C₄Me₄)Co(μ-η:η-C₄Me₄P)Fe(η-C₅Me₅)]PF₆ with a central tetramethylphospholyl ligand were synthesized by stacking reactions of cationic fragments [(η-C₅H₅)Fe]⁺ and [(η-C₄Me₄)Co]⁺ with nonamethylphosphaferrocene (η-C₄Me₄P)Fe(η-C₅Me₅). Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1647–1649, September, 2000.     

PVC matrix membrane electrodes based on cobalt and nickel phenanthroline complexes for selective determination of cobalt(II) and nickel(II) ions

Potentiometric sensors for determining cobalt and nickel ions are described. They are based on the use of cobalt and nickel tris(1,10-phenanthroline)-TPB as electroactive compounds dispersed in plasticized poly(vinyl chloride) matrix. The sensors exhibit fast, near-Nernstian responses for cobalt and nickel-phenanthroline cations over the pH range 3–11 with a slope of 30.3 ± 0.3 mV/concentration decade. In the presence of excess 1,10-phenanthroline reagent, cobalt(II) and nickel(II) ions at concentration levels as low as 4 × 10^–6 M are accurately determined. The results show an average metal ion recovery of 98.5% with a mean standard deviation of 0.5%. Cobalt in organometallic compounds and nickel in silicate rocks are determined by these sensors and results agreeing fairly well with atomic absorption spectrometry are obtained.     

Phase‐Junction Electrocatalysts towards Enhanced Hydrogen Evolution Reaction in Alkaline Media

To ensure sustainable hydrogen production by water electrolysis, robust, earth‐abundant, and high‐efficient electrocatalysts are required. Constructing a hybrid system could lead to further improvement in electrocatalytic activity. Interface engineering in composite catalysts is thus critical to determine the performance, and the phase‐junction interface should improve the catalytic activity. Here, we show that nickel diphosphide phase junction (c‐NiP₂/m‐NiP₂) is an effective electrocatalyst for hydrogen production in alkaline media. The overpotential (at 10 mA cm^?2) for NiP₂‐650 (c/m) in alkaline media could be significantly reduced by 26 % and 96 % compared with c‐NiP₂ and m‐NiP₂, respectively. The enhancement of catalytic activity should be attributed to the strong water dissociation ability and the rearrangement of electrons around the phase junction, which markedly improved the Volmer step and benefited the reduction process of adsorbed protons.