Transition Metal Sulfates Research Articles

Development of Low Cost Synthesis Route to Sodium Transition Metal Sulfate Systems

Efficient energy storage devices have come into the spotlight for both consumer devices, transport and large scale grid applications. Whilst Li-ion batteries are a popular choice for the portable electronics and transport market, Na-ion batteries are attracting significant attention for potential use in large scale grid storage, due to showcasing a similar chemistry to lithium but at a lower cost. Of particular interest are sulfate-based systems due to the advantageous inductive effect of the polyanion influencing the redox couples. Thus on this theme, one notable example which has attracted attention is alluaudite-type Na2Fe2(SO4)3whereby the Fe2+/Fe3+ redox delivered 3.8 V – the highest known redox couple for a sulfate system.1 Work by Driscoll et al., showed that new alluaudite systems, Na3M1.5(SO4)3-x(SeO4)x, could be obtained through dehydration of selenate doped Na2M(SO4)2.2H2O (M = Mn, Fe, Co and Ni).2 In this poster, we present an extension of this work, highlighting the relationship between the obtained structure type on dehydration and the metal cation size/polyanion size. 1 P. Barpanda, G. Oyama, S. I. Nishimura, S. C. Chung and A. Yamada, Nat. Commun., 2014, 5, 1–8. 2 L. L. Driscoll, E. Kendrick, K. S. Knight, A. J. Wright and P. R. Slater, J. Solid State Chem., 2018, 258, 64–71. Figure 1

The effects of transition metal sulfates on cellulose crystallinity during accelerated ageing of silver fir wood

During the hydrolytic degradation of cellulose caused by acidic transition metal sulphates, new low molecular products such as monosaccharides and their degradation products are usually formed which can increase the cellulose sensitivity to oxidation. This work was aimed at elucidation of the chemical and structural changes of cellulose in silver fir (Abies alba Mill.) wood treated with iron, copper and zinc salts to achieve a detailed understanding of cellulose deterioration during accelerated ageing. Cellulose samples were isolated from the wood by the Kurschner-Hoffer method and the Seifert method. Changes in cellulose structure were evaluated by wide-angle X-ray scattering (WAXS) measurements, Fourier transform infrared spectroscopy (FTIR), and high performance liquid chromatography. The presence of metal cations (Cu2+, Zn2+, Fe3+) caused a significant loss in the content of cellulose for treated and aged wood samples. Wet-thermal accelerated ageing led to a decrease (~ 20%) in the content of monosaccharides. The Seifert cellulose samples had a higher crystallinity than the Kurschner-Hoffer samples. A strong correlation was found between crystallinity indices obtained from the FTIR and WAXS measurements. Two cluster groups of cellulose samples, segregated from each other, were identified within each cellulose type in a multivariate cellulose trait analysis.

Oil Palm Empty Fruit Bunches Fiber-Supported Heterogeneous Acid Catalyst for Esterification of Oleic Acid: Effect of Different Transition Metal Sulfate

This paper presents the investigation of oil palm empty fruit bunch (EFB) fiber-supported heterogeneous acid catalyst that was prepared via direct impregnation method by using various types of transition metal sulfates, including Fe2(SO4)3, NiSO4.6H2O, and CuSO4. The EFB fiber-supported heterogeneous acid catalyst was applied for esterification of oleic acid. Hence, structural, chemical, morphological, and elemental properties of the catalyst were examined through the use of X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscope (SEM), and electron dispersive X-ray spectroscopy (EDX) analyses. Meanwhile, the acidity properties of each catalyst were characterized via acid density test. The prepared catalyst, which had been loaded with Fe2(SO4)3, exhibited the highest acid density up to 2.4 mmol/g. Next, the catalytic activity of the heterogeneous acid catalyst was further investigated through esterification of oleic acid at 60°C with 5 wt% catalyst loading for 2 hours of reaction time. The prepared catalyst, which was loaded with Fe2(SO4)3, again displayed the high esterification conversion rate at 93.90% and was used up to five reaction cycles.

Viscometric studies of divalent transition metal sulphates in mixtures of water–diethylene glycol at 298.15–318.15 K

Relative viscosities of divalent transition metal sulphates solutions, viz. manganese, cobalt, nickel, copper, zinc and magnesium sulphate has been determined in water–diethylene glycol mixtures. Effect of temperature on the viscosities at 298.15–318.15 K has been studied and B coefficients of Jones–Dole equation are determined for these solutions. The obtained parameters have been interpreted in terms of ion–ion and ion–solvent interactions. Magnesium sulphate is taken as the reference electrolyte to see the change in the behavior of divalent ions when we shift from divalent transition metal ions to some other divalent ions in these solutions. Here these transition metal and magnesium sulphates behave in the same manner i.e structure makers in both water and in DEG + water mixtures.

Conditioning Safety Index of Ni-Rich Cathode Oxides for Lithium Ion Batteries

Ni-rich cathode materials with high energy density has degradation issue of electrochemical performance due to the significant side reaction between electrolyte and cathode. To solve this, a Full Concentration Gradient (FCG) materials consisting of a high-Ni core and a relatively high-Mn outer layer was designed to provide improved stability as well as cycle life characteristic. However, a Ni-rich core still has some possibilities to be contact with electrolyte, especially if the particle in the core part is unexpectedly porous. We found the strategy to tune the particle porosity by controlling a feed rate of transition metal sulfate solutions and ammonium hydroxide solution during co-precipitation synthesis using Continuous Stirred Tank Reactor (CSTR). Additionally, the effect of surfactant was studied in the standpoint of the electrode stability. The structural characteristics was compared for the materials obtained by different feed rate with analysis of by X-ray diffraction, electron microscopy and dynamic light scattering. The interfacial kinetic reaction between the delithiated Ni-rich cathode and a nonaqueous electrolyte was investigated by our home-built high-precision leakage current measurement system. The result of this study indicated a different reaction phenomenon and further implies that the safety of Ni-rich cathode by co-precipitation could be controlled.

Morphology and dehydration mechanism of transition metal sulfate heptahydrates

Processes and thermodynamic parameters of dehydration of transition metal (Ni, Co, and Fe) sulfate heptahydrate crystals grown in aqueous solutions have been investigated by optical thermomicroscopy, X-ray analysis, and differential scanning calorimetry. Values of temperature and specific heat of the first stage of dehydration have been determined, as well as the conditions under which the process was reversible. The morphology of the common topochemical reaction, as well as the mechanism of this reaction, has been characterized. The dehydration process has been shown to depend on multiple physical parameters and to consist in the growth of non-oriented crystals of the new phase with concomitant exudation of the water of crystallization.

Activation Energy Parameters for Hydrodynamic Permeability of Binary Aqueous Solutions of Divalent Transition Metal Sulphates and Magnesium Sulphate Through an Inorganic Membrane of Aluminium Oxide

Activation Energy Parameters for Hydrodynamic Permeability of Binary Aqueous Solutions of Divalent Transition Metal Sulphates and Magnesium Sulphate Through an Inorganic Membrane of Aluminium Oxide

ChemInform Abstract: Activity of Transition‐Metal (Manganese, Iron, Cobalt, and Nickel) Phosphates for Oxygen Electrocatalysis in Alkaline Solution.

AbstractMn3PO4·3H2O, Fe3(PO4)2·8H2O, Co3(PO4)2·4H2O, and 4NiHPO4·Ni3 (PO4)2·22H2O with high surface areas are prepared by precipitation from transition metal sulfate solutions via addition of a 0.1 M phosphate buffer at ambient conditions.

Uncovering the Terahertz Spectrum of Copper Sulfate Pentahydrate.

Terahertz vibrational spectroscopy has evolved into a powerful tool for the detection and characterization of transition metal sulfate compounds, specifically for its ability to differentiate between various hydrated forms with high specificity. Copper(II) sulfate is one such system where multiple crystalline hydrates have had their terahertz spectra fully assigned, and the unique spectral fingerprints of the forms allows for characterization of multicomponent systems with relative ease. Yet the most commonly occurring form, copper(II) sulfate pentahydrate (CuSO4·5H2O), has proven elusive due to the presence of a broad absorption across much of the terahertz region, making the unambiguous identification of its spectral signature difficult. Here, it is shown that the sub-100 cm(-1) spectrum of CuSO4·5H2O is obscured by absorption from adsorbed water and that controlled drying reveals sharp underlying features. The crystalline composition of the samples was monitored in parallel by X-ray diffraction as a function of drying time, supporting the spectroscopic results. Finally, the terahertz spectrum of CuSO4·5H2O was fully assigned using solid-state density functional theory simulations, helping attribute the additional absorptions that appear after excessive drying to formation of CuSO4·3H2O.

Activation Energy Parameters for Hydrodynamic Permeability of Divalent Transition Metal Sulphates and Magnesium Sulphate in Binary Aqueous Mixtures of Ethylene Glycol

Activation Energy Parameters for Hydrodynamic Permeability of Divalent Transition Metal Sulphates and Magnesium Sulphate in Binary Aqueous Mixtures of Ethylene Glycol

Sodium-ion diffusion mechanisms in the low cost high voltage cathode material Na(2+δ)Fe(2-δ/2)(SO4)3.

Bond-valence site energy modelling, classical molecular dynamics and DFT simulations were employed to clarify Na(+) ion migration in monoclinic Na2+δFe2-δ/2(SO4)3, the recently reported first representative of a new promising class of alluaudite-type high voltage cathode materials for sodium-ion batteries. Empirical potential parameters derived from our softBV bond valence parameter set reproduce experimental unit-cell parameters. Migration energy barrier calculations based on both these empirical and on ab initio approaches consistently show a strongly anisotropic and fairly fast Na(+) ion mobility along partially occupied Na(3) channels in the c-direction. Nominally fully occupied Na(1) sites are attached to these paths with a moderate activation energy as sources of mobile ions. At elevated temperatures separate parallel Na(2) channels contribute to the ionic conductivity. As such one-dimensional pathways are highly vulnerable to blocking by structural defects, the experimentally observed favourable rate performance can only be understood as a consequence of cross-linking of the channels to a more robust higher-dimensional migration pathway network. Our static and dynamic bond valence pathway models for representative local structure models reveal that this cross-linking is achieved by the iron deficiency of the compound: iron vacancies act as low-lying interstitial sites that can be reached from both types of channels with moderate activation energies. Structural relaxations around the vacancies however reduce the sodium mobility along the channels. An analogous dual effect of blocking migration along the channels and promoting perpendicular migration would result from Na(+)/Fe(2+) antisite defects. Hence, further new alluaudite type transition metal sulphates can only be expected to yield a high rate performance, if their synthesis ensures the presence of a comparable transition metal sub-stoichiometry and/or a suitably tailored concentration of sodium/transition metal antisite defects.

Hydrothermal conversion of xylose, glucose, and cellulose under the catalysis of transition metal sulfates.

Hydrothermal conversion (HTC) is an important thermochemical process to upgrade low-cost biomass into valuable chemicals or fuels. As compared with non-catalytic HTC, catalytic HTC shows high energy efficiency on biomass upgradation. In this work, the catalytic performances of various transition metal sulfates (Mn(2+), Fe(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)) in the HTCs of xylose, glucose, and cellulose under different conditions were explored. Among these catalysts, Zn(2+) and Ni(2+) showed obvious effects on the conversions of xylose, glucose, and cellulose into lactic acid, while Cu(2+) and Fe(3+), which could significantly accelerate the hydrolysis of cellulose into glucose at 200°C, displayed high efficiency on converting glucose and cellulose into levulinic acid and formic acid at high temperature. Additionally, significant positive correlative relationships among xylose, glucose, and cellulose degradations were observed. This study is helpful for screening appropriate catalysts for biomass upgradation through catalytic HTC of monosaccharide.

Studies of complexation properties of receptors based on functionalized calix[4]arenes with various complexation centers

Heterophase extraction was used to study complexation properties of ligands on the calix[4]arene platform with separated and unseparated complexation centers with transition metal salts (Ni2+, Co2+, Fe2+, Mn2+, Cu2+). Calixarenes containing N-alkylcarboxamide substituents at the lower rim exhibit higher affinity to binding of transition metal sulfates (extraction degree E = 30–60%) than calixarenes containing ester moieties at the lower rim and N-alkylsulfonamide moieties at the upper rim. The opposite pattern was observed for calixarenes containing unsubstituted amide fragments. For Fe2+, Ni2+, and Mn2+ sulfates, the extraction degree exceeded 50%.

Li(Ni1-x-yCoxMny)O2계 이차전지 공정 스크랩으로부터 회수한 전이금속을 활용한 리튬이차전지 양극재 제조

Cathode materials and their precursors are prepared with transition metal solutions recycled from the the waste lithium-ion batteries containing NCM (nickel-cobalt-manganese) cathodes by a <TEX>$H_2$</TEX> and C-reduction process. The recycled transition metal sulfate solutions are used in a co-precipitation process in a CSTR reactor to obtain the transition metal hydroxide. The NCM cathode materials (Ni:Mn:Co=5:3:2) are prepared from the transition metal hydroxide by calcining with lithium carbonate. X-ray diffraction and scanning electron microscopy analyses show that the cathode material has a layered structure and particle size of about 10 <TEX>${\mu}m$</TEX>. The cathode materials also exhibited a capacity of about 160 mAh/g with a retention rate of 93~96% after 100 cycles.

Coordination polymers built with transition metal sulphates and angular 2,5-bis(imidazol-1-yl)thiophene (thim2): synthesis, structure and photoluminescent properties

Six new CPs, based on thim2 and metal sulphates have been synthesised. The photoluminescence properties of CPs 1 and 3 have been investigated.

Effects of two transition metal sulfate salts on secondary organic aerosol formation in toluene/NO x photooxidation

Aerosol phase reactions play a very important role on secondary organic aerosol (SOA) formation, and metal-containing aerosols are important components in the atmosphere. In this study, we tested the effects of two transition metal sulfate salts, manganese sulfate (MnSO4) and zinc sulfate (ZnSO4), on the photochemical reactions of a toluene/NO x photooxidation system in a 2 m3 smog chamber. By comparing photochemical reaction products of experiments with and without transition metal sulfate seed aerosols, we evaluated the effects of transition metal sulfate seed aerosols on toluene consumption, NO x conversion and the formation of ozone and SOA. MnSO4 and ZnSO4 seed aerosols were found to have similar effects on photochemical reactions, both enhance the SOA production, while showing negligible effects on the gas phase compounds. These observations are consistent when varying metal sulfate aerosol concentrations. This is attributed to the catalytic effects of MnSO4 and ZnSO4 seed aerosols which may enhance the formation of condensable semivolatile compounds. Their subsequent partitioning into the aerosol phase leads to the observed SOA formation enhancement.

Reversible color changes of chiral double salts of d-(+)-camphoric diammonium and transition-metal sulfates via gain and loss of crystalline and coordination water molecules

Six novel chiral double salts ( 1– 6) composed of d-(+)-camphoric diammonium (LH 2) and transition-metal sulfates, formulated as {[M(SO 4) 2(H 2O) 4](LH 2)}·2H 2O [M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)], have been prepared and fully characterized including single-crystal X-ray diffraction, Fourier transform infrared (FT-IR) and vibrational circular dichroism (VCD) spectral investigations. Co(II), Ni(II) and Cu(II) compounds 2– 4 exhibit reversible color changes between 20 and 140 °C via gain and loss of two crystalline and four coordination water molecules, which can be proved by their thermogravimetric (TG) and powder X-ray diffraction (PXRD) analyses. To the best of our knowledge, this is the first report on chiral double salts showing chromotropism properties.

Representation of Electrical Conductances for Polyvalent Electrolytes by the Quint-Viallard Conductivity Equation. Part 1. Symmetrical 2:2 Type Electrolytes. Dilute Aqueous Solutions of Alkaline Earth Metal Sulfates and Transition Metal Sulfates

Literature values of the electrical conductivities of dilute aqueous solutions of alkaline metal sulfates (BeSO4, MgSO4, CaSO4, SrSO4) and of transition metal sulfates (MnSO4, FeSO4, CoSO4, NiSO4, CuSO4, ZnSO4, CdSO4) were reexamined within the framework of the Quint-Viallard conductivity equations in order to obtain a uniform representation of conductivities. It was observed that the limiting conductances of electrolytes at infinite dilution are very similar irrespective of the applied conductivity equation, whereas the derived ion association equilibrium constants vary considerably. The ion association equilibrium constants are therefore of doubtful physical value and should be treated rather as just fitting parameters.

Hydrothermal Synthesis, Structures and Magnetic Studies of Transition Metal Sulfates Containing Hydrazine

By employing hydrothermal method, six transition metal sulfates containing hydrazine (N(2)H(4)) have been obtained: [M(SO(4))(2)(N(2)H(5))(2)](n) (M = Mn(1), Co(2), Ni(3)) and [M(N(2)H(4))SO(4)](n) (M = Mn(4), Co(5), Ni(6)). Their crystal structures and magnetic properties have been investigated experimentally and theoretically. Compounds 1-3 consist of one-dimensional sulfate bridged homometallic chains with protonated hydrazine molecule as terminal ligand, and compounds 4-6 are hydrazing-sulfate mixed bridged homometallic three-dimensional frameworks. Compounds 1-6 exhibit antiferromagnetic coupling between M(2+) ions, but their magnetic properties differ at low temperatures because of the different single-ion anisotropy and crystal structures. The magnetostructural correlations and the magnetic coupling mechanism are analyzed by density functional theory calculations (DFT).

Growth of Nanoscale Nickel Ferrite on Carbonaceous Matrix- A Novel Method of Turning Harmful Particulates into a Functional Nanocomposite: An XAFS Study

Particulate matter (PM) emission from residual oil combustion typically consists of carbonaceous material accompanied by inorganic matter notably transition metal sulfates. Often a minor sulfide form is found in the coarse fraction while an oxide form is more common in the fine and ultrafine fractions. A composite comprising of nanoscale nickel ferrite dispersed on carbonaceous matrix has been obtained following liberation of metal sulfates from the fine PM--a novel method of turning harmful particulates into a functional nanocomposite without the need for elaborate preparation using expensive precursors. The nickel ferrite content in the composite varies with the Fe/Ni ratio in particulate, fuel type, and combustion condition. Such variation may lead to the composite exhibiting diverse physical behaviors. Detailed structure and cation distribution in dispersed ferrite have been studied using Fe and Ni K-edges XAFS spectroscopy. Peaks are identified in the radial structure function with specific atom pair correlations within the spinel ferrite from which the relative occupancy of the cations in the octahedral and tetrahedral sites can be discerned. The results show that Ni(II) has strong preference for the octahedral site, while Fe(III) prefers both sites which is consistent with that of an inverted spinel ferrite.