Nickel Monosulfide Research Articles

Enhanced sodium storage performance by improving the utilization of NiS through electrode membrane 3D hierarchical porous structure

Transition metal sulfides are favorable candidates for anode materials in sodium-ion batteries (SIBs), but they are difficult to fully utilize owing to the agglomeration caused by high interfacial energy at the nanoscale during the process of nanoization or compounding with carbon materials. Herein, we make full use of the advantages of the porous structure of electrode membrane (EM) to obtain a new composite electrode material with nickel monosulfide (NiS) nanoparticles uniformly spread in the membrane pores through covalent bonds. The developed 3D hierarchical porous structure and high specific area of membrane matrix provide strong space for the exposure of NiS active sites, and the NiS nanolayers loaded in the membrane pores also exhibit high porosity, thereby greatly improving its utilization. Compared with pure NiS electrode, it exhibits excellent sodium storage performance during long-term cycles and delivers an inspiring reversible capacitance of 658.3 mA h g−1 at 50 mA g−1. Moreover, the designed composite electrode exhibits excellent flexibility and structural stability before and after long cycles. The favorable performance is the result of the synergy between the 3D hierarchical porous structure and the high utilization of NiS. Considering that the unique porous structure of membrane technology can provide a positive effect on the improvement of NiS utilization, this research provides a simple and feasible design idea for SIBs composite electrodes with high utilization of nano-active materials by porous structural materials.

Uptake of nickel by synthetic mackinawite

The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fraction, were as high as XNi=0.56 (Fe1−xNixS; 0≤x≤1). Greater than 99% Ni removal from solution occurred when Ni loading remained below 0.13±0.03 (1σ) mol Ni per mol FeS due to sorption of Ni at the mackinawite surface. Characterization of experimental solids using X-ray diffraction and Raman spectroscopy showed patterns characteristic of nanocrystalline mackinawite; no evidence of nickel monosulfide (α-NiS or millerite), polydymite (Ni3S4), or godlevskite [(Ni,Fe)9S8] formation was indicated regardless of the amount of Ni loading. Slight expansion of the c-axis correlated with increasing Ni content in synthetic mackinawite, from c=5.07±0.01Å at XNi=0.02 to c=5.10±0.01Å at XNi=0.38.Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra of synthetic Ni-bearing mackinawite are similar in phase and amplitude to the Fe K-edge EXAFS spectrum of Ni-free mackinawite, indicating that the molecular environment of Ni2+ in Ni-bearing mackinawite is similar to that of Fe2+ in Ni-free mackinawite. EXAFS data fitting of Ni-bearing mackinawite with XNi=0.42 indicated a coordination number of 4.04±0.30 and an average NiS bond distance of 2.28Å, in good agreement with the FeS bond distance of 2.26Å in mackinawite, tetrahedral Fe coordination, and slight lattice expansion along the c-axis. At lower Ni loadings (XNi=0.05–0.11), EXAFS analysis showed a decrease in NiS coordination towards CN=3, which reflects the influence of sorbed Ni. Continued Ni uptake, past the maximum amount of sorption, was accompanied by proportional molar release of Fe to solution. Interstitial occupancy of Ni within the mackinawite interlayer may be transitional to structural substitution of Fe.The Ni-mackinawite solid-solution is described by a one-site binary mixing model:lnKd=lnKe−WRT1−2XNiwhere Kd is the distribution coefficient, Ke is the ratio of equilibrium constants for Ni-mackinawite and mackinawite (14.4±1.3), W is an ion interaction parameter, and XNi is the mole fraction of end-member NiS in the solid solution. The experimentally determined value of W is 17.74±1.15kJ/mol and indicates significant non-ideality of the solid solution.Transformation processes were evaluated by aging Ni-mackinawite with polysulfides and solutions saturated with air. Reaction of Ni-mackinawite with polysulfides led to the formation of pyrite (FeS2) and Ni retention in the solid phase. When Ni-mackinawite was aged in the presence of dissolved oxygen, transformation to goethite (FeOOH) and violarite (FeNi2S4) was observed.

Preparation and characterization of Cu and Ni sulfides nanoparticles

In the present work we aimed to prepare two metal sulfides nanoparticles [copper monosulfide (CuS) and nickel monosulfide (NiS)] using two different sulfur sources (Potassium N′-[4-(N′-dithiocarboxy-hydrazino)-4-oxo-butyryl]-hydrazine carbodithionate (I) and thiourea (II)) by a simple chemical method in an aqueous ethanolic solution. The effect of the used sulfur source on the optical and structural properties of the prepared metal sulfides was investigated. The synthesized sulfides were characterized using X-ray diffraction (XRD), UV-visible spectrophotometry, Transmission Electron Microscope (TEM) and elemental analysis. The yield, lattice parameters, crystallite sizes, microstrains and the band gap energy of the prepared CuS and NiS nanoparticles were evaluated and compared. Using the organic salt (I) leads to obtaining single phase structure of CuS and NiS, while using thiourea lead to obtaining mixed phases structure. By using the organic salt (I) we obtained CuS nanoparticles having greater potential for solar cell applications and NiS nanoparticles very interesting for photo catalysis applications.

Thermal Expansion of Copper and Nickel Sulfides and their Alloys

Thermal expansion coefficients of metal sulfides and their alloys are important for technological processes calculations of sulfide processing materials, for example, the crystallization equipment of nickel and copper-nickel converter matte. The synthesized copper and nickel monosulfide, and nickel and copper-nickel matte have been used as the initial samples. Dilatometric analysis was carried out by dilatometer (Linseis L78 RITA). Differences in the values measured are accounted for by the synthesis samples facilities, the coexistence of several non-stoichiometric sulfide phases and interaction during heating. In the temperature 20-500°C range the coefficients of thermal expansion (α) for the sulfides of copper, nickel and their alloys are changed from 10.4 to 20.610-6 1/K. Changes in the value α are accounted for by phase transitions in sulfide samples at their heating. Considering the properties of the phase components are an additive it is shown the thermal expansion coefficient complex sulfide-metal alloys is possible to calculate.

Wet-Chemical Preparation and Oxygen Reduction Properties of Nickel-Based Sulfide Electrocatalysts for Polymer Electrolyte Fuel Cell

Metal-sulfides with high chemical stability in acidic condition were tried to develop as an alternative none-noble metal electrocatalyst for polymer electrolyte fuel cell (PEFC). In particular, various types of Ni-based sulfides have synthesized by wet-chemical method and analyzed for the cathodic performances. Among the NiS, NiS2, and Ni3S4, nickel-mono sulfide (NiS) system showed high oxygen reduction performance in 2N-H2SO4 at 70°C. In addition, Ni0.9Cu0.1S was found to show the highest oxygen reduction performance in the Ni-mono sulfide based catalysts.

Spectroscopy of nickel monosulfide in 450–560nm by laser-induced fluorescence and dispersed fluorescence techniques

Laser-induced fluorescence excitation spectrum of NiS in the wavelength range of 450 - 560 nm has been recorded and analyzed. Thirty-five vibronic transition bands have been observed, 29 of which are reported for the first time. Rotational analyses indicated that all the observed bands can be attributable to the [Omega = 0] - X^3 Sigma^- transitions of ^58 NiS (and ^60 NiS). Twenty-five bands have been suggested to be grouped into four vibrational progressions. Furthermore, through dispersed fluorescence measurements we directly obtained the energies for the ground-state vibrational levels up to v" = 6 as well as the vibrational frequency and the anharmonicity constant for the ground state of ^58 NiS.

Nickel sulfide formation at low temperature: initial precipitates, solubility and transformation products

Environmental context Remediation technologies often rely on manipulation of redox conditions or natural redox processes to favour microbial sulfate-reduction and mineral sulfide formation for treatment of inorganic contaminants in groundwater, including nickel. However, few data are available on the structural properties, solubility and mineral transformation processes involving nickel sulfides. These data are needed in order to constrain the long term performance of groundwater remediation efforts. Abstract The formation of nickel sulfides has been examined experimentally over the temperature range from 25 to 60°C. At all conditions studied, hexagonal (α-NiS) was the initial precipitate from solution containing Ni2+ and dissolved sulfide. Freshly precipitated nickel sulfide possesses significant residual Ni–O coordination as revealed by X-ray absorption spectroscopy. With progressive aging, residual Ni–O coordination is replaced by Ni–S coordination. The formation of millerite (β-NiS, rhombohedral) was not detected in any of the synthesis experiments. In the presence of elemental sulfur, hexagonal NiS converted to polydymite (Ni3S4) and vaesite (NiS2). Thus, conversion of nickel monosulfide to thiospinel and disulfide structures appears to be redox dependent, analogous to aging and transformation processes of iron sulfides. In the absence of elemental sulfur or with only hydrogen sulfide or bisulfide present, transformation of hexagonal NiS was not observed after 1680 h at 60°C. Low-pH solubility experiments yielded a solubility product for hexagonal NiS of log Ks0 = –2.69 ± 0.26. Solubility data at pH > 3 suggest that Ni–bisulfide complexation is important in controlling the solubility of Ni in sulfidic solutions.

Optical phonons in millerite (NiS) from single‐crystal polarized Raman spectroscopy

AbstractAlthough several fundamental physico‐chemical aspects of nickel sulfides have been studied in detail, particularly for millerite (nickel(II) monosulfide), the most common nickel sulfide mineral, no satisfactory investigation of optical vibrational modes has been reported previously. In this paper, we provide a definitive assignment of the optical phonons in millerite, investigated by polarized Raman spectroscopy on an oriented single crystal. The impact of the power of the incident laser beam on the spectra has also been investigated, revealing evidence for degradation in the quality of the spectra at sufficiently high laser power. Copyright © 2008 John Wiley & Sons, Ltd.

The kinetics of the α → β transition in synthetic nickel monosulfide

The kinetic behavior of the α-Ni 1 - x S → β-NiS transition was investigated via a series of anneal-quench experiments using Rietveld quantitative phase analysis of powder X-ray diffraction data. Initial compositions of α-Ni 1 - x S were found to play an important role in the kinetics of the transition. The activation energy (E a ) for this α- to β-phase transition is 16.0 (′0.5) kJ/mol for NiS in the temperature range 343 to 423 K, and 13.0 (′0.5) kJ/mol in the temperature range 523 to 623 K. For Ni 0 . 9 7 S, however, E a decreases from 73.0 (′0.5) to 17.0 (′0.5) kJ/mol over the course of the reaction in the temperature range 573 to 593 K. The relationship between E a and extent of transition (y) for the initial bulk Ni 0 . 9 7 S was derived using the Refined Avrami method. For Ni-deficient compositions, α-Ni 1 - x S, the transformation to β-NiS is accompanied by the exsolution of a progressively more Ni-deficient α-Ni 1 - x S and Ni 3 S 4 , and the reactions become more sluggish for more metal-deficient compositions.

Amplification of the Ect2 proto-oncogene and over-expression of Ect2 mRNA and protein in nickel compound and methylcholanthrene-transformed 10T1/2 mouse fibroblast cell lines

Occupational exposure of humans to mixtures of insoluble and soluble nickel (Ni) compounds correlates with increased incidences of lung, sinus, and pharyngeal tumors. Specific insoluble Ni compounds are carcinogenic to animals by inhalation and induce morphological and neoplastic transformation of cultured rodent cells. Our objectives were to (1) understand mechanisms of nickel ion-induced cell transformation, hence carcinogenesis and (2) develop biomarkers of nickel ion exposure and nickel ion-induced cell transformation. We isolated mRNAs from green nickel oxide (NiO), crystalline nickel monosulfide (NiS), and 3-methylcholanthrene (MCA) transformed C3H/10T1/2 Cl 8 cell lines, and determined by mRNA differential display that nine mRNA fragments were differentially expressed between Ni transformed and non-transformed 10T1/2 cell lines. Fragment R2-5 was expressed at higher steady-state levels in the transformed cell lines. R2-5 had 100% sequence identity to part of the coding region of Ect2, a mouse proto-oncogene encoding a GDP–GTP exchange factor. The 3.9-kb Ect2 transcript was expressed at 1.6- to 3.6-fold higher steady-state levels in four Ni transformed, and in two MCA-transformed, cell lines. Ect2 protein was expressed at 3.0- to 4.5-fold higher steady-state levels in Ni-transformed and in MCA-transformed cell lines. The Ect2 gene was amplified by 3.5- to 10-fold in Ni transformed, and by 2.5- to 3-fold in MCA transformed cell lines. Binding of nickel ions to enzymes of DNA synthesis likely caused amplification of the Ect2 gene. Ect2 gene amplification and over-expression of Ect2 mRNA and protein can cause microtubule disassembly and cytokinesis, contributing to induction and maintenance of morphological, anchorage-independent, and neoplastic transformation of these cell lines. Over-expression of Ect2 protein is a useful biomarker to detect exposure to nickel compounds and nickel ion-induced morphological and neoplastic cell transformation.

Molecular biology of nickel carcinogenesis: identification of differentially expressed genes in morphologically transformed C3H10T1/2 Cl 8 mouse embryo fibroblast cell lines induced by specific insoluble nickel compounds.

Inhalation of mixtures of insoluble and soluble nickel compounds by humans during nickel refining has been associated with excess lung and nasal sinus cancers. Insoluble nickel subsulfide (Ni3S2) and nickel oxide (NiO) are carcinogenic to rodents by inhalation. We previously showed that insoluble Ni3S2, crystalline nickel monosulfide (NiS), and green (high temperature, HT) and black (low temperature, LT) NiO, induced morphological transformation in cultured C3H/10T1/2 Cl 8 (10T1/2) mouse embryo cells. To understand molecular mechanisms of carcinogenesis by insoluble nickel compounds, we used random, arbitrarily primed-polymerase chain reaction (RAP-PCR) mRNA differential display and identified nine cDNA fragments that were differentially expressed between nontransformed and nickel-transformed cell lines in approximately 10.0% of the total mRNA. Expression of the calnexin gene (encoding a type I membrane protein/molecular chaperone), the ect-2 proto-oncogene, and the stress-inducible gene, Wdr1, was upregulated. Expression of six genes--the vitamin D interacting protein/thyroid hormone activating protein 80 (DRIP/TRAP-80) gene, the insulin-like growth factor receptor 1 (IGFR1) gene, the small nuclear activating protein (SNAP C3) gene, and three unknown genes, was down-regulated, in nickel-transformed cell lines. We hypothesize that these resulting aberrations in gene expression could contribute to the induction and/or maintenance of morphological transformation induced by specific insoluble nickel compounds.

Molecular biology of deregulated gene expression in transformed C3H/10T1/2 mouse embryo cell lines induced by specific insoluble carcinogenic nickel compounds.

In the past, exposure of workers to mixtures of soluble and insoluble nickel compounds by inhalation during nickel refining correlated with increased incidences of lung and nasal cancers. Insoluble nickel subsulfide and nickel oxide (NiO) are carcinogenic in animals by inhalation; soluble nickel sulfate is not. Particles of insoluble nickel compounds were phagocytized by C3H/10T1/2 mouse embryo cells and induced morphological transformation in these cells with the following order of potency: NiO (black) > NiO (green) > nickel subsulfide. Foci induced by black/green NiO and nickel monosulfide developed into anchorage-independent transformed cell lines. Random arbitrarily primed-polymerase chain reaction mRNA differential display showed that nine c-DNA fragments are differentially expressed between nontransformed and nickel compound-transformed 10T1/2 cell lines in 6% of total mRNA; 130 genes would be differentially expressed in 100% of the mRNA. Fragment R3-2 was a sequence in the mouse calnexin gene, fragment R3-1 a portion of the Wdr1 gene, and fragment R2-4 a portion of the ect-2 protooncogene. These three genes were overexpressed in transformed cell lines. Fragment R1-2 was 90% homologous to a fragment of the DRIP/TRAP-80 (vitamin D receptor interacting protein/thyroid hormone receptor-activating protein 80) genes and was expressed in nontransformed but not in nickel-transformed cell lines. Specific insoluble carcinogenic nickel compounds are phagocytized into 10T1/2 cells and likely generate oxygen radicals, which would cause mutations in protooncogenes, and chromosome breakage, and mutations in tumor suppressor genes, inactivating them. These compounds also induce methylation of promoters of tumor suppressor genes, inactivating them. This could lead to permanent overexpresssion of the ect-2, calnexin, and Wdr1 genes and suppression of expression of the DRIP/TRAP-80 gene that we observed, which likely contribute to induction and maintenance of transformed phenotypes.

Preparation of copper monosulfide and nickel monosulfide nanoparticles by sonochemical method

This paper presents a novel method for the preparation of copper monosulfide (CuS) and nickel monosulfide (NiS) nanoparticles via a sonochemical route from an aqueous solution containing metal acetate [Cu(CH 3COO) 2 or Ni(CH 3COO) 2] and thioacetamide (TAA) in the presence of triethanolamine (TEA) as a complexing agent under ambient air. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray analysis (EDAX). The as-prepared nanoparticles have regular shape, narrow size distribution and high purity. It is found to be a mild, convenient and efficient method for the preparation of CuS and NiS nanoparticles.

Preparation and characterization of nanocrystalline nickel monosulfide(h) via the ethanol-thermal reducing process

Nanocrystalline nickel monosulfide was prepared with NiCl 2·6H 2O and Na 2S 3 as the reactants and Zn as the reductant, via a solvo-thermal reducing process at 80–120°C. X-ray diffraction analysis indicated that the product was the hexagonal phase of NiS. Transmission electron microscopy showed that the average particle size was about 30 nm. The reaction route of the formation of NiS is also discussed.

A Brief Communication LONG-TERM TOXICITY FOLLOWING ACUTE ADMINISTRATION OF NICKEL

Nickel compounds have high potential risk for the health of populations and for this reason their toxic effects should be urgently established. To determine the effect of nickel monosulfidein themuscle at theinjection siteon pancreatic, hepatic, and osteogenic lesions and the potential therapeutic effect of Cu-Zn superoxide dismutase (SOD), male Wistar rats received single intramuscular injections of nickel monosulfide (NiS-7 mg Ni2+/Kg). A group of these experimental rats were injected intraperitoneally, with a single weekly dose of SOD covalently linked to polyethylene glycol (SOD-PEG). Rats were sacrificed at 2, 4, 6, and 8 months after Ni2+ injection. Nickel monosulfide produced tumors at the injection site. The increased phospholipid, alanine transaminase (ALT), alkaline phosphatase (ALP), and amylase levels in serum, in absence of SOD-PEG, reflected the toxic effects on pancreatic, hepatic, and osteogenic tissues of rats. SOD activity was increased in serum of rats receiving SOD-PEG throughout the experiment, and no significant difference was observed in biochemical parameters of control and experimental rats in presence of SOD-PEG. Superoxide radical generated by Ni2+ is of primary importance in the development of tum ors at the injection site. Superoxide anion (O2-.) is also an important toxic interm ediate with respect to hepatic, pancreatic, and osteogenic injury, since SOD-PEG has a potential therapeutic effect.

High rate molten salt cells employing barium nickel sulfide cathodes

Barium nickel sulfide (BaNiS 2) was investigated as a cathode material in high temperature molten salt cells using lithium—aluminum alloy as the anode and a eutectic mixture of lithium chloride and potassium chloride immobilized with magnesium oxide as the electrolyte. Results are presented on the cathode utilization, cathode energy and power densities obtained at current densities of 0.05 to 2.0 A/cm 2 at 400 °C. The performance of these cells is also compared with the performance of similar cells using nickel monosulfide or its mixture with barium sulfide as cathodes. The electrode reactions occurring at the positive electrode in these cells during charge and discharge operations are also discussed.

Morphological and neoplastic transformation of C3H/10T1/2 Cl 8 mouse embryo cells by insoluble carcinogenic nickel compounds

We studied induction of cytotoxicity and morphological transformation in C3H/10T1/2 Cl 8 (10T1/2) mouse embryo fibroblasts by soluble and insoluble carcinogenic nickel compounds. Soluble nickel sulfate and nickel chloride caused dose-dependent cytotoxicity in the concentration range from 0.5 microM to 100 microM after 48 hr treatments, but neither compound induced morphological transformation even at concentrations causing up to 94% cytotoxicity. Insoluble nickel subsulfide, nickel monosulfide, and nickel oxide caused dose-dependent cytotoxicity and a low, dose-dependent frequency of morphological transformation in the concentration ranges from 0.5 to 40 microM, 5 to 50 microM, and 50 to 400 microM, respectively, after 48 hr exposure of cells to these compounds. Foci were predominantly of type II morphology; type III foci were rare. The insoluble nickel compounds studied caused no induction of base substitution mutations to ouabain resistance in 10T1/2 cells over concentration ranges that induced morphological transformation. Nickel subsulfide and nickel monosulfide were taken into cells by phagocytosis, since particles were visible in intracytoplasmic vacuoles. Numerous nickel oxide particles were found associated with cells, but true phagocytic uptake was difficult to detect since no vacuoles were observed. We twice cloned type II and type III foci induced by insoluble nickel compounds, established independent cell lines, and characterized their phenotypes. Four of seven of these cell lines had three- to fourfold increased saturation densities compared to 10T1/2 cells, formed type II and type III foci in reconstruction assays, and grew in soft agarose. One cell line induced by nickel oxide formed tumors in nude mice. These data indicate that insoluble carcinogenic nickel compounds induced type II foci in 10T1/2 cells, some of which were tumorigenic, and that the 10T1/2 cell system is suitable for studying mechanisms of nickel compound-induced morphological transformation in mammalian cells.

Biological half-time in rats exposed to nickel monosulfide (amorphous) aerosol by inhalation

This study reports the biological half-time of amorphous nickel monosulfide(NiS(A)) aerosol retained in rat lungs. Wistar male rats were exposed to NiS(A) aerosols (mass median aerodynamic diameter:4.0 microns) for a single 4 h exposure, or for 7 h/d, 5 d/wk for 1 mo. The average exposure concentrations were controlled at 107 mg/m3 for the single exposure and at 8.8 mg/m3 for the repeated exposures by a dust generator consisting of a continuous fluidized bed with an overflow pipe and a screw feeder. After the exposures, the nickel contents in the rat organs, blood, and urine were measured and histopathological examinations were performed. The biological half time of NiS(A) in rat lungs was 20 h, which was extremely shorter than 21 mo of green nickel oxide (NiO(G)). There were no malignant tumors in any of the exposure groups.

An electron-optical study of nickel monosulfide

The high temperature form of nickel monosulfide, Ni (1− x) S has the nickel arsenide structure. It is nonstoichiometric in the range NiSNi 0.91S. Powder X-ray diffraction of synthetic samples suggests a simple solid solution, but high resolution electron microscopy reveals three different structural regions. One of these, previously reported elsewhere, has rhombohedral symmetry with a 3 × a repeat. The second region shows a 2 × a repeat, while the third appears to contain disordered vacancies. The effect of multiple scattering on the electron diffraction patterns and images is discussed.

Carcinogenic activity of particulate nickel compounds is proportional to their cellular uptake.

Particles (less than or equal to 5 micrometers) of the potent carcinogen crystalline nickel subsulfide were actively phagocytized by cultures of Syrian hamster embryo cells and Chinese hamster ovary cells. Cells did not take up significant quantities of similar-sized particles of the noncarcinogen amorphous nickel monosulfide. The carcinogenic activity of this and other metal compounds appears to be proportional to their cellular uptake.