A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.

Single-Phase Ternary Compounds with a Disordered Lattice and Liquid Metal Phase for High-Performance Li-Ion Battery Anodes

Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.

Assessment of the Level of Metal(loid)s Pollution and Bioactive Compounds Screening of Anthill Soil

The anthill soil is used by hypertensive elderly and teenagers from Oshikoto region (Namibia) and many of them testified stabilization of their blood pressure to normal after consuming the anthill soil-derived aqueous extracts. This study therefore investigated and/or assessed the physicochemical parameters, the contents of some metal(loid)s (and their associated potential health risks) and the qualitative composition of bioactive compounds of this anthill soil. The homogenous soil sample collected from various anthill soils in the Oshikoto region was used to obtain the measurements of physiochemical parameters. The elemental contents were determined (using an Inductively Coupled Plasma Optical Emission Spectrophotometer) after acid digestion in accordance with the EPA method 350B and their potential health risk assessments were performed. Methanol, aqueous methanol, and aqueous-based extracts were generated via maceration extraction process prior to the screening of bioactive compounds using standard diagnostic assays. The oxidation reduction potential (164.4 ± 16.6 mV) was the only physicochemical parameter whose value was within the World Health Organization limits for drinking water whereas, total dissolved solids (23 ± 5.5 mg/L), electrical conductivity (44 ± 10.1 uS/cm) and pH (5.35 ± 0.33) were out of specifications. Phenolic compounds, flavonoids, terpenoids, and cardiac glycosides were present in anthill soil (with respect to the extractants used) to which its antihypertensive properties can be attributed in addition to some of the studied mineral components. With respect to the pH, TDS and EC, and the contents of most metal(loid)s in relation to their health risk assessment values, the results suggest that aqueous extracts derived from this anthill soil can be deemed unsuitable for human consumption.

Catalytic removal of volatile organic compounds using ordered porous transition metal oxide and supported noble metal catalysts

Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.

STUDY ON DEGRADATION OF LDPE CATALYZED BY MULTI-VALENCE METALLIC ORGANIC COMPOUNDS AT COMPOST TEMPERATURE

The catalytic effects of the organic compounds of iron,tin and manganese on the degradation of low density polyethylene (LDPE) at compost temperature are discussed.A series of samples were aged in a simulating compost environment.The mechanical properties,viscosity average molecular weight (M η) of PE and hydroperoxide (POOH) concentration in the samples were measured.FT IR and DSC were also applied to characterize some samples.It was shown that the above mentioned metallic organic compounds can catalyze the degradation of LDPE efficiently.After 2 months aging,all samples with catalysts became fragile and the M η of the material decreased dramatically.Furthermore,the concentration of carbonyl and the degree of crystallinity of the material increased with the aging time.

Toxicity assessment of heavy metals and organic compounds using CellSense biosensor with E.coli

A new strategy using an arnperometric biosensor with Escherichia coli （E. coli） that provides a rapid toxicity determination of chemical compounds is described. The CellSense biosensor system comprises a biological component immobilized in intimate contact with a transducer which converts the biochemical signal into a quantifiable electrical signal. Toxicity assessment of heavy metals using E.coli biosensors could be finished within 30 min and the 50% effective concentrations （ECso） values of four heavy metals were determined. The results shows that inhibitory effects of four heavy metals to E.coli can be ranked in a decreasing order of Hg^2＋ 〉 Cu^2＋ 〉 Zn^2＋ 〉 Ni^2＋, which accords to the results of conventional bacterial counting method. The toxicity test of organic compounds by using CellSense biosensor was also demonstrated. The CellSense biosensor with E. coli shows a good, reproducible behavior and can be used for reproducible measurements.

A Reflectron Time-of-Flight Mass Spectrometer with a Nano-Electrospray Ionization Source for Study of Metal Cluster Compounds

An experiment facility has been set up for the study of metal cluster compounds in our laboratory, which consists of a nano-electrospray ionization source, an ion transmission and focus system, and a reflectron time-of-fight mass spectrometer. Taking advantage of the nano-electrospray ionization source, polyvalent ions are usually produced in the ＂ionization＂ process and the obtained mass resolution of the equipment is over 8000. The molecular ion peaks of metal cluster compounds [Au20（PPhpy2）10Cl2]（SbF6）4, where PPhpy2=bis（2- pyridyl）phenylphosphine, and [AuaAg2（C）L6]（BF4）4, where L=2-（diphenylphosphino）-5- methylpyridine, are distinguished in the respective mass spectrum, accompanied by some fragment ion peaks. In addition, the mass-to-charge ratios of the parent ions are determi- nated. Preliminary results suggest that the device is a powerful tool for the study of metal cluster compounds. It turns out that the information obtained by the instrumentation serves as an essential supplement to single crystal X-ray diffraction for structure characterization of metal cluster compounds.

Corrosion behavior of pure metals(Ni and Ti)and alloys(316H SS and GH3535)in liquid GaInSn

In this study,the interactions between a Ga-based liquid metal,GaInSn,and several metal materials,including pure metals(Ni and Ti)and alloys(316H stainless steel(SS)and GH3535),at 650℃were investigated.The aim was to evaluate the corrosion performance and select a suitable candidate material for use as a molten salt manometer diaphragm in thermal energy storage systems.The results indicated that the alloys(316H SS and GH3535)exhibited less corrosion than pure metals(Ni and Ti)in liquid GaInSn.Ga-rich binary intermetallic compounds were found to form on the surfaces of all the tested metal materials exposed to liquid GaInSn,as a result of the decomposition of liquid GaInSn and its reaction with the constituent elements of the metal materials.The corrosion mechanism for all the tested materials exposed to liquid GaInSn was also investigated and proposed,which may aid in selecting the optimal candidate material when liquid GaInSn is used as the pressure-sensing medium.

Physicochemical, Heavy Metals and Phenolic Compounds Analysis of Libyan Honey Samples Collected from Benghazi during 2009-2010

In the present work, the results of analysis of 10 Libyan honey samples, representing various floral honeys, collected from Benghazicity during different seasons in 2009-2010 were demonstrated. All samples were examined for the physicochemical quality parameters, phenolic compounds and heavy metals contents. The moisture;optical density (O. D.);electrical conductivity;water insoluble solids;ash content;pH;total acidity;hydroxylmethyl furfural (HMF);sugar contents and phenolic compounds content were detected according to AOAC 1990-Official Methods and reference methods. The results were compared with Libyan Standard Legislation and the European Standard Legislation. The obtained results indicated that the quality of the tested Libyan honey samples were very good and worth to the world standard properties of honey. Even more, the tested Libyan honey samples have high level of phenolic compounds content. On the basis of heavy metals content, three metals were determined (Cadmium, copper and lead) using atomic absorption spectrophotometer. The level of each metal-content was variable, which may be due to the conditions of processing, packing and storage conditions of Libyan honey samples.

Pollution of organic compounds and heavy metals in a coal gangue dump of the Gequan Coal Mine, China

Samples around a coal gangue dump of the Gequan Coal Mine were collected in April 2009. GC (gas chromatography) and GC/MS (gas chromatography/mass spectrometry) were employed to analyze the composition of organic matter in the samples. ICP-MS (inductively coupled plasma mass spectrometry) was used to determine the concentrations of heavy metals. The contents of organic extracts are within the range of 140-750 mg/kg. Alkand aro-ratios are relatively high. Compared to those of the background sample (GQ13 ), the contents of saturated hydrocarbon compounds in all the samples are relatively high. The contents of polycyclic aromatic hydrocarbons (PAHs) are relatively high with the distance getting closer to the coal gangue dump. These indicate that organic matter in the samples is from coal particles of the coal gangue dump. The distributions of heavy metals are very similar: the contents decrease with distance from the dump, which indicates that the harmful heavy metals from the coal gangue dump have polluted as thick as at least 500 m.

Synthesis and Crystal Structure of Dicopper(II) Compound Containing Oxalate and Reduced Imino Nitroxide Radicals

A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal structure was determined by X-ray diffraction method. The complex crystallizes in monoclinic, space group P21/n with a = 9.913(4), b = 19.057(8), c = 10.169(4) ? b = 114.292(7), V = 1751(1) 3, C26H38Cu2N8O14, Mr = 813.72, Dc = 1.543 g/cm3, m(MoKa) = 1.290 mm-1, F(000) = 840, Z = 2, the final R = 0.0398 and wR = 0.0986 for 1878 observed reflections (I>2s(I)). The imino nitroxide 2-(2-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl (im2-py) is reduced in the reaction to yield Him2-py which consists of oxalato-bridged centrosymmetric [Cu2(m-C2O4)(Him2-py)2(H2O)2]2+ ions and noncoordinated NO3- anions. Each copper(II) ion is in a distorted tetragonal pyramid environment: two nitrogen atoms from Him2-py and two oxygen atoms from the oxalate group are in the basal plane, and one water molecule at the axial position.

Adsorptive removal of nitrogen-containing compounds from fuel by metal-organic frameworks

The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.

Technology Development and Production of Certain Chemical Platinum Metals Compounds at JSC ＂Krastsvetmet＂

In recent years JSC "Krastsvetmet" has successfully developed the production of chemically pure compounds of precious metals.Currently methods have been developed and facilities have been provided for industrial production of the following platinum metals compounds:Rhodium(Ⅲ) chloride hydrate,rhodium(Ⅲ) chloride solution,rhodium(Ⅲ) nitrate solution,rhodium(Ⅲ) iodide,rhodium(Ⅲ) sulfate,hydrated rhodium(Ⅲ) oxide,ammonium hexachlororodiate,rhodium(Ⅲ) phosphate solution,rhodium electrolytes;Iridium(Ⅳ) chloride hydrate,iridium(Ⅲ) chloride hydrate,ammonium hexachloroiridate(Ⅳ),hexa chloriridium acid solution,hexachloriridium crystalline acid;Ruthenium(Ⅲ) chloride hydrate,ruthenium(Ⅳ) hydroxide chloride,ruthenium(Ⅳ) hydroxide chloride solution,ammonium hexachlororuthenate,ruthenium(Ⅲ) chloride solution,potassium,diaquaoctachloronitrido diruthenate.The quality of the production meets the requirements of Russian and foreign consumers.

SYNTHESES OF TETRAHEDRAL METAL CLUSTER COMPOUNDS

The carbyne compound [Br(CO)_2(Py)_2Mo(≡CC_6H_5)] (Py=pyridine) (1a) reacts with Co_2 (CO)_8, Fe_2(CO)_9 and Mn_2 (CO)_(10) to give tetrahedral tri-metal cluster compounds Co_2Mo(μ_3-CC_6H_5)Br(CO)_8(Py)_2 (2), Fe_2Mo(μ_3-CC_6H_5) Br(CO)_9(Py)_2 (3) and Mn_2Mo(μ_3-CC_6H_5)Br(CO)_(10) (Py)_2 (4) respectively. Tri-metal cluster compound Co_2Mo(μ_3-CC_6H_5)Br(CO)_8-(bipy) (bipy=α,α'dipyridyl) (5) is prepared in a similar reaction sequence from [Br(CO)_2(bipy)Mo(≡CC_6H_5)] (1b) and Co_2(CO)_8. IR, ~1H and ^(13)C NMR spectral data of these compounds are reported and discussed. The crystal structure of compound (5) has been determined by X-ray diffraction.

Examination of Polymeric Azomethine Compounds and Their Transition Metal Complexes by Using XRF and XRD Technique

In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.

AROMATIC BOND INCLUDING METALLIC ATOM IN COORDINATE COMPOUNDS AND SOME OF ITS PROPERTIES

Aromatic bond including metallic atom (Ni) is investigated by EHMO calculation.The NMR spectra and the mechanism for hydrolysis are discussed on the ground of results of computation.

STUDIES ON THE PROPERTIES OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS Ⅲ TRANSMETALLATION REACTION OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS WITH METALLIC TIN

The transmetallation reaction of 4 Schiff base type arylmercury compounds with metallic tin has been carried out in refluxing xylene.It was found that the reaction proceeds in the same manner as that of chloro[2-(phenylazo)phenyl]mercury(Ⅱ) to give dichlorobisaryltin(Ⅳ).The ~1H NMR spectra of the products provide evidence for the presence of N→Sn intramolecular coordination.The formation of dichlorobisaryltin(Ⅳ)as a unique product probably arises from the N→Sn intramolecular coordination which results in the increasing of the stability of the molecule.

Spontaneous Magnetic Transitions and Corresponding Magnetoelastic Properties of Intermetallic Compounds RMn_2Ge_2(R=Gd, Tb and Dy)

The spontaneous magnetic transitions and corresponding magnetoelastic properties of intermetallic compounds RMn2Ge2（R=Gd, Tb and Dy） were investigated by using the X-ray diffraction method and magnetic measurement. The results showed that the compounds experience two magnetic transitions, namely the second-order paramagnetic to antiferromagnetic transition at temperature TN（TN=368, 423 and 443 K for Gd Mn2 Ge2, Tb Mn2 Ge2 and Dy Mn2 Ge2, respectively） and the first-order antiferromagnetic-ferrimagnetic transition at temperature Tt（Tt=96, 80 and 40 K for Gd Mn2 Ge2, Tb Mn2 Ge2 and Dy Mn2 Ge2, respectively） as the temperature decreases. The temperature dependence of the lattice constant a（T） displays a negative magnetoelastic anomaly at the second-order transition point TN and, at the first-order transition Tt, a increases abruptly for Gd Mn2 Ge2 and Tb Mn2 Ge2, Da/a about 10^（-3）. Nevertheless, the lattice constant c almost does not change at these transition points indicating that such magnetoelastic anomalies are mainly contributed by the Mn-sublattice. The transitions of the magnetoelastic properties are also evidenced on the temperature dependence of magnetic susceptibility χ. The first-order transition behavior at Tt is explained by the Kittel mode of exchange inversion.

THE SYNTHESIS AND CHARACTERISTICS OF THE COORDINATION COMPOUNDS OF 2-MERCAPTOPYRIDINE-1-OXIDE WITH THE FIPST TRANSITION SERIES METALS

The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.

CHARACTERIZATION OF SOME SCHIFF BASES OF HETEROCYCLIC COMPOUNDS AND THEIR TRANSITION METAL COMPLEXES

Some new Schiff bases were synthesized by the condensation of equimolar quantities of salicylaldehyde and 2-amino-5-phenylazo-pyridine or its derivatives in dry benzene(1):Metal complexes of the type ML_2and M'L_3 where M=Cu^(2+),Co^(2+),Ni^(2+),Mn^(2+)Pd^(2+),M'=Fe^(3+)and L=different newly synthesized monobasic Schiff bases were prepared in absolute ethanolic medium(2)and characterized by elementary analysis,conductance measurements,infrared spectra,electronic spectra,magnetic moments studies.