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.

Research progress of transition metal compounds as bifunctional catalysts for zinc-air batteries

Zinc-air batteries(ZABs)are widely studied because of their high theoretical energy density,high battery voltage,environmental protection,and low price.However,the slow kinetics of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)on the air electrode limits the further application of ZABs,so that how to develop a cheap,efficient,and stable catalyst with bifunctional catalytic activity is the key to solving the development of ZABs.Transition metal compounds are widely used as cathode materials for ZABs due to their low cost,high electrocatalytic activity,and stable structure.This review summarizes the research progress of transition metal compounds as bifunctional catalysts for ZABs.The development history,operation principle,and mechanism of ORR and OER reactions are introduced first.The application and development of transition metal compounds as bifunctional catalysts for ZABs in recent years are systematically introduced,including transition metal oxides(TMOs),transition metal nitrides(TMNs),transition metal sulfides(TMSs),transition metal carbides(TMCs),transition metal phosphates(TMPs),and others.In addition,the shortcomings of transition metal compounds as bifunctional catalysts for ZABs were summarized and reasonable design strategies and improvement measures were put forward,aiming at providing a reference for the design and construction of high-performance ZABs cathode materials.Finally,the challenges and future in this field are discussed and prospected.

Mechanism research progress on transition metal compound electrode materials for supercapacitors

Supercapacitors(SCs)have remarkable energy storage capabilities and have garnered considerable interest due to their superior power densities and ultra-long cycling characteristics.However,their comparatively low energy density limits their extensive application in large-scale commercial applications.Electrode materials directly affect the performance of SCs.Thus,the development of cutting-edge electrode materials and modification of their morphological and structural properties are vital for advancing the performance of SCs.Transition metal compounds have a high specific capacity and good cycling durability,making them the most promising electrode active materials for high-energy density SCs.Nevertheless,their inadequate conductivity,unfavorable ion diffusion rates,substantial volume expansion and phase transitions during charging and discharging are obstacles to their stable and efficient integration into SCs.To address these challenges,this study provides a comprehensive summary of the current advancements in transition metal nanomaterials as electrode materials for SCs,an overview of the current research status,and the prevailing challenges.Furthermore,this study highlights synthetic techniques and management strategies for electrode materials derived from transition metal compounds,targeting the resolution of the aforementioned challenges.Finally,a concise discussion is provided on the future directions of SC development,with an emphasis on the utilization of transition metal compound electrode 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.

Recent progresses of micro-nanostructured transition metal compound-based electrocatalysts for energy conversion technologies

The rapid consumption of fossil fuels has caused increasingly climatic issues and energy crisis,which leads to the urgent demand for developing sustainable and clean energies.Electrocatalysts play a key role in the development of electrochemical energy conversion and storage devices.Especially,developing efficient and cost-effective catalysts is important for the large-scale application of these devices.Among various electrocatalyst candidates,earth abundant transition metal compound(TMC)-based electrocatalysts are being widely and rapidly studied owing to their high electrocatalytic performances.This paper reviews the recent and representative advances in efficient TMC-based electrocatalysts(i.e.,oxides,sulfides,selenides,phosphides,carbides and nitrides)for energy electrocatalytic reactions,including hydrogen evolution reaction(HER),oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Different compounds with different applications are summarized and the relative mechanisms are also discussed.The strategies for developing earth-abundant and low-cost TMC-based electrocatalysts are introduced.In the end,the current challenges and future perspectives in the development of TMC research are briefly discussed.This review also provides the latest advance and outlines the frontiers in TMC-based electrocatalysts,which should provide inspirations for the further development of low-cost and high-efficiency catalysts for sustainable clean energy technologies.

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.

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.

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.

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.

CALCULATIONS FOR CRYSTAL COHESIVE ENERGY OF TRANSITION METAL COMPOUND

Based on the empirital electron theory of solids and molecules and the treatment of thecrystal cohesive energy of alkali metal, alkaline-earth metal and transition metal, this paperpresents a calculation method for the transition metal compound, by which a number ofcomplex structures of several compounds have been calculated and some results in agreementwith the experimental values obtained.

Ionothermal Synthesis, Crystal Structure and Antibacterial Activities of a New 3d-4f Hetero-metallic Compound Containing Two Kinds of Ligands

A new 3d-4f（CuⅡ-CeⅢ） hetero-metallic compound containing two kinds of ligands, namely [CuⅡ（H2pdc）（phen）（H2O）]（HⅢ3O）2[CeⅢ（pdc）3][CuⅡ（phen）Ce（pdc）3]（1, H2 pdc = pyridine-2,6-dicarboxylic acid, phen = 1,10-phenanthroline）, has been synthesized by an ionothermal method using the ionic liquid 3-butyl-1-methylimidazolium bromide（[Bmim]Br） as solvent, and characterized by elemental analysis, energy-dispersive X-ray spectroscopy（EDS）, IR, XPS and single-crystal X-ray diffraction. The structure reveals that 1 belongs to the triclinic system, space group P1 with a = 12.044（7）, b = 14.841（8）, c = 22.305（13） A, α = 85.802（12）, β = 85.471（12）, γ = 89.174（11）°, Z = 2, V = 3964（4） A3, Dc = 1.804 g·cm-3, F（000） = 2140, μ = 1.757 mm-1, the final R = 0.0734, wR = 0.1094 and S = 1.013. The compound can be viewed as a two-dimensional layered structure composed by 3d-4f hetero-nuclear anions [Cu（phen）Ce（pdc）3]-, coordination cations [Cu（H2pdc）（phen）（H2O）]2＋, coordination anions [Ce（pdc）3]3- and protonated water molecules via hydrogen bonding interactions and π-π stacking. Moreover, the antimicrobial activities of 1 have been also investigated. The results indicated that its inhibitory activity is slightly higher than that of penicillin against Candida albicans.

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.

Effects of sodium benzoate on growth and physiological characteristics of wheat seedlings under compound heavy metal stress

In this study, we investigated the effect of exogenous sodium benzoate on wheat seedlings(Yangmai 16) grown under heavy metal stress. The results showed that 2.4 mmol kg-1 of heavy metals significantly inhibited growth and delayed emergence of wheat seedlings. Under compound heavy metal stress, application of 2-4 g L^-1 sodium benzoate significantly increased(P<0.01) chlorophyll content and chlorophyll fluorescence parameters Fv/Fm and Fv/Fo of wheat, compared to the control(water treatment). Further analysis showed that application of 2-4 g L^-1 sodium benzoate alleviated osmotic stress by promoting the accumulation of osmolytes such as soluble proteins and free proline, increased the activity of superoxide dismutase(SOD) and reduced malondialdehyde content(MDA). In contrast, higher concentrations of sodium benzoate solution(>6 g L^-1) inhibited the growth of wheat seedlings and even caused damage to seedlings. Correlation analysis showed that when the sodium benzoate concentration was in the range of 1.97-3.12 g L^-1(2016) and 1.58-3.27 g L^-1(2017), values of chlorophyll and its components, root activity, SOD activity, soluble protein, and free proline content were the highest. When the sodium benzoate concentration was raised to 2.59 g L^-1(2016) or 3.02 g L^-1(2017), MDA content was the lowest. Ultimately, exogenous sodium benzoate(2-4 g L^-1) facilitates root development and improves the root activity of wheat seedlings grown under compound heavy metals stress, thereby effectively alleviating the damage of compound heavy metal stress in wheat seedlings.

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.

Electrocatalytic oxygen evolution activities of metal chalcogenides and phosphides:Fundamentals,origins,and future strategies

The development of inexpensive and efficient electrocatalysts is key to commercializing energy-related electrocatalytic techniques such as water electrolyzers and metal-air batteries.In particular,novel oxygen evolution reaction(OER)pre-catalysts,such as transition metal chalcogenides(TMCs)and phosphides(TMPs),have evolved in recent years from traditional stable OER electrocatalysts,which show superior OER electrocatalytic performance compared with transition metal oxides(TMOs)or(oxy)hydroxides(TMOHs).In this feature article,we summarize recent advances in the development of TMCand TMP-based OER electrocatalysts,as well as approaches to improve the OER performance in terms of morphology,structure,composition,surface engineering,lattice-strained and in-situ transformation in the electrolysis process.In particular,the electrochemical stability of TMCs and TMPs in alkaline electrolytes and the evolution of morphology,structure and composition under OER conditions are discussed.In the last section,we discuss the challenges that need to be addressed in this specific area of research and the implications for further research.

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.

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.

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.