Recent Advances of Transition Metal Basic Salts for Electrocatalytic Oxygen Evolution Reaction and Overall Water Electrolysis

Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.

Influence of counter electrode material during accelerated durability test of non-precious metal electrocatalysts in acidic medium

Significant progress has been made in the development of non-precious metal electrocatalysts （NPMEs） during the past decade. Correspondingly, there is an urgent demand for an appropriate measurement method to be established for the reliable evaluation of NPMEs. In this study, platinum and graphite counter electrodes were used to investigate the impact of counter electrode material on the accelerated durability testing （ADT） of NPMEs in acidic medium. Platinum used as the coun- ter electrode in a traditional three-electrode electrochemical cell was found to dissolve in acidic medium and re-deposit on NPME coated on the working electrode during ADT. Such re-deposition causes the oxygen reduction reaction （ORR） performance of NPMEs to remarkably improve, and thus will seriously mislead our judgment of NPMEs if we are unaware of it. The phenomenon can be avoided using a graphite counter electrode.

Thermodynamic analysis on the direct preparation of metallic vanadium from NaVO_3 by molten salt electrolysis

A novel and environmentally friendly route to directly prepare metallic vanadium from NaV03 by molten salt electrolysis is proposed. The feasibility about the direct electro-reduction of NaV03 to metallic vanadi- um is analyzed based on the thermodynamic calculations and experimental verifications. The theoretical decomposition voltage of NaV03 to metallic vanadium is only 0.47 V at 800 ℃ and much lower than that of the alkali and alkali earth metal chloride salts. The value is slightly higher than that of low-valence vanadium oxides such as V203, V305 and VO. However, the low-valence vanadium oxides can he further electro-reduced to metallic vanadium thermodynamically. The thermodynamic analysis is verified by the experimental results. The direct preparation of metallic vanadium from NaV03 by molten salt electrolysis is feasible.

Electrocatalytic activity of non-precious metal catalyst Co-N/C toward oxygen reduction reaction

Metallic cobalt was deposited on acetylene black to synthesize a composite Co/C by chemical reduction method.A platinumfree electrocatalyst Co-N/C（800） for oxygen reduction reaction（ORR） was synthesized by mixing the composite Co/C with urea and heat-treating at 800℃.The results from linear sweep voltammograms indicated that the Co-N/C（800） is active to ORR.Theβ-Co and cobalt oxides are not the active site of the catalyst Co-N/C.However,the existence of cobalt facilitated the modification of nitrogen to carbon black and led to the formation of active site of catalyst Co-N/C（800）.

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.

Nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for oxygen reduction and oxygen evolution reactions

The oxygen reduction/evolution reactions(ORR/OER) are a key electrode process in the development of electrochemical energy conversion and storage devices,such as metal-air batteries and reversible fuel cells.The search for low-cost high-performance nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER alternatives to the widely-used noble metal-based catalysts is a research focus.This review aims to outline the opportunities and available options for these nanocarbon-based bifunctional electrocatalysts.Through discussion of some current scientific issues,we summarize the development and breakthroughs of these electrocatalysts.Then we provide our perspectives on these issues and suggestions for some areas in the further work.We hope that this review can improve the interest in nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER.

Characteristics and Nature of Metal Fog in Molten Salts

In this paper are reported the characteristics and nature of metal fog in molten cryolite-alumina mixtures on the basis of laboratory experiments and quantum chemistry studies.The metal fog is the finely divided metal particles in the molten salts, and it dissolves partly in the molten cryolite to form atomic clusters,such as(Al_nNa_m)^(x+) type.

Regulating non-precious transition metal nitrides bifunctional electrocatalysts through surface/interface nanoengineering for air-cathodes of Zn-air batteries

Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunctional electrocatalysts for air-cathode oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)processes,the practical application of rechargeable ZABs is seriously hindered.In the effort of developing high active,stable and cost-effective electrocatalysts,transition metal nitrides(TMNs)have been regarded as the candidates due to their high conductivity,strong corrosion-resistance,and bifunctional catalytic performance.In this paper,the research progress in TMNs-based material as ORR and OER electrocatalysts for ZABs is discussed with respect to their synthesis,chemical/physical characterization,and performance validation/optimization.The surface/interface nanoengineering strategies such as defect engineering,support binding,heteroatom introduction,crystal plane orientation,interface construction and small size effect,the physical and chemical properties of TMNs-based electrocatalysts are emphasized with respect to their structures/morphologies,composition,electrical conductivity,specific surface area,chemical stability and corrosion resistance.The challenges of TMNs-based materials as bifunctional air-cathode electrocatalysts in practical application are evaluated,and numerous research guidelines to solve these problems are put forward for facilitating further research and development.

Evaluation of properties of concrete using fluosilicate salts and metal (Ni,W) compounds

To improve watertightness and antibiosis of sewage structure concrete, the antimicrobial watertight admixture was made with fluosilicate salts and antimicrobial compounds. And fresh properties, watertightness, harmlessness and antibiosis of concrete were investigated experimentally. As a result, the fresh properties of concrete were similar to those of an ordinary concrete, without setting time delay. Compressive strength and carbonation resistance of concrete were better than those of an ordinary concrete. Finally it was confirmed that the antimicrobial watertight admixture of concrete had an antibiosis inhibiting SOB growth.

Synthesis of cyclic carbonates from epoxides or olefins and CO_2 catalyzed by metal-organic frameworks and quaternary ammonium salts

Catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbon- ates using tetrabutylammonium bromide as co-catalyst have been explored under mild reaction conditions （8 bar CO2, 25 ~C）. Styrene and propylene carbonates were formed with high yields （95% and 82%, respectively）. Catalytic performance of Cr-MIL-101 was compared with other MOFs： Fe-MIL-101, Zn-MOF-5 and HKUST-1, The catalytic properties of different quaternary ammonium bromides, Cr-MIL-101 as well as PW12/Cr-MIL-101 composite material have been assessed in oxidative carboxylation of styrene in the presence of both tert-butyl hydroperoxide and H202 as oxidants at 8-100bar CO2 and 25-80 ~C with selectivity to styrene carbonate up to 44% at 57% substrate conversion.

Synthesis and Selective Coloration of Monoaza Crown Ethers Bearing Picrylamino-type Side Arms for Alkali Metal Salts and Methylamine

N-pivot lariat ethers with picrylamino group as a chromophore (1, 2 and 3) have been prepared by reaction of N-(4-aminoaryl)monoaza crown ethers with picryl chrolide, and the selective coloration of 1, 2 and 3 for alkali metal salts and amines has been studied by UV-Vis spectra.

The Influence of Nitrate Salts and Complex Metal Ion to Regio-Selective Synthesis of 2-Nitro-5,10,15,20-Tetra- (4-Methoxyphenyl)Porphyrinato Metal

A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.

Synthesis of dual-doped non-precious metal electrocatalysts and their electrocatalytic activity for oxygen reduction reaction

The pyrolyzed carbon supported ferrum polypyrrole （Fe-N/C） catalysts are synthesized with or without selected dopants, p-toluenesulfonic acid （TsOH）, by a facile thermal annealing approach at desired temperature for optimizing their activity for the oxygen reduction reaction （ORR） in O2-saturated 0.1 mol/L KOH solution. The electrochemical techniques such as cyclic voltammetry （CV） and rotating disk electrode （RDE） are employed with the Koutecky-Levich theory to quantitatively obtain the ORR kinetic constants and the reaction mechanisms. It is found that catalysts doped with TsOH show significantly improved ORR activity relative to the TsOH-free one. The average electron transfer numbers for the catalyzed ORR are determined to be 3.899 and 3.098, respectively, for the catalysts with and without TsOH-doping. The heat-treatment is found to be a necessary step for catalyst activity improvement, and the catalyst pyrolyzed at 600℃ gives the best ORR activity. An onset potential and the potential at the current density of -1.5 mA/cm2 for TsOH-doped catalyst after pyrolysis are 30 mV and 170 mV, which are more positive than those without pyrolized. Furthermore, the catalyst doped with TsOH shows higher tolerance to methanol compared with commercial Pt/C catalyst in 0.1 mol/L KOH. To understand this TsOH doping and pyrolyzed effect, X-ray diffraction （XRD）, scanning electron microscope （SEM） and X-ray photoelectron spectroscopy （XPS） are used to characterize these catalysts in terms of their structure and composition. XPS results indicate that the pyrrolic-N groups are the most active sites, a finding that is supported by the correspondence between changes in pyridinic-N content and ORR activity that occur with changing temperature. Sulfur species are also structurally bound to carbon in the forms of C-Sn-C, an additional beneficial factor for the ORR.

Ultrasonically Assisted Regioselective Nitration of Aromatic Compounds in Presence of Certain Group V and VI Metal Salts

Ultrasonically assisted nitration reactions (USANR) with anilides, moderately activated and non-activated aromatic compounds underwent smoothly and afforded good yields of products with high regio selectivity. Observed longer reaction times (6 - 8 hrs.) in metal catalyzed reactions reduced to (1 - 2 hrs.) under sonication. When ortho position is blocked para derivatives are obtained, and ortho nitro products are obtained when para position is blocked. In case of USANR of aromatic carbonyl and related compounds the effect of sonication is much more effective. The reactions could be completed only in few minutes.

Applying ellipsometry to studying the effect of two kinds of rare earth metal salts on anodizing aluminum alloy

The effects of rare earth metal salts (REMs), cerium(IV) salt and lanthanum (III) salt, on the property of anodized coating of LD10 aluminum alloy are studied by corrosion tests including neutral salt spray test and copper accelerated acetic acid immersion test, polarization curves measurement, energy dispersion analyzer of X-Ray(EDAX) analysis, and in situ ellipsometry. The results show that the addition of either of the two REMs in anodizing solution hardly changes the composition of an anodized coating, while increases the thickness of barrier part and reduces the porosity of porous part, which contributed to the improvement of the corrosion resistance of the anodized coating. The results also demonstrate that the effect of cerium salt was better than that of lanthanum salt.

The Negative Effect of Heavy Metal Salts on the Body of Mammal Animals

The main purpose of this presented article was to explain the need to study the amount of heavy metal salts in the environment where animals live, in the water, in air, and in the food and fodder consumed. This article presents materials from the literature on the effects of heavy metal salts on the body of animals and the environment in which they live. The cited analytical data showed that the general information on the negative effects of heavy metal salts on the body is sufficient, but their effects on the digestive tract and morpho-functional properties of rabbits should be studied in depth. Therefore, we planned to focus our scientific work on this topic. The article mainly refers to salts of heavy metals cadmium, lead, and mercury (Cd, Pb, Hg). It is noted in the literature that heavy metal salts have a negative effect on the body of animals. We focused mainly on data on the effects of heavy metals on farm animals, including rabbits. But it is clear that the authors referred to were referring to experimental animals. These negative effects are manifested in the form of disorders of digestive functions, disorders of neurovegetative processes, increasing incidence of cardiovascular disease, rapid heart failure, deterioration of calcium metabolism, as well as impaired haemoglobin metabolism. Disorders of protein metabolism manifest themselves in the form of cases of hyperproteinaemia and dysproteinaemia. The results of the evaluation of the organism of healthy animals in chemically and radioactively contaminated areas showed the accumulation of significant levels of chemical elements in their organism. We mainly looked at the effects of heavy metal salts on farm animals. The cited analytical data showed that the general information on the negative effects of heavy metal salts on the body is sufficient, but the effects on the activity of organ systems in the body (respiration, blood and blood circulation, digestion, reproduction, productivity and immunological systems) have not been comprehensively studied.

Nonmetal-Metal Transition in Solutions of Metals in Molten Salts

Solutions of metals in molten salts present a rich phenomenology: localisatlon of electrons in disordered ionic media, activated electron transport increasing with metal concentration towards a nonmetal-metal (NM-M) transition, and liquid-liquid phase separation. A brief review of progress in the study of these systems is given in this article, with main focus on the NM-M transition. After recalling the known NM-M behaviour of the component elements in the case of expanded fluid alkali metals and mercury and of solid halogens under pressure, the article focuses on liquid metal-molten salt solutions and traces the different NM-M behaviours of the alkalis in their halides and of metals added to polyvalent metal halides.

Reversion of Bioluminescent Bacteria (Mutatox^(TM)) toTheir Luminescent State upon Exposure to OrganicCompounds, Munitions, and Metal Salts

Mutatox is a new genotoxicity bioassay which uses as the endpoint the bioluminescence produced on reversion of a dark strain of the marine bacterium Vibrio fischeri ±S9.Reversion can occur by several mechanisms, including base substitution, frame-shift, SOS induction, and DNA intercalation. For screening, Mutatox provides many advantages over the Salmonella trphimurium (Ames) assay: it requires minimal sterility, employs a shorter incubation period, and does not require culture maintenance. Eighteen organic chemicals (phenol, polynuclear aromatic hydrocarbons, nitrotoluenes, others), Na3PO4, and 4 genotoxic metals (Cu2+, Ni2+, As3+, Cd2+) were tested. Most of the organic compounds positive in S. typhimurium assays were positive in Mutatox. None of the metals was genotoxic in V. fischeri, possibly due to poor uptake from the saline medium

Enhanced preparation of dendritic metallic vanadium in recyclable NaCl-KCl-VCl_(2) molten salt by V_(2)CO electrolysis

A promising method for the preparation of pure metallic vanadium via V_(2)CO anode electrolysis was proposed and confirmed.The simple and controllable synthesis of a molten chloride salt containing VCl_(2) by an insitu reaction between VCl_(3) and metallic vanadium was verified through thermodynamic analysis and experiments.NaCl-KCl-VCl_(2) molten salt exhibited excellent recycling performance and could be repetitively used to prepare metallic vanadium by V_(2)CO electrolysis.The V^(2+) ions remained in the molten salt after electrolysis.The electrolysis conditions,such as the cathode diameter,current density,V^(2+) ion concentration,and temperature,were optimised to maximise the current efficiency.Electrolysis was also simulated to reveal the regulatory mechanism.The highest current efficiency was 85%.The purity of metallic vanadium was up to 99.8%.In this study,an easy and efficient preparation of pure metallic vanadium was achieved.

A novel approach for one-step forming ε-caprolactam from cyclohexane nitrozation catalyzed by transition metal salt

The nitrozation reaction of cyclohexane in one-step reaction to form ε-caprolactam has been studied using transition metal salt as catalysts in this work. The results indicated that the catalysts play an especially important role. This method is expected to be a novel way to synthesize other lactam by similar reaction. The possible mechanism was suggested.