Direct electrochemical preparation of solid Fe(VI) ferrate,and super-iron battery compounds

The electrochemical generation of Fe(VI) salts eliminates requirements for chemical oxidants and decreases the synthesis complexity. An alternate electrochemical synthesis from an iron anode in alkaline electrolyte is presented for the in situ direct synthesis of the solid Fe(VI) salts, such as BaFeO₄. A variety of electrolysis conditions including cell configuration, applied current density, temperature, synthesis duration, electrolyte composition and concentration, and the molar ratio between the reactants have been explored. In situ electrochemically synthesized BaFeO₄ exhibits similar valence, IR absorption spectrum and X-ray powder diffraction as the chemically synthesized material.     

电化学合成镍配合物的研究

采用金属镍为“牺牲”阳极，首次在无隔膜电解槽中，电化学溶解金属镍一步 制备了纳米NiO前驱体Ni(Oet)2,Ni(Obu)2,Ni(Oet)2(acac)2，Ni(Obu)2(acac)2 [acac为乙酰丙酮基].产物通过红外光谱（FT-IR）、拉曼光谱（Raman spectrum） 进行表征。同时讨论了影响电合成镍醇盐及其配合物的关键因素。实验表明，防止 阳极钝化，温度控制在30-40℃，采用有机胺溴化物为导电盐，可以提高电合成效 率。     

钛醇盐电化学合成的研究

采用钛金属为“牺牲”阳极,首次在无隔膜电解槽中,电化学一步法制备了纳米TiO~2前驱体钛醇盐Ti(OEt)~4,Ti(OPr-i)~4,Ti(OBu)~4。产物通过元素分析、红外光谱(FT-IR)、拉曼光谱进行表征。电化学一步法直接制备纳米材料前驱体钛醇盐,克服了传统化学方法合成金属醇盐步骤多、产率低、纯度达不到要求及后续分离繁琐等缺点。本文同时讨论了影响电合成钛醇盐的关键因素及可能的反应机理,实验表明钛在醇溶液中呈点蚀行为,钛醇盐卤化物Ti(Ⅲ)(OR)~nBr~m在阳极形成,然后被氧化为Ti(Ⅳ)(OR)~nBr~m,这种物质在阴极上ROH参与下被还原生成钛醇盐Ti(OR)~4,钛阳极表面拉曼光谱证实了上述观点。防止阳极钝化,温度控制在50～60℃之间,彩有机胺溴化物为导电盐,可以提高电合成收率。     

Electrochemical studies of potassium ferrate(VI)

The electrochemical reduction of potassium ferrate(VI) in 6N-KOH occurs in three steps, at approximately +0.3, ?0.7, and ?1.4 V vs. Hg/HgO, 6N-KOH. The first reduction appears as a voltammetric wave on a platinum electrode and the second two are observed as polarographic waves with a dropping mercury electrode. Controlled potential coulometric, voltammetric, and chronopotentiometric studies indicate the reduction proceeds stepwise first to iron(III), then to iron(II) and finally to iron(0).     

Direct sonochemical preparation of high-surface-area nanoporous ceria and ceria-zirconia solid solutions

For the first time, nanoporous ceria and ceria-zirconia solid solutions with high surface area have been successfully synthesized directly via high-intensity ultrasound irradiation without thermal post-treatment. The ceria and the solid solutions were characterized by XRD, TEM, and nitrogen adsorption. It was found that the nanoporous structures of the materials obtained were formed by the agglomeration of monodispersed nanoparticles under high-intensity ultrasound irradiation.     

基于次氯酸钙的高铁酸钾制备与表征

为提高化学氧化法制备高铁酸钾的安全性,以次氯酸钙和碳酸钾反应制备碱性饱和次氯酸钾,继而氧化九水硝酸铁制备高铁酸钾。对制备条件进行了优化,结果表明次氯酸钾浓度1.15mol/L,反应时间60min,重结晶碱浓度15.48mol/L,正戊烷和无水乙醇交替洗涤除杂条件下所制备的高铁酸钾纯度较高。采用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)以及紫外-可见吸收光度法对样品进行定性分析,证实所制备样品为高铁酸钾。采用邻菲罗呤分光光度法定量测定样品纯度,高铁酸钾含量大于97%。     

EQCM studies of composition and electrochemical performance of film prepared by electrochemical reduction of sodium ferrate

A solid film was prepared by electrodepositing on a gold-film-coated quartz crystal electrode in Na₂FeO₄ solution, and characterized in 1?M LiClO₄/propylene carbonate (PC) + 1, 2-dimethoxyethane (DME; 1:1 by volume) electrolyte using electrochemical quartz crystal microbalance (EQCM). The EQCM experimental and X-ray photoelectron spectroscopy results indicate that the composition of the electrodeposited solid film prepared in the potential range of 0.18 to ?0.57?V vs. Ag/AgCl is FeOOH; and almost 1?mol lithium ions can be intercalated into and then extracted from 1?mol FeOOH film during discharge/charge process in 1?M LiClO₄/PC + DME electrolyte. The discharge/charge experiment indicates that the specific capacity of FeOOH film stabilizes at a value close to its theoretical specific capacity after 20 cycles, and FeOOH film maintains a specific capacity of about 300?mAh?g^?1 at the end of 170 cycles. It is therefore concluded that the FeOOH film has a good electrochemical cycle ability in 1?M LiClO₄/PC + DME electrolyte.     

Efficient iodination of aromatic compounds using potassium ferrate supported on montmorillonite

Potassium ferrate impregnated on montmorillonite is a mild,cheap,and non-toxic reagent for the iodination of phenols, including naphthol,aromatic amines,and heterocyclic substrates in fair to excellent yields by a simple isolation procedure.     

The kinetics of oxidation of low molecular weight aldehydes by potassium ferrate

Summary Oxidation of simple aldehydes is shown to follow a mixed order rate equation(¹), which contains three terms: the first, first order in the concentration of potassium ferrate (K₂FeO₄); the second, second order in K₂FeO₄; and the third contains the conditional rate constants which are substrate (aldehyde) concentration dependent. The third term is first order dependent on (K₂FeO₄). Aldehydes studied included chloral, acetaldehyde, and trimethylacetaldehyde.     

The kinetics of oxidation of simple aliphatic sulphur compounds by potassium ferrate

Potassium ferrate (K₂FeO₄) is highly soluble in water and a very strong oxidizing agent^{(1, 2)}. Other properties include a strong bacteriacidal action which has been documented by Murmann and Robinson⁽¹⁾. These characteristics, and others, suggest that potassium ferrate would be useful in the advanced treatment of municipal waste water. The efficiency of oxidation of various organic compounds by potassium ferrate must be investigated before conclusions can be drawn.When K₂FeO₄ is placed into aqueous solution a purple colour is produced which disappears as K₂FeO₄ is reduced. At a spectrophotometric wavelength of 505 nm this affords a convenient method for measuring the decomposition kinetics of K₂FeO₄.Rate constants were obtained by algorithmic analysis of spectral absorbance data by the Cornell method⁽³⁾. This work will present a mechanism of reaction for oxidation of simple aliphatic sulphur compounds by potassium ferrate. The oxidation of simple aliphatic sulphur compounds produces the corresponding sulphoxide or sulphone^{(4, 5)} Compounds studied included dimethyl sulphoxide, diethylsulphide, dimethylsulphone, and 2,2-thiodiethanol.     

相转移催化下复合高铁酸钾氧化甲苯的研究

制备了高稳定性的复合高铁酸钾氧化剂,并进行了表征.研究了高铁酸钾溶液的pH值和浓度对高铁酸钾稳定性的影响,并确定了高铁酸钾稳定存在的溶液环境.以复合高铁酸钾为氧化剂,采用相转移催化氧化甲苯法合成苯甲酸.考察了相转移催化剂种类、催化剂用量、反应时间以及反应温度等因素对苯甲酸收率的影响.结果表明,以十六烷基三甲基溴化铵作相...     

Direct electrochemical oxidation of polyacrylates

A promising elimination treatment of non-biodegradable organic pollutants is the direct electro-oxidation. In this work has been proposed the electrochemical elimination of polyacrylates by using boron-doped diamond (BDD) as anodic material. The complete elimination of organic contaminants has been obtained and this is the first case of successful electrochemical treatment of polymeric and bio-refractory species. The tests of the electrochemical oxidation have been conducted at constant current conditions and a complete elimination of organic species has been reached. The decrease of the COD value with time follows the behaviour of an ideal anode as in the case of low molecular organic compounds.     

高铁酸钾氧化脱除模拟轻质油中的含硫化合物

考察了K2FeO4对模拟轻质油中苯并噻吩（BT）及二苯并噻吩（DBT）的氧化性能。结果表明,水相中K2FeO4对BT、DBT的氧化活性比较低,水的存在使K2FeO4水解成黄色的Fe(OH)3而失去氧化有机硫化物的能力;在冰乙酸反应介质中,K2FeO4对BT及DBT的氧化活性有了明显的提高;固体催化剂KM的加入显著提高了乙酸反应介质中K2FeO4对BT及DBT的氧化活性。常温、常压,醋酸/模拟油体积比为1.0,K2FeO4/S摩尔比为1.0,KM/K2FeO4质量比为1.0的条件下,DBT的转化率达98.4%,BT的转化率为70.1%。     

The kinetics and mechanism of the oxidation of seleno-DL- methionine by potassium ferrate

The kinetics of the reaction of seleno-DL-methionine with potassium ferrate were investigated under pseudo first-order conditions. The oxidation to the selenoxide is complete within the timeframe of 7.5ms to 2s. The kinetics are first-order in each of the hydrogen ion, selenomethionine and ferrate ion concentrations over the pH range 8.53 to 10.13, but zeroth-order in hydrogen ion concentration at lower pH values. The results are very similar for methionine, except that the overall rate constant is over two orders of magnitude lower. The proposed mechanism involves a rate- determining step between selenomethionine and the protonated ferrate ion.     

The adsorption of silver on potassium cyanocobalt(II)ferrate(II)

A procedure is described for recovering silver from industrial sewage (mining and photo-industry etc) with the aid of the ion-exchanger potassium cyanocobalt(II)ferrate(II) (KCFC). Silver is easily removed by simple mixing with KCFC, even from solutions containing less than 1 g of silver per ton of solution. The process is performed at room temperature at pH < 7. There is no interference from a 600-fold amount of Ca, Cu(II), Zn, Cd, Pb, and Fe(II). Pure silver may be obtained by dissolution of the ion-exchanger in potassium cyanide solution, subsequent precipitation as sulphide, and roasting, or by melting it out of the ion-exchanger after heat treatment in a high-frequency furnace. With 1 kg of KCFC, 1.25 kg of silver may be extracted from solution. The process is simple and economic.     

Facile preparation of potassium 32P-phosphonate

Simple and easy to operate experimental assemblies were for the first time designed for the successful preparation of potassium ³²P-phosphonate from ³²P-orthophosphate. Phosphate was first converted to phosphoryl chloride by reacting with phosphorus pentachloride. Then the phosphoryl chloride formed was reduced to phosphorus trichloride by heating with charcoal at 650 °C. The latter was absorbed in aqueous potassium hydroxide to obtain potassium ³²P-phosphonate at a yield of about 75%. The chemical purity of ³²P-phosphonate was assayed using ion-chromatography and the radiochemical purity was also determined.The authors thank Shri. J. K. Ghosh, Chief Executive, BRIT and Dr. N. Sivaprasad, General Manager, RPh & ILCJ, BRIT for their support and encouragement throughout this work.