Oxidation of chlorinated ethenes by potassium permanganate: a kinetics study

The kinetics of oxidation of perchloroethylene (PCE), trichloroethylene (TCE), three isomers of dichloroethylene (DCE) and vinyl chloride (VC) by potassium permanganate (KMnO(4)) were studied in phosphate-buffered solutions of pH 7 and ionic strength approximately 0.05 M and under isothermal, completely mixed and zero headspace conditions. Experimental results have shown that the reaction appears to be second order overall and first order individually with respect to both KMnO(4) and all chlorinated ethenes (CEs), except VC. The degradation of VC by KMnO(4) is a two-consecutive-step process. The second step, being the rate-limiting step, is of first order in VC and has an activation energy (E(a)) of 7.9+/-1 kcal mol(-1). The second order rate constants at 20 degrees C are 0.035+/-0.004 M(-1) s(-1) (PCE), 0.80+/-0.12 M(-1) s(-1) (TCE), 1.52+/-0.05 M(-1) s(-1) (cis-DCE), 2.1+/-0.2 M(-1) s(-1) (1,1-DCE) and 48.6+/-0.9 M(-1) s(-1) (trans-DCE). The E(a) and entropy (DeltaS(*)) of the reaction between KMnO(4) and CEs (except VC) are in the range of 5.8-9.3 kcal mol(-1) and -33 to -36 kcal mol(-1) K(-1), respectively. Moreover, KMnO(4) is able to completely dechlorinate CEs, and the increase in acidity of the solution due to CE oxidation by KMnO(4) is directly proportional to the number of chlorine atoms in CEs.     

镁合金微弧氧化着色膜研究

镁合金在电子工业中的快速发展对装饰性能提出了更高的要求.主要研究了如何在微弧氧化的同时进行氧化着色.膜层制备选取的基材为AZ91,电解溶液由硅酸盐为主的碱性溶液组成,配方为:Na2SiO3 5～30g/L,KMnO4 1～20g/L,NaOH 1～5g/L,KF 5～8g/L,Na3 C6H5O70.5～2g/L,EDTA 0.5～2g/L.在电解液中添加着色盐KMnO4,形成了颜色各异的黄色陶瓷膜层.研究发现,膜层呈现出黄色主要是由于在膜层中生成了Mg6MnO8相,该物相在氧化膜中含量不同和分布差异将导致样品颜色深浅不同.     

MnOx/AC的制备及电催化氧化降解苯酚

采用活性炭还原KMnO4制备MnOx/AC催化剂,利用SEM、XPS对其进行表征。结果表明,Mn以MnO2的形式存在于活性炭表面。辊压成型法制成MnOx/AC电极,以所制MnOx/AC电极为阴极、Ti/RuO2电极为阳极,对苯酚废水进行电解氧化处理,研究了电流密度、电极间距离、初始pH值、电解质溶液浓度等因素对处理效果...     

Design and synthesis of MnO₂/Mn/MnO₂ sandwich-structured nanotube arrays with high supercapacitive performance for electrochemical energy storage

We demonstrate the design and fabrication of novel nanoarchitectures of MnO(2)/Mn/MnO(2) sandwich-like nanotube arrays for supercapacitors. The crystalline metal Mn layers in the MnO(2)/Mn/MnO(2) sandwich-like nanotubes uniquely serve as highly conductive cores to support the redox active two-double MnO(2) shells with a highly electrolytic accessible surface area and provide reliable electrical connections to MnO(2) shells. The maximum specific capacitances of 937 F/g at a scan rate of 5 mV/s by cyclic voltammetry (CV) and 955 F/g at a current density of 1.5 A/g by chronopotentiometry were achieved for the MnO(2)/Mn/MnO(2) sandwich-like nanotube arrays in solution of 1.0 M Na(2)SO(4). The hybrid MnO(2)/Mn/MnO(2) sandwich-like nanotube arrays exhibited an excellent rate capability with a high specific energy of 45 Wh/kg and specific power of 23 kW/kg and excellent long-term cycling stability (less 5% loss of the maximum specific capacitance after 3000 cycles). The high specific capacitance and charge-discharge rates offered by such MnO(2)/Mn/MnO(2) sandwich-like nanotube arrays make them promising candidates for supercapacitor electrodes, combining high-energy densities with high levels of power delivery.     

Magnetic Fe(2)MO(4) (M:Fe, Mn) activated carbons: fabrication, characterization and heterogeneous Fenton oxidation of methyl orange

We present a simple and efficient method for the fabrication of magnetic Fe(2)MO(4) (M:Fe and Mn) activated carbons (Fe(2)MO(4)/AC-H, M:Fe and Mn) by impregnating the activated carbon with simultaneous magnetic precursor and carbon modifying agent followed by calcination. The obtained samples were characterized by nitrogen adsorption isotherms, X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), and the catalytic activity in heterogeneous Fenton oxidation of methyl orange (MO) was evaluated. The resulting Fe(2)MnO(4)/AC-H showed higher catalytic activity in the methyl orange oxidation than Fe(3)O(4)/AC-H. The effect of operational parameters (pH, catalyst loading H(2)O(2) dosage and initial MO concentration) on degradation performance of the oxidation process was investigated. Stability and reusability of selected catalyst were also tested.     

基于阴离子还原剂制备的超级电容器用中孔MnO2研究

以Na2S2O3为还原剂,KMnO4为氧化剂制备了超级电容器用MnO2,采用SEM、N2吸附-脱附和XRD对样品进行了分析.用循环伏安和恒流充放电测试对样品的电化学性能进行了表征.结果表明,实验制备的MnO2为无定型结构,呈类球状,直径为20～40nm,比表面积和平均孔径分别为182.6m2/g和6.2nm.在1mol/L (NH4)2SO4水溶液中,在-0.4～0.5V(vs.SCE)的电位范围内,MnO2具有典型的赝电容特性和高功率特性.在10mA/cm2的电流密度下,MnO2比容达到397F/g,且具有高循环效率.     

Adsorption of fluoride in aqueous solutions using KMnO4-modified activated carbon derived from steam pyrolysis of rice straw

Fluoride in drinking water above permissible levels is responsible for human and skeletal fluorosis. In this study, activated carbons (AC) prepared by one-step steam pyrolysis of rice straw at 550, 650, 750 degrees C, respectively, were modified by liquid-phase oxidation using HNO3, H2O2 and KMnO4. Characterization of these 12 carbons was made by their surface area, porosity, acidity, basicity, pH(pzc), pH and ability to remove fluoride anion. Based on the data of the latter factor, the RS2/KMnO4 carbon was selected. Along with batch adsorption studies, which involve effect of pH, adsorbate concentration, adsorbent dosage, contact time, temperature, and Co-ions (SO4(2-), Cl-, Br-). The effects of natural organic matter (NOM) were also made to remove the fluoride from natural water. On the basis of kinetic studies, specific rate constants involved in the adsorption process using RS2/KMnO4 carbon was calculated and second-order adsorption kinetics was observed. Equation isotherms such as Langmuir (L), Freundlich (F), Langmuir-Freundlich (LF) and Dubinin-Radushkevich (DR) were successfully used to model the experimental data. From the DR isotherm parameters, it was considered that the uptake of F- by RS2/KMnO4 carbon proceeds by an ion-exchange mechanism (E=10.46 kJ mol(-1)). The thermodynamic parameters of fluoride sorption were calculated and the sorption process was chemical in nature. The ability of RS2/KMnO4 to remove F- from Egyptian crude phosphoric acid (P(2)O(5)=48.42%) was tested and the adsorption capacity of F- in H(3)PO(4) was greater than that in distilled water. This is may be due to fluoride adsorption enhanced at lower pH of crude acid.     

铝合金表面铈锰化学转化

以硝酸铈和高锰酸钾为主盐,在6063铝合金表面制备了Ce-Mn化学转化膜。研究了室温下成膜时间、转化液pH值、硝酸铈和高锰酸钾浓度对Ce—Mn转化膜电化学性能的影响,获得了最佳成膜工艺：7g／LCe（NO3）3,2g／LKMnO4,时间9min,pH值2．3。采用极化曲线考察了所得转化膜的耐蚀性,并通过扫描电镜和能谱仪分析了膜的表面微观形貌和组成。结果表明：Ce．Mn转化膜比6063铝合金具有更低的腐蚀电流密度和更大的极化电阻,表现出良好的耐腐蚀性能;Ce-Mn转化膜主要成分是铝、镁、铈、锰和氧。     

Voltammetric determination of tryptophan at a single-wall carbon nanotubes modified electrode

A single-wall carbon nanotubes (SWNT)-film coated glassy carbon electrode (GCE) was described for the determination of tryptophan. In pH 2.5 Na2HPO4-citric acid buffer, tryptophan yields a well-defined and very sensitive oxidation peak at about 1.08 V at the SWNT-film coated GCE. The oxidation peak current increases greatly and the peak potential shifts toward more negative direction at the SWNT-modified GCE in contrast to that at the bare GCE. Under optimized conditions, the oxidation peak current is proportional to the concentration of tryptophan over the range from 4 x 10(-8) to 1 x 10(-5) mol/L. The detection limit is 1 x 10(-8) mol/L at 3 min of accumulation. Using the proposed method, tryptophan in the human's blood serum samples was determined.     

高锰酸钾对炭微球表面的改性

首先采用化学气相沉积法,在氩气气氛下,以脱油沥青为原料制备了炭微球(CMSs);然后用不同浓度的KMnO4溶液对CMSs进行处理,使得CMSs表面被氧化并包覆一层MnO2;最后用草酸洗涤产物,除去MnO2。通过场发射扫描电镜对CMSs氧化前后的形貌进行观察,用X-射线衍射对产物进行结构表征,并考察了氧化前后的CMSs在水和乙醇中的分散性。结果表明:当用0.1mol/L的KMnO4氧化改性CMSs后,CMSs表面包覆了一层MnO2,形成MnO2/CMSs复合材料。经过量的草酸进行洗涤,得到的产物在水中分散效果很好,且在乙醇中也有一定分散性。氧化后CMSs的表面存在亲水活性位点,为CMSs的进一步功能修饰奠定了基础。     

Extent of oxidation of Cr(III) to Cr(VI) under various conditions pertaining to natural environment

Calculations show that oxidation of chromium oxide (Cr2O3) by oxygen and oxidation of chromium hydroxide (Cr(OH)3) by manganese dioxide (MnO2) are thermodynamically feasible in both aerobic and mildly anoxic environments. Experiments were carried out to determine the rate and extent of chromium oxidation under various conditions, i.e., when Cr2O3 was heated in the presence of oxygen, when Cr(OH)3 and MnO2 mixtures were suspended in aerobic or anoxic aqueous media at various pH values, when Cr(OH)3 and MnO2 mixtures interacted in moist aerobic conditions and when chromium assumed to be Cr(OH)3 and manganese assumed to be MnO2 interacted in the presence of competing electron donors/acceptors, as is the case in chromium-contaminated sludge. Results indicate that trivalent chromium in Cr2O3 could be readily converted to hexavalent chromium at a temperature range of 200-300 degrees C, with conversion rates of up to 50% in 12 h. In aqueous media, Cr(OH)3 was slowly converted to dissolved Cr(VI) in the presence of MnO2, both in aerobic and anoxic conditions, with conversion rates of up to 1% in 60 days. In moist aerobic conditions and in the presence of MnO2, Cr(OH)(3) slowly converted to hexavalent chromium, with up to 0.05% conversion observed in 90 days. Chromium oxidation also occurred in sludge samples, especially under aerobic conditions. However, such transformation was found to be transitory, with the Cr(VI) formed being ultimately reduced back to Cr(III) due to the presence of various reducing agents in the sludge. Nevertheless since up to 17% conversion of Cr(III) to Cr(VI) occurred in sludge under aerobic conditions by 30 days, there is real danger under field conditions of spreading Cr(VI) pollution due to possible intervening rainfall, runoff and percolation.     

Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors

In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE).     

纯钛材微弧氧化电参数对陶瓷层组织结构的影响

以往就纯钛材表面微弧氧化陶瓷层表面积对提供羟基磷灰石生长条件的研究不多,为此,在Na2HPO4电解液中,采用微弧氧化法在纯钛材表面制得多孔结构的二氧化钛陶瓷层.研究了正向电压、频率对微弧氧化陶瓷层组织结构的影响.结果表明,随正向电压升高,膜厚增加,孔径增大,表面变得粗糙;随频率的增加,膜层表面变得光滑,孔径减小,膜厚减...     

Degradation of trichloroethylene by Fenton reaction in pyrite suspension

Degradation of trichloroethylene (TCE) by Fenton reaction in pyrite suspension was investigated in a closed batch system under various experimental conditions. TCE was oxidatively degraded by OH in the pyrite Fenton system and its degradation kinetics was significantly enhanced by the catalysis of pyrite to form OH by decomposing H(2)O(2). In contrast to an ordinary classic Fenton reaction showing a second-order kinetics, the oxidative degradation of TCE by the pyrite Fenton reaction was properly fitted by a pseudo-first-order rate law. Degradation kinetics of TCE in the pyrite Fenton reaction was significantly influenced by concentrations of pyrite and H(2)O(2) and initial suspension pH. Kinetic rate constant of TCE increased proportionally (0.0030 ± 0.0001-0.1910 ± 0.0078 min(-1)) as the pyrite concentration increased 0.21-12.82 g/L. TCE removal was more than 97%, once H(2)O(2) addition exceeded 125 mM at initial pH 3. The kinetic rate constant also increased (0.0160 ± 0.005-0.0516 ± 0.0029 min(-1)) as H(2)O(2) concentration increased 21-251 mM, however its increase showed a saturation pattern. The kinetic rate constant decreased (0.0516 ± 0.0029-0.0079 ± 0.0021 min(-1)) as initial suspension pH increased 3-11. We did not observe any significant effect of TCE concentration on the degradation kinetics of TCE in the pyrite Fenton reaction as TCE concentration increased.     

Effects of pH on dechlorination of trichloroethylene by zero-valent iron

The surface normalized reaction rate constants (k(sa)) of trichloroethylene (TCE) and zero-valent iron (ZVI) were quantified in batch reactors at pH values between 1.7 and 10. The k(sa) of TCE linearly decreased from 0.044 to 0.009l/hm(2) between pH 3.8 and 8.0, whereas the k(sa) at pH 1.7 was more than an order higher than that at pH 3.8. The degradation of TCE was not observed at pH values of 9 and 10. The k(sa) of iron corrosion linearly decreased from 0.092 to 0.018l/hm(2) between pH 4.9 and 9.8, whereas it is significantly higher at pH 1.7 and 3.8. The k(sa) of TCE was 30-300 times higher than those reported in literature. The difference can be attributed to the pH effects and precipitation of iron hydroxide. The k(sa) of TCE degradation and iron corrosion at a head space of 6 and 10ml were about twice of those at zero head space. The effect was attributed to the formation of hydrogen bubbles on ZVI, which hindered the transport the TCE between the solution and reaction sites on ZVI. The optimal TCE degradation rate was achieved at a pH of 4.9. This suggests that lowering solution pH might not expedite the degradation rate of TCE by ZVI as it also caused faster disappearance of ZVI, and hence decreased the ZVI surface concentration.     

Oxidation of Cr(III) in tannery sludge to Cr(VI): field observations and theoretical assessment

Sludge, soil and leachate samples collected from a chromium-contaminated tannery waste dumping site in Kanpur, India, were found to contain considerable amounts of Cr(VI), despite the fresh tannery sludge containing little or no Cr(VI). Literature reports suggested that dry Cr(III) precipitates could be converted to Cr(VI) when heated in the presence of oxygen. Also, Cr(III) in aqueous phase could be oxidized through interaction with manganese dioxide (MnO2) surface to Cr(VI). Measurement of manganese in the sludge samples collected from the site showed concentrations up to 0.6 mg/g. Based on equilibrium calculations, it was determined that both dry phase Cr(III) oxidation by atmospheric oxygen and aqueous phase Cr(III) oxidation by MnO2 surface were thermodynamically feasible. It was further suggested that in aqueous phase, manganese may act effectively as an electron transporter between Cr(III) and dissolved oxygen during Cr(III) oxidation, leading to regeneration of MnO2 solid phase. Further, as dissolved Cr(III) is oxidized, dissolution of Cr(OH3) will take place to maintain the equilibrium between the dissolved and solid phases of Cr(III). In the pH range of 3-10, and at oxygen partial pressure (P(O2)) of 10(-6) atm or higher, equilibrium conditions stipulate nearly complete conversion of Cr(III) to Cr(VI). At P(O2) of 10(-20) atm or lower, very little Cr(VI) is expected to be present under equilibrium conditions. In the intermediate P(O2) regions, incomplete dissolution of the Cr(OH3) solid phase and only partial conversion of chromium from +3 to the +6 oxidation state is expected, especially at lower pH values.     

Interfacial synthesis: amphiphilic monomers assisted ultrarefining of mesoporous manganese oxide nanoparticles and the electrochemical implications

Amphiphilic monomers, namely pyrrole and aniline, were used to reduce permanganate ion (MnO(4)(-)) at the dichloromethane/water interface for the preparation of ultrafine manganese oxide (MnO(x), x ≤ 2) nanoparticles (NPs). These monomers did not undergo polymerization upon oxidation by MnO(4)(-), but exerted an interesting effect of ultrarefining the produced MnO(x) NPs from reducing MnO(4)(-) at the organoaqueous interface. This was attributed to the ability of the monomer to access the interfacial reaction sites from both organic and aqueous phases, and hence retard the as-produced MnO(x) nuclei from aggregation at the interface. Such obtained products were mesoporous matrixes of three-dimensionally interconnected and uniform pseudospherical MnO(x) NPs (<20 nm). On the contrary, using a more hydrophobic monomer, i.e., o-aminophenol, to reduce MnO(4)(-) produced a composite of nanobelts of poly(o-aminophenol) embedded in micrometer-sized MnO(x) blocks. The ultrafine MnO(x) NPs prepared from using aniline or pyrrole exhibited highly capacitive behavior in aqueous Na(2)SO(4), promising their use in supercapacitors. It was also found that the MnO(x) NPs prepared from pyrrole-assisted synthesis possessed higher specific capacitance than that from aniline-assisted synthesis, despite the latter having a higher specific surface area. This difference is discussed in terms of crystallographic properties and water contents of these two samples.     

Characterization of Functional Nanofilms on InP by Ultrasoft X-ray Emission and Infrared Spectroscopies

Inorganic Materials - The thermal oxidation of InP in the presence of both a MnO2 chemical stimulator layer produced on its surface by magnetron sputtering and a Mn3(PO4)2 modifier introduced...     

Facile synthesis and characterization of potassium-doped MnO2 nanowires

A new type of potassium doped manganese oxide nanowires were synthesized using a simple hydrothermal route. The reduction of MnO4- in the presence of acetate species led to the formation of the Multi-filamentous nanowire structure. Detailed TEM and chemical characterizations indicated that potassium ions were homogeneously distributed in the nanowires. XPS results show a clear binding energy shift (1 eV) for K(2p) peak in nanowires compared with its starting material of KMnO4. Detailed synthetic condition investigation indicated that the presence of acetate ions played an important role in the formation of such a type of nanowires other than layered structures.     

Characterisation of K, Na, and Li birnessites prepared by oxidation with H2O2 in a basic medium. Ion exchange properties and study of the calcined products

Birnessites containing Na, K or Li in the interlayer have been prepared by oxidation of Mn(II) cations with H₂O₂ in a basic medium with different alkaline cation/Mn molar ratios. The solids prepared have been characterised by elemental chemical analysis, powder X-ray diffraction, thermal analyses (differential thermal analysis and thermogravimetric analysis), FT-IR spectroscopy and surface texture assessment by adsorption of N₂ at –196°C. Crystalline birnessites are obtained for A/Mn ratios (A = K, Li) larger than 3.4, but MnO(OH) has been also identificed when such a ratio is smaller than 3.4. Ion exchange is topotactic, but is not complete for exchanging Na, K, or Mg for pre-existing Li. The solids are stable up to 400°C, and formation of spinels and solids with tunnel structures is observed at this temperature. Li-containing birnessites are transformed to LiMn₂O₄ spinel at 400°C, and co-crystallization of bixbyte (Mn₂O₃) is observed at higher temperatures. Bixbyte and cryptomelane are formed at 500°C for the K-containing birnessites.