Electrochemical dissolution of Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> in acid solutions

The present study deals with the electrochemical reductive dissolution of Mn₃O₄, which was added to carbon-paste electroactive electrodes (CPEEs) in acid solutions. It was found that in the experimental conditions the thermodynamically stable form of manganese was . Kinetic features of the electrochemical reductive dissolution of Mn₃O₄, which was realized under potential cycling conditions (+1.0 V→−0.7 V→+1.0 V), were determined by the electrode polarization direction. It was shown that the cathodic reduction of Mn₃O₄ was accomplished in three stages. Manganese was dissolved in the supporting solution only at the third stage. The first two stages involved solid-phase reactions. The anodic cycling stage included an active dissolution of Mn₃O₄ and the lower manganese oxide (MnO) accumulated on the electrode surface during the cathodic reduction.     

钾锰氧化物：电化学控制合成及其电容器性质

Potassium manganese oxides were prepared by cathodic deposition from aqueous KMnO4 solution on an indium tin oxide slide. The products were characterized by XRD, XPS and SEM techniques. The as-prepared products were potassium manganese oxides with different manganese valence states. The component, morphology and size of the products could be controlled through adjusting the preparation parameters such as deposition potential, deposition time and acidity of the electrolyte. The results show that the deposition of potassium manganese oxide from aqueous KMnO4 is a pH value dependent procedure. Due to the facilitating of intercalation and deintercalation of cations, the specific capacitance of the products deposited for 500 s is higher than that indicate that the reversibility and performance of these potassium manganese oxides are also changed with the deposition time.     

Photometric study of the kinetics of TiO<Subscript>2</Subscript> hydrosol coagulation in electrolyte solutions

The aggregative stability of TiO₂ sols in aqueous solutions of NaCl, KCl, BaCl₂, and LaCl₃ is studied by photometry at pH 3.2 and natural values of pH (5.0–5.6). Dramatic effects of coion type and charge on the aggregation kinetics and characteristics of resulting aggregates are revealed.     

Electrosurface properties of microcrystalline cellulose dispersions in aqueous solutions of aluminum chloride, nitrate, and sulfate

The method of microelectrophoresis is employed to study the dependence of the ζ-potential of microcrystalline cellulose particles on the concentration (10^?6–10^?3 M) and pH (2–11) of aqueous aluminum chloride, nitrate, and sulfate solutions. It is shown that, in the absence of aluminum salts, the isoelectric point (IEP) of the particles is independent on the nature of acid anions and is observed at pH 3.2. The addition of aluminum salts in concentrations as low as 2 × 10 ^?6 M for chloride and nitrate and 1 × 10^?5 M for sulfate causes a shift of IEP to a less acidic region (pH 3.8), the value of which is virtually independent of the nature of the salt. As the concentration of salts is increased, the ζ-potential becomes positive, rises with an increase in pH to a maximum magnitude at pH 5.0–6.0, and decreases further until the second IEP (pH ～ 6.5–7.0) is reached. At higher pH values, the ζ-potential becomes negative again. The observed ζ(pH) dependences are explained by the formation of hydrolyzed aluminum species exhibiting different adsorbabilities on microcrystalline cellulose particles. It is shown that positively charged hydroxocomplexes formed in aluminum sulfate solutions are characterized by a lower adsorbability than hydroxocomplexes formed in chloride and nitrate solutions.     

The Permanganate Oxidation of Triethylamine; Evidence for the Formation of Manganate Ion in Potassium Permanganate/Triethylamine Reagent

The active oxidant of KMnO_4/Et₃N reagent has been verified as potassium manganate by ultraviolet spectrometry, and the final oxidation product as manganese(IV) oxide by iodometric titration.     

Thorium adsorption on graphene oxide nanoribbons/manganese dioxide composite material

A functional graphene oxide nanoribbons/manganese dioxide composite material (MnO₂-GONRs) was synthesized by hydrothermal method using graphene oxide nanoribbons (GONRs) as raw material which were formed by longitudinal unzipping of multi-walled carbon nanotubes with KMnO₄ and H₂SO₄. The microstructure of MnO₂-GONRs was characterized by SEM and FT-IR. The various factors affecting the adsorption of Th(IV) in aqueous solution such as pH, solid–liquid ratio, contact time, initial concentration and temperature were investigated by batch static adsorption experiments, and the adsorption mechanism is also discussed. The results showed that MnO₂-GONRs had a good adsorption effect on Th(IV) with a maximum adsorption of 166.11 mg/g.

     

Stabilization of Oil-in-Water Emulsions with SiO<Subscript>2</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles

Stabilization of oil-in-water Pickering emulsions with SiO₂ and Fe₃O₄ nanoparticles has been studied. Emulsions containing three-dimensional gel networks formed by aggregated nanoparticles in the dispersion media have been shown to be stable with respect to flocculation, coalescence, and creaming. Concentration ranges in which emulsions are kinetically stable have been determined. Stabilization with mixed Ludox HS-30 and Ludox CL SiO₂ nanoparticles leads to the formation of stable emulsions at a weight ratio between the nanoparticles equal to 2 and pH 6.7. In the case of stabilization with Ludox CL and Fe₃O₄ nanoparticles, systems resistant to aggregation and sedimentation are obtained at pH 8. The use of mixed Ludox HS-30 and Fe₃O₄ nanoparticles has not resulted in the formation of emulsions stable with respect to creaming, with such emulsions appearing to be resistant only to coalescence at pH 2–6.     

Physicochemical properties of manganese oxides obtained via the sol–gel method: The reduction of potassium permanganate by polyvinyl alcohol

Experimental data on the sol–gel synthesis of manganese oxides formed during the reduction of potassium permanganate by polyvinyl alcohol in an aqueous medium are presented. The physicochemical properties of the obtained manganese oxide systems that depend on the conditions of the synthesis are studied by means of DTA, XRD, SEM, and the low temperature adsorption–desorption of nitrogen. It is found that the obtained samples have a mesoporous structure and predominantly consist of double potassium–manganese oxide K₂Mn₄O₈ with a tunnel structure and impurities of oxides such as α-MnO₂, MnO, α-Mn₂O₃, and Mn₅O₈. It is shown that the proposed method of synthesis allows us to regulate the size and volume of mesopores and, to a lesser extent, the texture of the obtained oxides, which can be considered promising sorbents for the selective extraction of strontium and cesium ions from multicomponent aqueous solutions.     

SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> nanoparticles in Aerosol OT reverse microemulsions: Synthesis and characterization

Stable SiO₂ and TiO₂ organosols were prepared by hydrolyzing tetraethyl orthosilicate (TEOS) in the presence of 6–12 M NH₃ and titanium(IV) isopropylate (TTIP) in reverse microemulsions of 0.12–0.25 M bis(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT) in n-decane with the aqueous pseudophase content of 2–3 vol %, 0.018–0.090 M TEOS, and 0.15–0.55 vol %, 0.003–0.025 M TTIP. The degree of hydrolysis was monitored by IR spectroscopy (for TEOS) and spectrophotometry (for TTIP). Oxide nanoparticles were characterized by photon-correlation spectroscopy (PCS) (D _h = 8–100 nm) and laser electrophoresis (ζ-potential = 7.4–11.6 mV). The occurrence of surface potential made it possible to separate the oxides from the excess of surfactant by nonaqueous electrophoresis and to determine particle sizes (7–40 nm) by means of transmission electron microscopy (TEM).     

Characterization of anionic and cationic functionalized bacterial cellulose nanofibres for controlled release applications

Bacterial cellulose (BC) is a biocompatible biopolymer synthesized by Gluconacetobacter xylinus. In this study, BC was oxidized and aminated to produce hydrogels for biomedical applications, and the products were characterized. A carboxyl (pK_a of 3.9 ± 0.1) content of 1.13 ± 0.02 mmol/g was obtained with the TEMPO-catalyzed oxidation. Epichlorohydrin-mediated amination introduced amine groups (pK_a of 11.0 ± 0.1) up to 1.74 ± 0.06 mmol/g. The oxidation of BC caused a decrease in its ζ-potential to ?103 ± 6 mV, and amination increased the ζ-potential to ?4 ± 6 mV. The fibre diameter decreased after both reactions. The high absolute value of the ζ-potential for oxidized BC led to superior colloidal stability in water, and a 390 % increase in water retention. The oxidized BC hydrogel was also found to increase in water retention fivefold from pH 1 to 7, making it a smart hydrogel. The cationic and anionic BC hydrogels described here could be used for several biomedical applications, including self-assembling drug delivery devices.     

High effective electrocatalytic oxidation of cyclohexanol on stable Fe-Mn/Mn<Subscript>2</Subscript>O<Subscript>3</Subscript> membrane electrode

A new composite electrode material with iron-manganic oxide coating (Fe-Mn/Mn₂O₃) was prepared, and its catalytic performance for oxidizing cyclohexanol was investigated in this work. The new electrode material, based on iron substrate covered with electrolytic manganese, was obtained by further coating the manganese surface with 50 % manganese nitrate solution and then conducting program thermal decomposition treatment. X-ray diffraction (XRD) was used to determine the surface crystal phase compositions, which were Mn and Mn₂O₃. The catalytic results showed an excellent electrocatalytic performance on the oxidation of cyclohexanol, and the main products were cyclohexanone and hexanedioic acid. According to our experiment results and the literature reports, the existence of mixed valent Mn^III and Mn^IV played a key role in the electrocatalytic oxidation process. A probable process was proposed: the Mn^IV seized the hydrogen from cyclohexanol, the resulting cyclohexaneoxy radical was oxidized into cyclohexanone, and then the absorbed cyclohexanone was further oxidized into hexanedioic acid.     

Electrophoretic Deposition of Thin-Film Coatings of Solid Electrolyte Based on Microsize BaCeO<Subscript>3</Subscript> Powders

Results are presented of an electrophoretic deposition of thin-film coatings based on doped barium cerate BaCeO₃ on a cathode substrate La₂NiO₄ (LNO), which are of interest for the technology of medium-temperature solid-oxide fuel cells. Suspensions for electrophoretic deposition in a mixed dispersion medium isopropanol/acetylacetone = 70/30 vol %, prepared from microsized powders BaCe_0.8Sm_0.2O_3–δ (BCSO) and BaCe_0.89Gd_0.1Cu_0.01O_3–δ (BCGCuO) synthesized by the citrate-nitrate method, demonstrated a high positive ζ-potential (+25 mV) suitable for deposition. A combination of the ultrasonic treatment and centrifugation made it possible to diminish the hydrodynamic diameter of BCSO and BCGCuO particles to 880 and 294 nm, respectively. It was shown that the BCGCuO film deposited onto an LNO cathode substrate has a higher density as compared with the BCSO film, which is due to the properties of the suspensions obtained. Upon a cyclic electrophoretic deposition in six stages, the total mass and thickness of the BCGCuO coating were 3.2 mg cm^–2 and 5 μm, which is sufficient for a unit solid-oxide cell to be formed. According to SEM data, the BCGCuO film is dense and has fully formed grains with sizes of 1 to 7 μm. Methods are discussed for eliminating the loss of Ba in sintering of a thin film based on BaCeO₃.     

Sorption characteristics of nano manganese oxide: efficient sorbent for removal of metal ions from aqueous streams

Nanocrystalline manganese oxide was prepared and characterized using various techniques like XRD, surface area analyzer and zeta potential measurements. The sorption characteristics with respect to uptake of various ions including uranyl have been evaluated. Various experimental conditions which affect the sorption characteristics have been studied. Nanocrystalline manganese oxide was prepared by the hydrolysis of KMnO₄ and the nano oxide were found to have a size of 8 nm and surface area of 145 m²/g. Due to the high surface area, the sorption property of the nano oxide was good. It was found that the sorption was achieved at different pH values and with varying time of equilibration. Thus it is seen that the kinetics was an important aspect for the possible separation of metal ions.     

The Effect of Interactions between γ-AlOOH and SiO2 Hydrosols on the Phase Formation in Their Mixed Products during Thermal Treatment

The effect of the sign and the value of a relative change in the -potentials of -AlOOH and SiO₂ sols on the composition homogeneity of the products of their mixing, as well as on the phase formation during thermal treatment of the latter is studied. A sample prepared by mixing -AlOOH and SiO₂ sols at pH 2.5 demonstrates the highest homogeneity of mixed gels and forms the only phase of mullite 3Al₂O₃ · 2SiO₂ during its thermal treatment (1350°C). At this pH value, a slow heterocoagulation of the sol particles with different signs of the -potential takes place. The coagulation of the sols at pH 1.5 and 5.0 results in the preparation of more or less heterogeneous mixed products and the formation of several phases during thermal treatment.     

Comparison of the photonic effects of Mn-CNT/TiO<Subscript>2</Subscript> composites modified by different oxidants

Manganese-carbon nanotubes (CNTs) on titania (TiO₂) composites modified by different oxidants (KMnO₄, (NH₄)₂S₂O₈ and m-chlorperbenzoic acid (MCPBA)) were prepared with a sol-gel method. These composites were comprehensively characterized by the Brunauer-Emett-Teller (BET) method, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy EDX, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis absorption spectroscopy. The photoactivity of these materials prepared under visible light irradiation was tested using methylene blue in aqueous solution. The result shown that among the three oxidants, the MCPBA was the best one for the surface functionalization of CNTs and the manganese treated CNT/TiO₂ composite can enhance the photocatalytic activity. The proposed mechanism of the photodegradation of methylene blue on Mn-CNT/TiO₂ composites was present.     

Synthesis of CeO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> hydrosols via peptization at elevated temperature

A method for synthesizing aggregation-stable CeO₂-ZrO₂ hydrosols with different particle compositions is developed based on the peptization of hydrated oxide precipitates at elevated temperature. It is shown that, by varying heat treatment time, sols can be obtained with particles that have different degrees of crystallinity and sizes of no larger than 6 nm.     

Colloid chemical properties of hydrated tungsten trioxide hydrosols

Hydrosols of hydrated tungsten trioxide WO₃ ? nH₂O have been synthesized via peptization of a precipitate obtained by hydrolysis of potassium tungstate. It has been shown that the resulting sols are stable to aggregation in a pH range of 3.0–4.5. Hydrodynamic diameters and ζ potentials of WO₃ ? nH₂O particles have been determined as functions of dispersion medium pH. In addition, their density and degree of hydration have been found for the stable sols. The thickness of particle surface layers has been estimated.     

Exploring the physicochemical and morphological properties of peptide-hybridized dendrimers (DendriPeps) and their aggregates

This article presents an integrated experimental and computational study of DendriPeps, a novel class of dendrimers featuring a polyamidoamine (PAMAM) backbone hybridized with peptide segments. Hydroxyl-terminated Generation 2 (G.2) DendriPeps, comprising either four lysines (Lys) or four glutamic acids (Glu), and G.3 DendriPeps, comprising 8 Lys or 8 Glu, were first characterized in terms of hydrodynamic radius (R_h) and ζ-potential in aqueous solution. Unlike PAMAM dendrimers, DendriPeps form aggregates with R_h between 60 and 980 nm and ζ-potential between −130 and 80 mV despite their strong net charge. Upon application of shear, all aggregates disassemble into monomeric DendriPeps (R_h ~ 1–3 nm), but reform rapidly as shear is removed. Rheological characterization confirmed that DendriPep aggregates are disrupted by mild shear, but reform reversibly. Molecular dynamics simulations, informed by titrimetry, suggest that DendriPep aggregation derives from their multipolar structure and ability to rearrange the intermolecular/intramolecular pairing of titratable moieties at different pH values.     

Chemical bonding and electronic structure of LaMnO<Subscript>3</Subscript> and La<Subscript>0.75</Subscript>MnO<Subscript>3</Subscript> orthorhombic crystals

The electronic structure of the LaMnO₃ orthorhombic crystal of a stoichiometric composition and of La_0.75MnO₃ crystals with a La vacancy in the unit cell is calculated in the LSDA+U approximation of density functional theory. The calculations showed that LaMnO₃ is an insulator with a forbidden gap of 0.5 eV and with antiferromagnetic ordering of magnetic moments. The magnetic moment on the manganese ions is 3.78 BM. The La atom has ionic bonds in the lattice, while the bond between oxygen and manganese is covalent. After lanthanum has been removed, geometry optimization of the unit cell leads to La_0.75MnO₃ stable structures. In one of the structures, which is lower in energy, the states of manganese may be attributed to Mn⁴⁺ ions. In both structures with removed lanthanum, the oxygen ions have reduced effective charge, so that one can speak about O^? ions appearing along with O^2? in the structure. The oxygen, as well as lanthanum and manganese, ions are nonequivalent in these structures; their nonequivalence is primarily reflected by the local densities of states. This leads to charge and magnetic nonequivalence of ions. In La_0.75MnO₃ crystals, the degree of bond covalence between manganese and oxygen decreases.     

Studies on the synthesis of higher alcohol over modified Cu/ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

Higher alcohol has been considered as a potential fuel additive. Higher alcohol, including C₂–C₄ alcohol was synthesized by catalytic conversion of syngas (with a ratio of CO/H₂?=?1) derived from natural gas over modified Cu/ZnO/Al₂O₃ catalyst. Modified Cu/ZnO/Al₂O₃ catalysts promoted by alkali metal (Li) for higher alcohol synthesis (HAS) were prepared at different pH (6, 6.5, 7, 8, and 9) by co-precipitation to control Cu surface area and characterized by N₂ physisorption, XRD, SEM, H₂-TPR and TPD. The HAS reaction was carried out under a pressure of 45 bar, GHSV of 4000 h^?1, ratio of H₂/CO?=?1, and temperature ranges of 240 and 280 °C. It was found that the malachite phase of copper causes the size of copper to be small, which is suitable for methanol synthesis. Methanol and HAS share a common catalytic active site and intermediate. It was also found that the productivity to higher alcohol was correlated with Cu surface area.