Reversible electrochemical insertion of anions in poly-p-phenylene from aqueous electrolytes

Poly-p-phenylene (PPP) was synthesized from benzene according to the Kovacic method. Electrodes were made from this electronic insulator by cold- or hot-pressing of the loose, brown powder, under the addition of 7.5 wt. % soot (Corax L^®, Degussa AG). The electrochemical insertion and removal of anions HSO⁻₄, ClO⁻₄ in this material in aqueous solutions of the corresponding acids was investigated by slow cyclic voltammetry.

Initially, only a surface layer of about 0.1 mm thickness takes part in the electrochemical processes, which are reversible. A maximum concentration of anions in the solid of [(−C₆H₄−)⁺₇ A⁻] is attainable. The maximum degree of insertion is equal to 0.14. The insertion potential U_I shifts strongly into the negative direction with increasing concentration c of the acid. A linear U_I/c relationship is observed as in the case of graphite, where the intercalation potential is more positive by 20–200 mV for the same electrolyte. The round trip current efficiency for the insertion/removal cycle increases with increasing acid concentration attaining 100% in 14 M H₂SO₄ or 11.3 M CHlO₄. For a given concentration, increases in the same order as with graphite (H₂SO₄ < HClO₄ < HBF₄), being somewhat lower for a given electrolyte composition. From anodic current limitation (j_lim = 5–10 mA cm⁻²), a diffusion coefficient of about D = 2 × 10⁻⁷ cm² s⁻¹ is derived for the transport of anions in the bulk of PPP. The striking similarity of our results to former findings with graphite is thoroughly discussed. Some general conclusions are derived thereof.     

Differential capacitance of the platinum/aqueous-solution interphase

The differential capacitance of polycrystalline platinum in aqueous H₂SO₄ and NaOH solutions has been investigated as a function of bias potential. A capacitance minimum is observed at 0·56 V in H₂SO₄ and − 0·34 V in NaOH solution. There is strong evidence for the irreversible adsorption of oxygen/OH⁻ ions and oxide-film formation. Addition of n-butylamine hinders the adsorption of oxygen/OH⁻ ions and it is itself strongly adsorbed.     

State of hydration of the proton and the transition between molten-salt and aqueous-solution double-layer and kinetic behaviour

The influence of the state of hydration of the proton, from H₃O⁺ in the room-temperature melt, H₃O⁺. CF₃SO⁻₃, to 1 M aqueous in CF₃SO₃H solution in water, on the interfacial capacitance behaviour of the Au electrode is reported. The results allow the transition from “molten-salt” to “aqueous-solution” double-layer capacitance behaviour to be evaluated.

At positive potentials, near the potential for onset of surface oxidation of Au by OH, the interfacial capacitance is dominated by a pseudo-capacitance associated with chemisorption of the anion CF₃SO⁻₃, with charge transfer. At negative potentials in the range in which cathodic H₂ evolution occurs, the capacitance varies from ca 23 to ca 50 μF cm⁻², with the maximum arising around a degree of proton hydration corresponding to H₇O⁺₃.

Cathodic H₂ evolution kinetics have been studied from the same proton sources and show characteristic dependences of log i_o and the heat of activation on the hydration-state of H⁺. The Tafel slopes decrease with increasing temperature, giving a further example of non-conventional behaviour of the transfer coefficient.     

Some experimental observations of aerosol formation in the photo-oxidation of sulphur dioxide

The formation of particles in the u.v. photolysis of ppm concentrations of SO₂ in pure nitrogen and in nitrogen-oxygen mixtures has been studied in a flow system. Both the number of particles and the mass of the H₂SO₄ aerosol produced was determined over a range of SO₂ and water vapour concentrations.

In the near u.v. (λ = 290–400nm) the mass conversion of SO₂ to H₂SO₄ was too small to be measured, but particles were detected on a condensation nucleus counter above a threshold SO₂ concentration when the H₂SO₄ formation rate was sufficient to achieve an appreciable nucleation rate. The number of stable particles formed increased with water vapour concentration at a given H₂SO₄ production rate. These experimental data agree reasonably well with recent theoretical calculations of aerosol nucleation and growth rate in the H₂SO₄/H₂O system.

At short wavelengths (λ = 185 nm) a much higher H₂SO₄ formation rate was achieved. Although nucleation occurred at < 1 per cent r.h. the aerosol growth process was slow at low water vapour concentrations. A r.h. of 30 per cent was required for the incorporation of the bulk of the H₂SO₄ into the aerosol phase.     

质子化氮化碳的制备及其复合材料的光催化性能

分别采用硫酸、盐酸和硝酸对尿素热解得到的体相块状石墨相氮化碳(g-C_3N_4)进行质子化改性,超声剥离得到氮化碳纳米片,考察3种质子化氮化碳纳米片对亚甲基蓝染料的光催化降解性能,利用XRD、FT-IR、SEM、BET、UV-DRS、UV-VIS等对其结构、形貌、比表面积、禁带宽度进行分析。结果表明,硫酸改性后的g-C_3N_4比表面积最大(60. 9 m~2·g~(-1)),亚甲基蓝降解效果最好,降解率为46. 7%,相比于体相块状g-C_3N_4的29. 2%提高了17. 5个百分点。以硫酸质子化改性的g-C_3N_4为前驱体,采用搅拌法制备得到质子化g-C_3N_4/石墨烯复合材料,其光催化降解亚甲基蓝的降解率为81. 7%,较硫酸质子化g-C_3N_4提高了35. 0个百分点。     

Promotion of zirconia acidity by addition of sulfate ion

The promotion of zirconia by SO₄²⁻ is studied by percolating of zirconia with aqueous solutions of several sulfur compounds and several concentrations of H₂SO₄ as sources of sulfur. The presence of SO₄²⁻ is necessary to have catalytic activity to isomerize n-butane and produces a great increase in the stability of the physical texture to thermal treatments. The more convenient solution is 1N H₂SO₄·S0₄²⁻/ZrO₂ has the greatest catalytic activity after calcination at 893 K, where the tetragonal phase of ZrO₂ predominates. The catalytic activity was found proportional to the specific surface area and surface SO₄²⁻ concentration.     

The homogeneous nucleation rates of H2SO4-H2O aerosol particles in air

The homogeneous nucleation rates for H₂SO₄---H₂O solution droplets at 25, 0 and −55°C are calculated and plotted as a function of H₂SO₄ concentration and H₂O concentration. The plotted contours are very useful for quick estimates of the nucleation rates of H₂SO₄---H₂O aerosols in smog chambers, polluted atmospheres and the stratosphere under different environmental conditions. The effect of the uncertainty in the saturated vapor pressure of H₂SO₄ on the nucleation rate is also discussed.     

Mass transfer by free convection at horizontal electrodes

Limiting currents were measured in an unstirred cell at horizontal cathodes facing upward. Electrolyte composition ranged from 0·01 to 0·7 M CuSO₄ in 1·5 M H₂SO₄. Cathode sizes varied from 0.1–30 by 10 cm, and the free height above the electrode from 1–16 cm. Limiting currents for deposition of copper ranged from 0·68–129 mA/cm². For electrode width larger than 20 mm the data is well represented by the general correlation

Nu′ = 0.19 (Sc. Gr) , where Nu′, Sc, and Gr are the Nusselt number for mass transfer, the Schmidt, and Grashof numbers, respectively. The experimental range used in the correlation included 10⁸ < (Sc. Gr) < 1·4 × 10¹² The results indicate that the boundary layer is turbulent, as it is in the case of the analogous heat-transfer model.     

Effect of alkalies on portland cement hydration II. Alkalies present in form of sulphates

Alkalies present in cement in the form of Na₂SO₄ and/or K₂SO₄ do not alter the progress of C₃S and C₃A hydration. The setting time becomes accelerated especially with K₂SO₄ due to the formation of syngenite CaSO₄·K₂SO₄·H₂O. The compressive strength is lowered significantly.     

Kathodisches Verhalten von konzentrierter Schwefelsäure

The cathodic behaviour of 85–100% sulphuric acid was investigated in relation to cathode material, temperature and water concentration. The basic curve is situated at relatively negative potentials in 85–92% sulphuric acid; electroreductions are therefore possible in this solvent. At low water concentrations, the basic curve rises to much more positive potentials, due to the reduction of the H₂SO₄ molecule. A sequence with various cathode materials is obtained, which follows the well known sequence for the hydrogen overpotential.

A “prewave” (at –140 mV(sce) for mercury and +500 mV (sce) for platinum cathodes) increases strongly in water-poor systems. It is explained as the reduction of solvated SO₃, which is in equilibrium with H₂SO₄. The electron number is 2.

Practical consequences in reference to the material for electrodes and diaphragms for electro-reductions in this system are discussed.

Zusammenfassung

Le comportement cathodique de l'acide sulfurique à 85–100% a été étudié en relations avec la substance cathodique, la température et la teneur en eau. La courbe de base se situe à des potentiels relativement négatifs dans l'acide sulfurique à 85–92%; les électro-réductions sont par conséquent possibles dans ce solvant. Pour de faibles teneurs en eau, la courbe de base atteint des potentiels plus positifs, ce qui est dû à la réduction de la molécule H₂SO₄. On obtient un ordre de classement des diverses substances cathodiques; il concorde avec celui bien connu relatif aux surtensions d'hydrogène.

Une “pré-vague” cathodique (à −140 mV (sce) pour le mercure et +500 mV (sce) pour le platine) s'élève notablement dans les systèmes pauvres en eau. Elle s'explique par la réduction de SO₃ solvaté en équilibre avec H₂SO₄. Le nombre d'électrons est 2.

L'on discute les conséquences pratiques relatives aux matériaux des électrodes et aux diaphragmes utilisés pour les électro-réductions dans de tels systèmes.     

四元体系Rb+, Cs+, Mg2+ // SO42- - H2O 298.2 K相平衡研究

采用等温溶解平衡法研究了298.2 K下四元体系Rb⁺, Cs⁺, Mg²⁺ // SO₄^2- - H₂O的相平衡关系,测定了该体系的溶解度、密度以及折射率,并绘制了相应的稳定相图、水图、密度-组成图和折射率-组成图。研究表明：298.2 K下,该四元体系为复杂四元体系,有复盐Cs₂SO₄·MgSO₄·6H₂O和Rb₂SO₄·MgSO₄·6H₂O以及固溶体[(Rb, Cs）₂SO₄]生成。其稳定相图由4个四元共饱点、9条单变量曲线以及6个结晶区组成。四元共饱点中E₁、E₂、E₃为相称共饱点,E₄为不相称共饱点。6个结晶相区分别对应3种单盐Rb₂SO₄、MgSO₄·7H₂O、Cs₂SO₄,2种复盐Cs₂SO₄·MgSO₄·6H₂O、Rb₂SO₄·MgSO₄·6H₂O和1种固溶体[(Rb,Cs）₂SO₄]。其中,复盐Rb₂SO₄·MgSO₄·6H₂O结晶区最大,表明其在该体系中最易结晶析出;Cs₂SO₄结晶区最小。平衡液相的密度和折射率随着溶液中Cs₂SO₄含量变化呈规律性变化。该体系稳定相图将为硫酸镁亚型盐湖卤水中的铷、铯等资源开发利用提供理论依据。     

PRECIPITATION IN THE Mg+2-Na+-SO3-2-SO4-2 AQUEOUS SYSTEM

Spontaneous precipitation in the aqueous system Mg₊₂-Na₊-SO₃^-2-SO₄^-2 affected by mixing solutions of MgSO₄ and Na₂SO₃, together was studied for temperature varying from 40 to 80°C and for pH from 5,5 to 9. The initial composition of a precipitating system was 0·67 and 1·17 mol of MgSO₃ and Na₂SO₄ per liter and 0·82 mol of MgSO₃ and Na₂SO₄ together with 0·83 mol of MgSO₄ per liter, respectively. Depending on the prevailing reaction conditions, solid phase consisting of MgSO₃ 6H₂O, MgSO₃ 3H₂O, Mg₂NaOH(SO₃)₂ H₂O or their mixture is formed. Each solid phase forms crystals of typical size and shape. The precipitation diagrams drawn in the temperature and pH coordinates for three different initial composition of the studied system are presented.     

Photoluminescence and molecular orbital theory in anodic oxide films formed on aluminium

We use molecular orbital theory (MOT) to explain the existence of one or two excitation maxima in photoluminescence excitation spectra of Al₂O₃ formed on Al in different aqueous electrolytes (H₂SO₄, H₃PO₄, H₂CrO₄, Na₂CO₃, H₂C₂O₄ and HCOOH). All oxides were formed at the same temperature and current density. Comparing experimental and calculated values of the maximum of the excitation wavelength λ_max we concluded: (a) that structural change in the formed oxides occurred; (b) that differences in λ_max are in connection with different types of incorporated anions or anion fragments.     

微波法制备膨胀石墨及其膨胀特性

以鱼鳞片石墨为原料, 浓硫酸作为插层剂, 高锰酸钾作为氧化剂, 采用化学氧化法制备石墨插层物, 再利用微波辐射石墨插层物快速制备膨胀石墨。膨胀后的石墨颗粒呈"蠕虫"状, 蓬松粗大。随着鳞片石墨尺寸的减小, 膨胀石墨颗粒变得更加纤细, 达到最大膨胀体积时高锰酸钾的用量也随之减少。最佳微波时间为30～60 s, 此时间段内石墨膨胀完全并且无烧蚀。对于3种不同尺寸的鳞片石墨, 颗粒度大于0.42 mm的鳞片石墨在混合质量比m(石墨):m(H₂SO₄):m(KMnO₄)=5:10:4时, 达到最大膨胀体积为285 ml·g^-1。     

氧化石墨烯固定化α-淀粉酶

以石墨粉为原料,使用改进Hummer法制备氧化石墨烯,采用沉积法固定化α-淀粉酶,并对固定条件进行优化。分别采用NaOH-CH₂ClCOOH法和HNO₃-H₂SO₄法制备羧基化氧化石墨烯,并将其用于固定化α-淀粉酶。结果表明,沉积法固定化酶的最适宜温度为65 ℃,最适宜pH=7.0。连续催化反应9次后,固定化酶活力仍能保持初始固定化酶活力的47.81%。经比较发现,NaOH-CH₂ClCOOH法更有利于羧基化氧化石墨烯的制备,该方法制备的羧基化氧化石墨烯产率为HNO₃-H₂SO₄法的1.2倍。     

Aerosol growth studies — IV. Phase transformation of mixed salt aerosols in a moist atmosphere

The phase transformation and subsequent droplet growth of the mixed salt aerosols NaCl—KCl and (NH₄)₂SO₄—H₂SO₄ were investigated in a continuous-flow apparatus at 25 and 30°C as a function of relative humidity. Monodisperse salt aerosols (d = ≈ 0.5 μm, OG = 1.07–1.13) were prepared and mixed with N₂ carrier gas at controlled humidities. The particle-size distribution of the aerosol before and after growth by water vapor condensation was continuously monitored with an optical particle counter. It was found that mixed salt aerosols were characterized by stage-wise growth when the relative humidity in the atmosphere was increased. The onset of growth took place at a specific deliquescence humidity determined by the water activity at the eutonic composition. Thus, mixed NaCl—KCl aerosols deliquesce at 73.8 ± 0.5% r.h. regardless of initial compositions. For sulfate aerosols containing 0.75 to 0.95 mole fraction (NH₄)₂SO₄ (the balance being H₂SO₄), the onset of growth occurs at 69.0 ± 0.5% r.h.. In the composition range of 0.5 to 0.75, a deliquescence humidity of 39.0 ± 0.5% is noted. Below 0.5 mole fraction, however, the mixed-sulfate aerosols are expected to exhibit hygroscopic properties on the basis of thermodynamic considerations.     

Influence of chemisorbed carbon monoxide on the impedance of a smooth Pt wire at cathodic polarization in sulfuric acid solution

The ohmic and capacitive components of the impedance of a smooth Pt wire electrode were measured at a cathodic current density of −1 mA cm⁻² at frequencies ν between 10,000 and 25 Hz at different coverages of chemisorbed carbon monoxide in 0.5 M H₂SO₄. The linear dependence upon ω^−1/2, characteristic for predominant H₂ diffusion on clean Pt electrodes, disappears at carbon monoxide coverages above 0.2. The hindrance of the H₂ evolution reaction increases with the coverage of CO_ad in a gradual fashion below 0.7 and rapidly at larger coverages. The hindrance is considerably larger on the Pt wire than on Pt foils, investigated previously. The change of the attenuation factor, caused by the blocking of the free surface, cannot account for the observed effect on the Pt wire electrode. Simple models, based on the Volmer—Tafel or Volmer—Heyrovsky mechanisms for H₂ evolution, cannot describe the experimental frequency dependence of the impedance at coverages above 0.2.     

Pt-H2SO4/Zr-montmorillonite:An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane,polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D4) was investigated over Pt-H2SO4/Zr-montmorillonite catalyst.Montmorillonite(Mt),Zr-Mt,H2SO4/Mt,H2SO4/Zr-Mt and Pt-H2SO4/Zr-Mt were also detected for evaluation.The catalysts were characterized by X-ray fluorescence,X-ray diffraction,nitrogen adsorption-desorption,NH3-TPD and pyridine-FTIR measurements.In comparison to activate clay which is used in the industry of catalyst,Zr-Mt catalyst displayed stronger acidity and more excellent catalytic activity in the polymerization of D4,polymethylhydrosiloxane(D4H)and hexamethyldisiloxane(MM)to low-hydro sili-cone oil.Relative to Zr-Mt,the acidity of H2SO4/Zr-Mt was noticeably improved and the catalyst exhibited a higher capability of ring-opening of D4conversion and yield of low-hydro silicone oil.To enhance the stability of H2SO4/Zr-Mt catalyst,a small amount of metals(Pt)was doped.The nitrogen adsorption-desorption results indicated that pore textural parameters of the Pt-H2SO4/Zr-Mt had not changed with larger specific surface area.Compared with H2SO4/Zr-Mt,the total acidity of Pt-H2SO4-Zr/Mt catalyst retained,but the content of the Br?nsted acid increased and the content of the Lewis acid decreased.The Pt-H2SO4-Zr/Mt catalyst displayed higher catalyst reproducibility.After 40 h reaction of polymerization,the yield of low-hydro silicone oil decreased from 93% to 42% over H2SO4/Zr-Mt catalyst,while the yield of low-hydro silicone oil reduced from 93% to 78% over Pt-H2SO4/Zr-Mt catalyst.A sharp decrease in catalytic activity after 35 h of Pt-H2SO4/Zr-Mt catalyst was detected.Furthermore,Pt-H2SO4/Zr-Mt was completely regenerated under appropriate condition and appeared good repeatability in the D4,D4H and MM to low-hydro silicone oil.     

-15℃下Na+, K+, Mg2+// Cl-, SO4-2-H2O体系相平衡

采用等温溶解平衡法,研究了Na⁺, K⁺, Mg²⁺//Cl^-, SO₄^-2-H₂O, 五元水盐体系在-15℃下NaCl·2H₂O饱和时的相平衡关系,测定了溶解度和密度,并绘制出相应的相图。研究结果表明:该五元体系平衡相图中有3个四盐共饱点,7条单变量溶解度曲线及5个两盐结晶区,5个两盐结晶区分别对应于KCl+NaCl·2H₂O、Na₂SO₄·10H₂O+ NaCl·2H₂O、MgSO₄·7H₂O+NaCl·2H₂O、MgCl₂·8H₂O+NaCl·2H₂O、KCl·MgCl₂·6H₂O+ NaCl·2H₂O;所 得-15℃相图和25℃下相图相比,相图结构大为简化:K₂SO₄·MgSO₄·4H₂O、KCl·MgSO₄·3H₂O、Na₂SO₄·3K₂SO₄、Na₂SO₄·MgSO₄·4H₂O、MgSO₄·(4～6)H₂O、K₂SO₄·MgSO₄·6H₂O结晶区均消失,Na₂SO₄结晶区转变为Na₂SO₄·10H₂O且结晶区扩大,KCl、MgSO₄·7H₂O、KCl·MgCl₂·6H₂O结晶区缩小,MgCl₂·6H₂O结晶区转变为MgCl₂·8H₂O。在此基础上研究了不同组成的盐湖卤水在降温过程中的结晶规律,为低温盐田工艺的开发提供了理论依据。     

β-SiC粉体中常见金属杂质的亚临界水热去除工艺

高纯β-SiC粉体作为原料,广泛应用于半导体晶圆、半导体窑具、半导体芯片设备用陶瓷器件等产品。高温高压可以促进水热反应,采用亚临界水热法可去除工业合成β-SiC粉体中的金属杂质。研究不同酸体系下β-SiC粉体中常见金属杂质的去除效果。利用电感耦合等离子原子发射光谱仪(ICP-OES)检测微量元素的含量,通过X射线衍射仪(XRD)和扫描电镜(SEM)对β-SiC粉体的物相组成和微观结构进行表征。结果表明,对于Cr和Zr去除效果较好的是HCl体系,对于Ca、Fe、Mg和Ti去除效果较好的是HCl+HF+HNO₃体系,对于Al和K去除效果较好的是H₂SO₄+(NH₄)₂SO₄体系。采用HCl体系处理的最佳反应温度为200 ℃,采用HCl+HF+HNO₃体系处理的最佳反应温度是220 ℃,采用H₂SO₄+(NH₄)₂SO₄体系处理的最佳反应温度是200 ℃。其中,H₂SO₄+(NH₄)₂SO₄体系可将β-SiC粉体中常见金属杂质含量降低至最少(杂质总含量为920.31 mg/L),因此该体系为β-SiC粉体除杂的最优方案。