Electrooxidation Mechanism of Methanol at Pt-Ru Catalyst Modified GC Electrode in Electrolytes with Different pH Using Electrochemical and SERS Techniques

The electrochemical and in-situ surface-enhanced Raman spectroscopy （SERS） techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon （Pt-Ru/GC） electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable.     

Electrochemical behaviour of an indium electrode in concentrated KOH solutions at different temperatures

Summary The electrochemical behaviour of pure indium in KOH solutions (1–4M) was studied at different temperatures (25–70°C) by potentiostatic techniques. Two anodic peaks corresponding to the formation of In(OH)₃ and In₂O₃ were observed. The heights of the two peaks increased with the increase of alkali concentration. An increase of temperature increased the peak currents and shifted their corresponding potentials to more negative values. The variation of the peak currents and peak potentials with scan rate suggested that the anodic dissolution of indium was a diffusion controlled process. In cyclic voltammetry, the reverse scan consistently showed one peak which was attributed to the reduction of anodic oxidation products into indium. X-ray diffraction analysis confirmed the presence of In(OH)₃ at the first anodic peak, In(OH)₃ and In₂O₃ at the second anodic peak and In₂O₃ in the permanent passive region.

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Zum elektrochemischen Verhalten einer Indium-Elektrode in konzentrierter Kalilauge bei verschiedenen Temperaturen

Zusammenfassung Es wurde das Verhalten von reinem Indium in 1 – 4M KOH-Lösungen bei Temperaturen zwischen 25 und 70°C mittels potentiostatischer Methoden untersucht. Zwei anodische Peaks, entsprechend der Bildung von In(OH)₃ und In₂O₃, traten auf. Die Höhe der beiden Peaks wurde mit zunehmender Alkalikonzentration gesteigert. Eine Temperaturerhöhung verstärkte die Peakströme und verschob die entsprechenden Potentiale zu negativeren Werten. Die Abhängigkeit der Peakströme und Peakpotentiale von der Scangeschwindigkeit legte den Schluß nahe, daß die anodische Lösung von Indium in einem diffusionskontrollierten Prozeß stattfindet. Bei der cyclischen Voltammetrie zeigte der reverse Scan einheitlich einen Peak, der der Reduktion der anodischen Oxidationsprodukte zu Indium zugeschrieben wurde. Röntgendiffraktionsanalyse bestätigte die Präsenz von In(OH)₃ beim ersten anodischen Peak, In(OH)₃ beim zweiten Peak und In₂O₃ im permanent passiven Bereich.

     

Photoacoustic Spectrometry Investigation and Determination of Rare Earth Ions Ho3+ and Nd3+ in a Solution

A home-made high sensitive photoacoustic transducer was used to determine the photoacoustic signal in a solution. The photoacoustic spectra of Ho in different solvents were measured and comparedwith its absorption spectrum. The affection factors of photoacousticsensitivity are discussed. The trivalent rare earth ions Ho3+ and Nd3+in an aqueous acetonitrile solution were determined. The detection limit is 5×10-8 mol/L for Ho3+ and 1.0 ×10-7 mol/L for Nd3+, and corresponds to the absorbance of 1.5×10 and 6.3×10-7.respectively.     

校正峰电位漂移偏最小二乘极谱催化波同时测定轻稀土

应用Ｍ２７３．Ａ电化学系统中的线性扫描技术，确定了８．０×１０－５ｍｏｌ／Ｌ二甲酚橙及ｐＨ４．０ＨＡｃ－ＮａＡｃ缓冲体系为偏最小二乘极谱法同时测定Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ的最佳极谱体系。６种稀土元素的线性范围均在１．０× １０－７～１．２ × １０－５ｍｏｌ／Ｌ。并对极谱峰电位随浓度漂移进行了校正，提高了方法的准确度。     

Determination of rare earth elements in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry

A home made column of commercially available iminodiacetate resin, Muromac A-1 (50–100 mesh) was used to concentrate rare earth elements (REEs) (15 elements: Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in seawater. An automated low pressure flow analysis method with on-line column preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) is described for the determination of REEs in seawater. Sample solutions (adjusted to pH of 3.0) passed through the column. After washing the column with water, the adsorbed elements were subsequently eluted into the plasma with 0.7 M nitric acid. Calibration curves were accomplished by means of purified artificial seawater with a sample loading time of 120 s. Detection limits (DLs) of the on-line column preconcentration/ICP-MS by eight replicate operations were between 0.040 and 0.251 pg ml⁻¹ for REEs in the artificial seawater. The precision was less than 8.9% for REEs and one sample can be processed in 7 min using a 7 ml of sample. The proposed method was applied to determine REEs in coastal seawater of Hiroshima Bay, Japan.     

Theoretical investigation of isotopic scrambling mechanisms in 2-chloroethyl methyl sulfide

Ab initio and semiempirical molecular orbital calculations have been applied to study the concerted and stepwise isotopic scrambling mechanisms of 2-chloroethyl methyl sulfide in the gas phase and in aqueous solution. The calculations reveal the structural details of the reactants, transition structures, and intermediates involved in this reaction and provide relative energy estimates. The concerted mechanism is found to be competitive with the stepwise mechanism in the gas phase, but the stepwise mechanism is favored in aqueous solution as no true transition structure for the concerted mechanism could be found using the solvation models. A combined approach of evaluating solvation energies with the generalized-Bom-plus-surface-tensions SM _x solvation models of Cramer and Truhlar at ab initio optimized geometries is found to deliver the best agreement with experimentally determined reaction barriers. Together with the recent experimental results of McManus and co-workers, the present study provides insights into the controlling factors involved in the elementary reaction steps of sulfur mustards and a solid foundation for investigations into more complex reactions of related compounds.     

New odorless method for the Corey-Kim and Swern oxidations utilizing dodecyl methyl sulfide (Dod-S-Me)

Development of the odorless dodecyl methyl sulfide (Dod-S-Me, 1) as an alternative for dimethyl sulfide (DMS) and new odorless methods for the Corey-Kim and Swern oxidations are described. These reactions have been developed with a view toward green chemistry, utilizing Dod-S-Me (1) and common solvents instead of dichloromethane.     

掺铬铝酸钇红色颜料的合成、结构和性能表征

研究了高温固相合成制备掺铬铝酸钇红色颜料的方法，着重考察了灼烧温度（1000-1400℃）、灼烧时间（1-2h）、主要原料配比（Al／Y：1：0．5—1：1．5，Cr2O3％：0．3％-5％）等实验条件对产物结构和色泽的影响。XRD等方法对样品进行的相态分析表明，主相为铝酸钇石榴石相；运用反射光谱对红色颜料的色泽进行了反射峰位和相关强度的表征。当Y2O3：Al2O3摩尔比为1：1，掺杂3％的Cr2O3作显色剂，在少量矿化剂存在时，在1300℃下灼烧1 h，得到了色坐标为x=0．577，Y=0．401的红色陶瓷颜料。     

Removal of H2S from Exhaust Gas by Use of Alkaline Activated Carbon

The purpose of this research was to select an activated carbon and alkaline solution blend that generated the best H₂S adsorption on alkaline-activated carbon. RB₂ (activated carbon) impregnated with NaOH solution was shown to have the optimum H₂S removal efficiency. The optimum NaOH concentration was 50 mg per gram of carbon. H₂S adsorption via RB₂-NaOH₅₀ was five times that of a corresponding fresh-activated carbon. The adsorption equivalent of H₂S is nearly 1 (mol-H₂S/mol-AOH), therefore, H₂S + AOH AHS + H₂O was the major reaction. The H₂S adsorption isotherm corresponded to the Freundlich isotherm.     

含铈多元氧化物的活性结构及在丙烯氨氧化中的作用

本文利用流化床反应器研究了多元复合氧化物PMo_(12)Bi_3Fe_(8-x)Ce_xK_(0.1)O_y(x=0-8)中稀土元素铈对丙烯氨氧化的催化作用,并用x-射线衍射、红外光谱、扫描电镜和热重技术表征了催化剂的结构,发现x=2-3时,丙烯腈的收率最高。催化剂中存在Fe_2(MoO_4)_3,Ce_2(MoO_4)_3、α-Bi_2O_3、3MoO_3。这三种物相的互相溶解和凝结形成固溶体和准均相,使活源。份在各物相表面或界面上均匀分布,由此产生的各活性组份的协调作用是催化活性的主要来性组铈能抑制MoO_3升华,稳定活性相结构。