Electrooxidation of methanol at platinum–ruthenium catalysts prepared from colloidal precursors: Atomic composition and temperature effects

The electrocatalytic oxidation of methanol was investigated on PtRu electrodes of different atomic compositions at several temperatures (from 25 to 110 °C). Very active catalyst nanoparticles supported on active carbon (Vulcan XC 72) were obtained using the colloidal synthesis developed by Bönnemann et al. [11], allowing easy variation of the atomic composition. These electrocatalysts were characterized by TEM, EDX and XRD; results indicate that they consist of platinum nanoparticles decorated by ruthenium. Methanol oxidation was studied as a function of composition, temperature and methanol concentration. Two effects were investigated: the effect of the working temperature and the effect of the atomic composition. It appeared that for lower methanol electrooxidation overvoltages, the best catalysts are ruthenium-rich, whereas at higher overvoltages the best one is the Pt + Ru (80:20)/C composition, irrespective of the working temperature, either in half-cell or in a single DMFC.     

Direct Amide Synthesis from Alcohols and Amines by Phosphine‐Free Ruthenium Catalyst Systems

Amides are synthesized directly from alcohols and amines in high yields using an in situ generated catalyst from easily available ruthenium complexes such as the (p‐cymene)ruthenium dichloride dimer, [Ru(p‐cymeme)Cl₂]₂, or the (benzene)ruthenium dichloride dimer, [Ru(benzene)Cl₂]₂, an N‐heterocyclic carbene (NHC) ligand, and a nitrogen containing L‐type ligand such as acetonitrile. The phosphine‐free catalyst systems showed improved or comparable activity compared to previous phosphine‐based catalytic systems. The in situ generated catalyst from [Ru(benzene)Cl₂]₂, an NHC ligand, and acetonitrile showed excellent activity toward reactions with cyclic secondary amines such as piperidine and morpholine.     

EXAFS Study on Structural Change of Charcoal-supported Ruthenium Catalysts during Lignin Gasification in Supercritical Water

Lignin gasification in supercritical water over charcoal supported ruthenium trivalent salts was studied using a batch reactor at 673 K. Ruthenium (III) nitrosyl nitrate on charcoal (Ru(NO)(NO₃)₃/C) was more active than ruthenium (III) chloride on charcoal (RuCl₃/C) for the gasification reaction. EXAFS analysis revealed that ruthenium metal particles were formed in both RuCl₃/C and Ru(NO)(NO₃)₃/C catalysts during the lignin gasification and that the size of ruthenium metal in Ru(NO)(NO₃)₃/C was smaller than that in RuCl₃/C. It was concluded that well-dispersed ruthenium metal particles were active for the lignin gasification in supercritical water.     

A study about the effect of the temperature of hydrogen treatment on the properties of Ru/Al2O3 and Ru/C and their catalytic behavior during 1-heptyne semi-hydrogenation

The 1-heptyne selective hydrogenation carried out at 150 kPa, and at 283 and 303 K using Ru/Al₂O₃ and Ru/C as catalysts, was studied. Catalysts were prepared by the incipient wetness impregnation technique using RuCl₃ as precursor. Ru/Al₂O₃ was treated in hydrogen at 373 or 573 K and Ru/C only at the last temperature. Catalysts were characterized by hydrogen chemisorption, TPR and XPS. Ru dispersion after treatment in hydrogen at the highest temperature is similar for both catalysts. Ru is present as Ru⁰ in Ru/C, while Ru⁰ and Ru electron-deficient species are present on the catalysts surface after hydrogen treatment at the two temperatures using Al₂O₃ as support. The best catalytic behavior was observed for the highest temperature of hydrogen treatment and for 303 K reaction temperature. As a consequence of a shape selectivity effect of the C support, the best conversion is obtained with the alumina supported catalyst.     

光助电催化降解活性艳红X-3B的研究

以采用溶胶-凝胶法制备固定膜Ru／TiO2光催化剂的钛网为基材,并对其施加不同的电压和电流,对活性艳红X-3B印染废水进行了光助电催化研究,讨论了阳极电流、不同电解质、pH值以及Cl^-1浓度对活性艳红X-3B降解效率的影响规律,并比较了光助电催化降解与光催化降解、电解处理对活性艳红降解率的差异。结果表明：相同条件下,光助电催化降解X-3B的速率明显快于单纯的电解和光催化降解速率。     

Investigations of ruthenium pyrochlores as bifunctional oxygen electrodes

The lead–ruthenates oxides were synthesized and characterized by X-ray diffraction and thermogravimetric analysis. Compounds in which part of the ruthenium is substituted with iridium were also prepared. The performance of these oxides for oxygen reduction and generation reactions was investigated in porous, gas-fed electrodes. The performance of pyrochlore oxide electrodes was shown to be excellent for oxygen reduction and generation reactions. It was observed that iridium substituted pyrochlores exhibit somewhat better performance for oxygen reduction than the unsubstituted compounds. The anodic corrosion resistance of pyrochlore-based porous electrodes was improved by using two different anionically conducting polymer overlayers, which slow down the diffusion of ruthenates and plumbate out of the electrode. The use of the conducting polymer overlayers resulted in improved performance of these electrodes.     

Characterization of multi-walled carbon nanotube electrodes functionalized by electropolymerized tris(pyrrole-ether bipyridine) ruthenium (II)

We synthesized new electropolymerizable [Ru(bpy)_nL_m](PF₆)₂ (L = 4,4 bis(3-pyrrol-1-ylpropyloxy)bipyridyl) derivatives. The introduction of electron donating ether groups in the bipyridine ligand induced a negative shift of the Ru(III)/(II) redox couple. The electrochemical behavior of complex Ru1 (n = 2, m = 1) and complex Ru2 (n = 0, m = 3) were compared using platinum and Multi-Walled Carbon Nanotube (MWCNT) electrode. Higher polymerization yields and surface concentrations were obtained at MWCNT electrodes. Furthermore, MWCNT electrodes increase polymer permeability and decrease the charge trapping phenomenon involved in the oxidation and reduction of the polypyrrolic skeleton of the Ru(II) functionalized polymers.     

TPPS_4在 Ru(Ⅳ)-TPPS_4-CTMAB-Cd 中测定贵金属钌

卟啉作为一种高灵敏度显色剂,近年来倍受分析工作者的重视.据文献报道已用于十多种金属的测定.但在贵金属中,还只见于钯、铑的分析.本文探讨了在一定镉存在下。pH 值为12.0的硼砂介质中,水溶性卟啉 TPPS_4与贵金属四价钌的显色反应.其最大吸收波长为416.4nm;表观摩尔吸光系数为6.0×10~6L/mol·cm;线性范围在0～4.0 μg/25 mL 之间;方法简便,快速、灵敏、稳定.并对排除外来离子的干扰进行了试验,用于回收实验,获得了比较满意的结果.本文还研究了表面活性剂的加入及加入条件对该反应的影响。测定了配合物的组成为TPPS_1∶Ru(Ⅳ)=1∶1,并对反应机理进行了探讨.     

Solution- and crystal-phase covalent modification of lysozyme by a purpose-designed organoruthenium complex. A MALDI-TOF MS study of its metal binding sites

Study of the reaction between the transition organometallic complex 4-ruthenocenyl 2,6-dimethylpyrylium tetrafluoroborate and the enzyme hen egg white lysozyme (HEWL) in solution and by diffusion in crystals was performed by use of a combination of spectroscopic and chromatographic methods. Conjugation involving the lysine residues of lysozyme appeared to occur readily, yielding very stable ruthenocenyl pyridinium adducts with average degrees of incorporation ranging from 0.2 to 1.8 metal complexes per protein molecule, depending on reaction conditions. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) revealed that the protein conjugates were in fact mixtures of unmodified, mono-, di- and sometimes tripyridinium adducts. In combination with reversed-phased HPLC, we were able to show that six different monoruthenocenyl pyridinium adducts were formed in solution. This result was confirmed by trypsin digestion of a ruthenocenyl pyridinium conjugate and MALDI-TOF MS analysis of the peptide mixture, which showed that lysines 1, 13, 33, 96, 97 and 116 were involved in the reaction with the pyrylium complex, lysines 13, 33 and 116 being the major binding sites. In the tetragonal crystal state, no binding of the ruthenium complex was shown to occur at lysine 116, owing to steric hindrance at this particular position.     

97Tc制备方法

为了采用同位素稀释质谱分析法准确测定环境中的痕量⁹⁹Tc，需要以⁹⁷Tc作稀释剂。采用天然Ru为辐照原料，建立了碱熔→水浸取→沉淀→萃取→阴离子交换的化学分离流程，确定了⁹⁷Tc的制备工艺。该流程的化学产额大于70％，对Ru的去污因子大于10^７。 