Electrocatalytic activity of palladium–polypyrrole nanocomposite in the formaldehyde oxidation reaction

Palladium–polypyrrole nanocomposite materials with high electrocatalytic activity toward formaldehyde in an alkaline solution (methylene glycolate) have been synthesized via a one-step redox route. Key factors that have an effect on the sensor properties of palladium nanoparticles have been determined. It has been demonstrated for the first time that the emergence of not only the forward but also the reverse wave of formaldehyde oxidation on palladium particles is associated with the oxidation of methylene glycolate rather than intermediate species.     

Cation-anion palladium complexes: the effect of the hydrogen bond character on their stability and biological activity

The results of study of a new class of biologically active palladium complexes (AH _n ) _m [PdCl₄] have been reported. This class of compounds has been discovered by us on the basis of systemic research of composition-structure-biological activity relationships for different classes of platinum metal complexes. It has been shown that the stability of cation-anion palladium complexes and their biological activity are determined by the nature of protonated amines acting as cations and the acid-base properties of the cations-tetrachloropalladate anion systems, manifested in the character and stability of hydrogen bonds that appear in these systems. For the first time, it has been demonstrated in vivo that it is possible to synthesize palladium compounds superior to cisplatin in antitumor activity and not exhibiting immunosuppressive activity, as well as palladium compounds with immunostimulatory and radiomodifying activity. A combination of cytostatics used in oncology or irradiation with palladium complexes leads to significant synergism of their effects and to a considerably higher therapeutic efficiency of such combinations as compared with the treatment effect of each of them alone.     

The effect of palladium dispersion and promoters on lactose oxidation kinetics

Lactose oxidation was investigated at 70 °C and at pH 8 using oxygen as an oxidant over a comprehensive set of commercially available mono- and multi-metallic as well as promoted Pd catalysts with active carbon, alumina and calcium carbonate as catalyst supports. An optimum cluster size of 6–10 nm resulted in the highest initial turnover frequencies. High conversion levels above 90% were achieved on Pd/C catalyst, as well as over Pd/Al₂O₃ and (Pd–Pb)/CaCO₃, whereas (Pd–V)/C catalyst gave only 30% conversion after 200 min. The latter catalyst was relatively inactive due to its high support acidity and profound deactivation during oxidation. Besides the main oxidation product, lactobionic acid, also, lactulose was generated as a result of lactose isomerisation under alkaline conditions. The electrochemical potentials of the catalysts were measured during lactose oxidation. The main result of these measurements was that, when the electrochemical potential of the catalyst increased very quickly, its oxidation activity was low due to metal over-oxidation. The selectivities to the desired product, lactobionic acid, were relatively high, above 80% for most of the catalysts, except for (Pd–V)/C. Furthermore, the selectivity to the lactobionic acid decreased with increasing metal dispersion, thus, indicating that the optimum metal particle sizes for producing high amounts of lactobionic acid is above 3 nm.     

The effect of ethanol on the catalytic oxidation of methanol on silver

Thermal desorption, radioactive indicators, and a kinetic method involving frozen radicals were used to study the catalytic oxidation of methanol in the presence of ethanol on silver. The increase in the yield of aldehydes in the combined oxidation of these alcohols on silver is related to a change in the nature of the adsorption and homogeneous steps of this reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1174–1176, May, 1990.     

Thermal stability and activity in hydrogen oxidation of palladium catalysts supported on fibrous sulfonic cation exchanger in the hydrogen and magnesium forms

The effect of reduced palladium on the thermal stability of the hydrogen and magnesium forms of FIBAN K-1 fibrous sulfonic cation exchanger was studied. The activity of palladium catalyst supported by the H and Mg forms of the cation exchanger in hydrogen oxidation was determined, as influenced by the temperature of treatment of the catalyst with the reaction mixture.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1510–1515.Original Russian Text Copyright © 2004 by Egiazarov, Radkevich, Kravchuk, Ivko.     

Hysteresis effect and autooscillation phenomena in the oxidation of 1-hexene on palladium

The gas-phase oxidation of 1-hexene on a palladium film has been investigated in a gradient-free reactor at atmospheric pressure and temperatures of 293–693 K, at flow rates of 0.3–0.15 liter/min and an initial concentration of hexene in air of 15.5·10^–4 M. Autooscillation phenomena have been observed and a hysteresis effect in the reaction rate as function of temperature, caused by the branched-chain heterogeneous-homogeneous reaction mechanism.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 24, No. 1, pp. 107–110, January–February, 1988.     

The negative activity limit of stability and the coagulation values of silver halides

Summary The negative stability limit of AgI shifts with increasing concentrations of the solvents ethanol, acetone and glycine in water asymptotically to a lower limiting pAg value. The main shift occurs in 10 mol% of acetone and ethanol and 1.8 mol% of glycine from pAg 6.2 in water to 3.0, 4.2 and 3.0 resp. In solutions of the same solvent content the coagulation values remain practically equal to the coagulation values in pure water, the change being less than 0.2. In the negative stability region from pI 1 to the negative stability limit in the water solvent mixture the coagulation values of cations of valency 1,2 and 3 are practically constant and independent of the activity of the potential determining ion in excess. The negative limit in 10 to 15 mol% acetone and ethanol in the AgBr system is 4.7 and 5.4 resp. The present results were shown to confirm well the ion exchange theory of coagulation.

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Zusammenfassung Die negative Stabilit?tsgrenze von AgI verlagert sich mit steigenden Konzentrationen der L?sungsmittel ?thylalkohol, Aceton und Glycin in Wasser asymptotisch zu niedrigeren pAg-Grenzwerten. Die Hauptverschiebung findet in 10 Mol%igem Aceton und ?thylalkohol und 1,8 Mol%igem Glycin von pAg 6,2 in Wasser zu 3,0, 4,2 und 3,0 resp. statt. In L?sungen vom selben Gehalt bleiben die Koagulationswerte praktisch gleich denen im reinen Wasser; die ?nderung ist kleiner als 0,2. Im negativen Stabilit?tsbereich von pI 1 zur negativen Stabilit?tsgrenze in Wasser-L?sungsmittel-Gemischen sind die Koagulationswerte von Kationen der Valenz 1–3 praktisch konstant und unabh?ngig von der Aktivit?t des potentialbestimmenden Ions. Die negative Grenze ist in 10–15 Mol% Aceton und ?thyl?ther im AgBr-System 4,7 und 5,4 resp. Diese Resultate best?tigen gut die Ionenaustauschtheorie der Koagulation.

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Contribution No. 102 from the Department of Physical Chemistry, Faculty of Science, University of Zagreb, Zagreb, Yugoslavia.     

Platinum monolayers stabilized on dealloyed AuCu core-shell nanoparticles for improved activity and stability on methanol oxidation reaction

Deposition of platinum(Pt)monolayers(PtML)on Au substrate represents a robust strategy to maximally utilize the Pt atoms and meanwhile achieve high catalytic activity towards methanol oxidation reaction for direct methanol fuel cells owing to a substrate-induced tensile strain effect.However,recent studies showed that Pt(ML)on Au substrate are far from perfect smooth monoatomic layer,but actually exhibited three-dimensional nanoclusters.Moreover,the Pt(ML)suffered from severe structural instability and thus activity degradation during long-term electrocatalysis.To regulate the growth of Pt(ML)Au surface and also to improve its structural stability,we exploit dealloyed AuCu core-shell nanoparticles as a new substrate for depositing Pt(ML).By using high-resolution scanning transmission electron microscopy and energy dispersive X-ray elemental mapping combined with electrochemical characte rizations,we reveal that the dealloyed AuCu core-shell nanoparticles can effectively promote the deposition of Pt(ML)closer to a smooth monolayer structure,thus leading to a higher utilization efficiency of Pt and higher intrinsic activity towards methanol oxidation compared to those on pure Au nanoparticles.Moreover,the Pt(ML)deposited on the AuCu core-shell NPs showed substa ntially enhanced stability compared to those on pure Au NPs during long-term electrocatalysis over several hours,during which segregation of Cu to the Au/Pt interface was revealed and suggested to play an important role in stabilizing the Pt(ML)catalysts.     

钯纳米晶体在电催化甲酸氧化反应中的形貌效应

本文基于课题组前期工作,选用适当的金属前驱物、还原剂、稳定剂和保护剂,通过调控氧化刻蚀和反应动力学等,成功合成了形貌和尺寸均不相同的Pd纳米晶.经过认真的纳米粒子清洗和电极修饰组装,考察了它们在电催化甲酸氧化反应中的形貌与性能的关系.研究结果表明,Pd纳米晶样品的最大电流密度以纳米八面体（nanooctahedra）、纳米线（nanowires）、纳米立方体（nanocubes）、纳米瓜子（nanotapers）、凹面纳米立方体（concave nanocubes）的顺序递增,催化甲酸氧化反应的起始氧化电位均小于0.2V.研究结果印证了Pd纳米晶催化甲酸氧化反应的催化性能在尺寸效应上主要受活性表面积的影响,扣除表面积效应后的催化性能与其尺寸没有明确关系.该系列Pd纳米晶的催化性能主要取决于其表面结构,得出Pd纳米晶催化甲酸氧化反应遵循{111}晶面〈{100}晶面〈高指数晶面的性能活性顺序.综合最大电流密度和最小操作电位因素发现,Pd凹面纳米立方体和Pd纳米瓜子具有相对较好的商用价值.     

Correction to: Catalytic oxidation of hydrogen on platinum

Journal of Thermal Analysis and Calorimetry - Due to a fault (oversight) of the authors, L’vov BV, Galwey AK, in Fig 1 of the article: ‘Catalytic oxidation of hydrogen on...     

Effect of palladium on the reducibility of Mn based materials: correlation with methane oxidation activity

Mn-based oxide supports were synthesized using different procedures: (i) carbonate co-precipitation method, leading to the formation of a hexaaluminate crystallized solid (La(0.2)Sr(0.3)Ba(0.5)MnAl(11)O(19)) and (ii) solid-solid diffusion method, leading to the formation of a doped theta-Al(2)O(3) crystallized solid (nominal composition: 60 wt% La(0.2)Sr(0.3)Ba(0.5)MnAl(11)O(19) + 40 wt% Al(2)O(3)). Impregnation of 1.0 wt%Pd was carried out on both oxides. The solids were tested for the catalytic methane combustion up to 700 degrees C. It was observed that adding palladium resulted in an important increase in the catalytic activity. The combined use of H(2)-TPR and XPS techniques reveals that only Mn(3+)/Mn(2+) redox "couple" is present in the solids, whatever the synthesis procedure used. The fraction Mn(3+)/Mn is proportional to the total Mn content in the solid support, whatever the sample structure (hexaaluminate or doped theta-Al(2)O(3)) and its morphology (large crystals or aggregates of small particles, respectively). Pd impregnation and further calcination at 650 degrees C has no significant effect on the Mn(3+)/Mn fraction. However, some changes in Mn(3+) reduction profile are observed, depending on the solid structure. Indeed, palladium addition strongly affects the manganese reducibility with an important shift of the reduction process to lower temperatures (approximately 100 degrees C). On the basis of redox properties observed for the different catalysts, a Mars-van-Krevelen redox mechanism, with oxygen transfer from support oxides to palladium particles, is proposed to explain the difference in terms of catalytic conversion and stability with respect to a 1.0 wt%Pd/Al(2)O(3) reference sample.     

Synergistic effect in the electrocatalytic oxidation of methanol on platinum+palladium alloy electrodes

The electrocatalytic oxidation of methanol has been investigated on platinium+palladium alloy electrodes of different compositions in acid, neutral and alkaline aqueous solutions.The surface characteristics (composition and roughness factor) of the alloys and the stability of the electrodes in contact with different electrolytic solutions have been studied using cyclic voltammetry. In particular, a surface enrichment in platinum due to a preferential dissolution of palladium and an increase of the roughness factor with an increase of the palladium content has been shown.The electrocatalytic activity of different alloys for methanol oxidation has been characterized by exchange current densities obtained from extrapolation of Tafel lines of calculated equilibrium potential. The plot of these current densities vs. the surface composition leads to a synergistic effect, particularly important in alkaline medium. A reasonable explanation of this enhanced electroactivity at about 15 at.% in Pd is given on the basis of a decrease of electrode poisoning.     

The effect of interfacial microstructure on the lipid oxidation stability of oil-in-water emulsions

Novel rattle-type magnetic mesoporous carbon spheres are successfully prepared using composite spheres with Fe(3)O(4) as core and mesoporous SiO(2) as shell plus solid SiO(2) as a middle layer as templates. These rattle-type spheres possess the magnetization strength of as high as 37.5 emu/g, high and tunable specific surface areas (382-512.6 m(2)/g) due to mesoporous carbon shells. This magnetic rattle-type structure and the readily accessible mesoporous shell are very favoring for the fast adsorption and release of guest objects triggered by external stimulus, for example, the spheres showed very good adsorptive property to dye.     

The effect of fructose derived carbon shells on the plasmon resonance and stability of silver nanoparticles

Carbon nanoparticles between 10 and 50 nm in diameter and carbon shells of various thickness around silver nanoparticles were synthesized by the hydrothermal reaction of fructose. The effect of the carbon shells on the plasmon resonance of the silver nanoparticles and their stability in sodium chloride solutions was investigated. The shell thickness can be adjusted to have insignificant damping of the plasmon resonance and provide stabilization of the particles in solutions with high ionic strength. Hydrazine–carbonyl cross-linking reactions were performed to link fluorescent dye molecules to carbonyl groups on the carbon shell surface.     

Influence of silver dispersity on its specific catalytic activity in ethylene oxidation

Specific catalytic activity for massive (powders and films) and supported (Ag/SiO₂) silver catalysts have been studied in ethylene oxidation. It has been found to be approximately constant for metal particles whose size is above 30 nm.

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, (, ) (Ag/SiO₂), . 30 .

     

The effect of oxidation on the stability of G:C base pair: a MP2 study

The base-pairing energies of eleven oxidized G:C base pairs were characterized by Møller–Plesset perturbation theory. The analysis was focused on the base pairs consisting of guanine and one of the following cytosine derivatives: G:C1 (5-hydroxycytosine); G:C2 (5-hydroxyuracil); G:C3 (5,6-dihydroxy-cytosine); G:C4 (5,6-dihydroxy-uracil); G:C5 (cytosine glycol);G:C6 (isodialuric acid); G:C7 (uracil glycol), and the base pairs between cytosine and one of the following guanine derivatives: G8:C (8-oxo-guanine); G9:C (6-enol-8-keto-guanine); G10:C (xantho-sine); and G11:C (8-hydroxy-guanine). Full geometry optimizations have been performed for the studied complexes by MP2 method. The interaction energies were corrected for the basis-set superposition error (BSSE), using the full Boys-Bernardi counterpoise correction scheme. The results obtained show that the interaction energies of the base pairs decrease in the following order: G8:C > G:C5 ~ G:C1 > G:C3 ~ G:C ~ G11:C > G:C2 > G:C4 > G:C7 > G:C6 > G10:C > G9:C.     

Model reaction related to cytochrome P-450: effect of substitution on the rate of naphthalene oxidation

A kinetic method for measuring the relative rates of hydroxylation of naphthalene derivatives/cyclohexene has been developed. With this technique a linear relationship between the logarithm of the rates of oxidation products and the oxidation potentials of the naphthalene derivatives has been observed. Plots of σ Hammett and σ⁺ Hammett–Brown with logarithm of relative rates have been linear and shown ρ = −0.98 and ρ⁺ = −0.58, respectively. This contrast aromatic oxidation in protic solvents in which the oxidation products are naphthoquinones and provides further evidence for the intermediacy of carbocation in the hemin catalyzed hydroxylation of aromatic rings.     

Nucleation-growth kinetics of the oxidation of silver nanocrystals to silver halide crystals

The electrochemical oxidation of silver nanocrystals to silver halide crystals proceeds by a process of nucleation and growth. The mechanism is confirmed by analyzing chronopotentiograms using a new extension of nucleation theory. The theory makes it possible to derive plots of nucleation-growth currents vs potential, and growth rates vs potential, directly from experimental data. Such plots yield powerful insights into the reaction kinetics. In situ AFM imaging reveals that a few thousand of silver nanocrystals are oxidized to only a few tens of silver halide crystals, without pronounced loss of active material. The mechanism of this remarkable process is described in this paper. In particular, it is shown that the decrease in crystal population proceeds via an oversaturated silver solution, i.e., a process that is mediated by “driven” Ostwald ripening across the electrode surface. At the same time, the low solubility of silver species in bulk solution means that few silver ions escape from the surface. This combination of features explains why the transformation from silver to silver halide is near-stoichiometric yet highly reconstructive.Dedicated to our friend and colleague Professor Dr. Alan Bond on the occasion of his 60th birthday