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In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts. [ABSTRACT FROM AUTHOR]

A force field of the triclinic framework of AlPO4-34, important in methanol–hydrocarbon conversion reactions, was developed using an empirical potential function. Molecular dynamics simulation of an AlPO4-34 triclinic framework segment of 1216 atoms, containing the template molecules isopropylamine and water, was performed with explicit consideration of atomic charges. The average RMS difference between instantaneous positions of the framework atoms during 1 ns simulation and their positions in the structure determined from single crystal X-ray diffraction was calculated, and the average structure of the flexible framework was determined. The computed Debye-Waller factors and simulated FTIR spectra are in good agreement with the experimental data. The new force field permits detailed molecular dynamics simulations of flexible, charged aluminophosphate molecular sieves which should lead to a better understanding of the catalytic processes and the crucial role played by templating molecules. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [ABSTRACT FROM AUTHOR]

Feed composition cycling as a transient kinetic technique provides detailed information about elementary steps in CO oxidation over a nanostructured Cu0.1Ce0.9O2-y catalyst. This catalyst has a great potential as a future PROX reactor catalyst since it has great oxygen storage capacity as well as high reoxidation rate under oxygen rich conditions. [ABSTRACT FROM AUTHOR]

Kinetics and product analysis of detritylation of N-tritylamlodipine by benzenesulfonic acid in methanol, methanol-chloroform (volume ratio 9:1), ethanol, 2-propanol, and methanol/2-propanol (mole ratio 1:1) have been investigated by HPLC; amongst these reaction conditions are ones closely similar to those of one method of manufacturing amlodipine benzenesulfonate. Kinetics of detritylation of Ntritylamlodipine have also been investigated in methanol-d4 by 1H NMR spectroscopy and the agreement with the results by HPLC is good. The rate of detritylation increases with increasing concentrations of benzenesulfonic acid, and p-methoxy-substituents in the trityl group have been shown to lead to faster reactions. In methanol, the rate is hardly affected by 10 % (vol. fraction) chloroform. These studies relate to mechanistic investigations of acid-catalysed deaminations of methoxy-substituted tritylalkylamines, and Arrhenius activation parameters (Ea and A) are similar indicating a common generic mechanism. Acid- catalysed trans-esterification has been shown by HPLC to accompany detritylation in methanol, and attendant protium-deuterium exchange in the methyl at C6 by reversible acid-catalysed iminium ion formation in the 4-aryl-1,4-dihydropyridine moiety of both N-tritylamlodipine and amlodipine has been investigated in deuteriated methanol by ¹H, 13C, and 15N NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Abstract: Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300–380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt–CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated. [Copyright &y& Elsevier]

Proton conducting membranes for fuel cells were prepared by the sol-gel process from two different ureasil organic-inorganic hybrid precursors: bis[(N-(3-triethoxysilylpropyl)ureido]-terminated poly(propylene glycol) 4000 (PPGU) and bis[3-(N-(3-triethoxysilylpropyl)ureido)propyl]-terminated poly(dimethylsiloxane) 1000 (PDMSU). Heteropoly silicotungstic acid was added to actuate the reactions of hydrolysis and condensation and to introduce proton conductivity. XRD measurements of membranes revealed the presence of a diffraction peak at 6.3º, which could be ascribed to gradual formation of R--(SiO3/2) silsesquioxane clusters, i.e. arrangement of the Si--O--Si skeleton on the nano-scale. TG and DSC measurements showed thermal stability of the membranes above 120 °C. Proton conductivities at room temperature were of the order of 10-4 to 10-3 S/cm, classifying the membranes in the group of super ionic conductors. At elevated temperatures up to 160 °C and at conditions of autogenous pressure, conductivities increased up to values acceptable for fuel cells of 10-1 S/cm, which could be the result of the presence of H3O+ ions. The protonation of the urea groups and the formation of amidonium ions [C(OH)=NH+] were followed using IR ATR spectroscopy. [ABSTRACT FROM AUTHOR]

In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.