Local Catalytic Ignition during CO Oxidation on Low-Index Pt and Pd Surfaces: A Combined PEEM, MS, and DFT Study

Shedding light on light-off: Photoemission electron microscopy, DFT, and microkinetic modeling were used to examine the local kinetics in the CO oxidation on individual grains of a polycrystalline sample. It is demonstrated that catalytic ignition (“light-off”) occurs easier on Pd(hkl) domains than on corresponding Pt(hkl) domains. The isothermal determination of kinetic transitions, commonly used in surface science, is fully consistent with the isobaric reactivity monitoring applied in technical catalysis

Crossover from directed percolation to compact directed percolation

We study critical spreading in a surface-modified directed percolation model in which the left- and right-most sites have different occupation probabilities than in the bulk. As we vary the probability for growth at an edge, the critical exponents switch from the compact directed percolation class to ordinary directed percolation. We conclude that the nonuniversality observed in models with multiple absorbing configurations cannot be explained as a simple surface effect.Comment: 4 pages, Revtex, 5 figures postscrip

Nitrides as ammonia synthesis catalysts and as potential nitrogen transfer reagents

In this article, an overview of the application of selected metal nitrides as ammonia synthesis catalysts is presented. The potential development of some systems into nitrogen transfer reagents is also described

Effect of Solution Composition on the Energy Production by Capacitive Mixing in Membrane-Electrode Assembly

The final edited version of the paper can be found at: http://pubs.acs.org/articlesonrequest/AOR-c9UMxSzGY3eiU5SENNgT The complete citation is: Ahualli, S.; et al. Effect of Solution Composition on the Energy Production by Capacitive Mixing in Membrane-Electrode Assembly. Journal of Physical Chemistry, 118(29): 15590-15599 (2014). DOI:10.1021/jp504461mOpen access in the Journal on May 26, 2015In this work we consider the extent to which the presence of multi-valent ions in solution modifies the equilibrium and dynamics of the energy production in a capacitive cell built with ion-exchange membranes in contact with high surface area electrodes. The cell potential in open circuit (OCV) is controlled by the difference between both membrane potentials, simulated as constant volume charge regions. A theoretical model is elaborated for steady state OCV, first in the case of monovalent solutions, as a reference. This is compared to the results in multi-ionic systems, containing divalent cations in concentrations similar to those in real sea water. It is found that the OCV is reduced by about 25 % (as compared to the results in pure NaCl solutions) due to the presence of the divalent ions, even in low concentrations. Interestingly, this can be related to the “uphill” transport of such ions against their concentration gradients. On the contrary, their effect on the dynamics of the cell potential is negligible in the case of highly charged membranes. The comparison between model predictions and experimental results shows a very satisfactory agreement, and gives clues for the practical application of these recently introduced energy production methods.The research leading to these results received funding from the European Union 7th Framework Programme (FP7/2007-2013) under agreement No. 256868. Further financial support from Junta de Andalucia, Spain (PE2012-FQM 694) is also acknowledged. One of us, M.M.F., received financial support throughan FPU grant from the Universityof Granada

The vitamin D, ionised calcium and parathyroid hormone axis of cerebral capillary function: Therapeutic considerations for vascular-based neurodegenerative disorders

Blood-brain barrier dysfunction characterised by brain parenchymal extravasation of plasma proteins may contribute to risk of neurodegenerative disorders, however the mechanisms for increased capillary permeability are not understood. Increasing evidence suggests vitamin D confers central nervous system benefits and there is increasing demand for vitamin D supplementation. Vitamin D may influence the CNS via modulation of capillary function, however such effects may be indirect as it has a central role in maintaining calcium homeostasis, in concert with calcium regulatory hormones. This study utilised an integrated approach and investigated the effects of vitamin D supplementation, parathyroid tissue ablation (PTX), or exogenous infusion of parathyroid hormone (PTH) on cerebral capillary integrity. Parenchymal extravasation of immunoglobulin G (IgG) was used as a marker of cerebral capillary permeability. In C57BL/6J mice and Sprague Dawley rats, dietary vitamin D was associated with exaggerated abundance of IgG within cerebral cortex (CTX) and hippocampal formation (HPF). Vitamin D was also associated with increased plasma ionised calcium (iCa) and decreased PTH. A response to dose was suggested and parenchymal effects persisted for up to 24 weeks. Ablation of parathyroid glands increased CTX- and HPF-IgG abundance concomitant with a reduction in plasma iCa. With the provision of PTH, iCa levels increased, however the PTH treated animals did not show increased cerebral permeability. Vitamin D supplemented groups and rats with PTH-tissue ablation showed modestly increased parenchymal abundance of glial-fibrillary acidic protein (GFAP), a marker of astroglial activation. PTH infusion attenuated GFAP abundance. The findings suggest that vitamin D can compromise capillary integrity via a mechanism that is independent of calcium homeostasis. The effects of exogenous vitamin D supplementation on capillary function and in the context of prevention of vascular neurodegenerative conditions should be considered in the context of synergistic effects with calcium modulating hormones

Oxidation of carbon monoxide over palladium on zirconia prepared from amorphous Pd1Zr2 alloy I.: bulk structural, morphological, and catalytic properties of catalyst

Catalysts highly active for the oxidation of carbon monoxide have been prepared by oxidation of amorphous and crystalline Pd1Zr2 metal alloys. The oxidation was carried out in situ; i.e., the fresh metal alloys were exposed to CO-oxidation conditions at temperatures of 473–553 K. Under these conditions, the initially almost inactive metal alloys underwent a series of solid state reactions and were finally transformed into stable and highly active microporous catalysts. Bulk structural characterization using X-ray diffraction and electron microscopy revealed that the final catalysts were made up of small intergrown and poorly crystalline domains of different palladium and zirconia phases. Palladium was present in three forms in the active catalysts, as a solid solution of palladium and oxygen, as metallic palladium, and as PdO. Zirconia existed in monoclinic and tetragonal forms. Comparative kinetic measurements carried out in a differential fixed bed reactor in the temperature range 300–500 K indicated that the activity of the palladium species in the catalysts derived from the metal alloys was more than an order of magnitude higher than the activity of the palladium species in a palladium on zirconia catalyst prepared by impregnation. The comparison of the activities was based on turnover frequencies calculated on the basis of accessible palladium sites determined by CO chemisorption. The higher activity of the catalysts derived from the metal alloys is attributed to their unique structural and chemical properties leading to extremely large interfacial areas and possibly to enhanced oxygen transfer via the solid-solid interphase