In this paper, pneumatochemical impedance spectroscopy is used to analyze multistep reaction mechanisms such as those observed in solid solution domains of LaNi5-H2(g) systems. It is shown that hydrogen sorption is a two-step mechanism including (i) dissociative surface chemisorption of molecular hydrogen and (ii) atomic hydrogen bulk transport by diffusion. Data fitting of experimental transfer functions with model equations yields the value of the kinetic parameter associated with each individual reaction step, i.e., surface sorption resistances and hydrogen bulk diffusion coefficients. The technique is used to follow the activation procedure of the sample as well as the degradation of sorption properties in oxygen-containing hydrogen atmospheres. A decrease in sorption kinetics is attributed to surface oxidation, whereas bulk properties remain unchanged. The perspectives offered by the technique which potentially can be used to optimize surface and bulk composition of IMC for increased sorption rates are discussed.
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http://dx.doi.org/10.1021/jp053351e | DOI Listing |
Rev Sci Instrum
December 2007
Institut de Chimie Moléculaire et des Matériaux, UMR CNRS 8182, Université Paris-sud 11, 15 rue Georges Clémenceau, 91405 Orsay, Cedex, France.
Hydrogen storage remains a bottleneck process on the way to the hydrogen economy. For practical applications, metal hydride systems offer interesting features, in particular, the possibility of reversibly storing large amounts of hydrogen at low or moderate pressure. However, they still suffer from unfavorable specific energy, with mass-fraction values ranging from 0 up to 5 wt % whereas transport applications require 6 wt % and more.
View Article and Find Full Text PDFJ Phys Chem B
December 2005
Laboratoire de Chimie Inorganique, Université Paris Sud, bâtiment 420, 91405 Orsay cedex, France.
In this paper, pneumatochemical impedance spectroscopy is used to analyze multistep reaction mechanisms such as those observed in solid solution domains of LaNi5-H2(g) systems. It is shown that hydrogen sorption is a two-step mechanism including (i) dissociative surface chemisorption of molecular hydrogen and (ii) atomic hydrogen bulk transport by diffusion. Data fitting of experimental transfer functions with model equations yields the value of the kinetic parameter associated with each individual reaction step, i.
View Article and Find Full Text PDFJ Phys Chem B
December 2005
Laboratoire de Chimie Inorganique, Université Paris Sud, bâtiment 420, 91405 Orsay cedex, France.
Pneumatochemical impedance spectroscopy (PIS) is the indirect transposition of electrochemical impedance spectroscopy (EIS) to solid-gas reactions. In PIS analysis, an analogy is made between pressure and electrical potential on one hand and gas flow and electric current on the other hand, and pneumatochemical transfer functions are derived from gas-phase measurements. Potentially, this spectroscopy can be used to analyze the dynamics of any solid-gas system including adsorption (surface) and absorption (bulk) phenomena, gas (H2) permeation across metallic membranes, and electrocatalysis in gaseous fuel cells.
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