scholarly journals Microkinetic Modeling of the Oxidation of Methane Over PdO Catalysts—Towards a Better Understanding of the Water Inhibition Effect

Catalysts ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 922
Author(s):  
Kevin Keller ◽  
Patrick Lott ◽  
Henning Stotz ◽  
Lubow Maier ◽  
Olaf Deutschmann
Keyword(s):  
Active Sites ◽  
Catalyst Deactivation ◽  
Field Approximation ◽  
Mean Field Approximation ◽  
Excess Oxygen ◽  
Total Oxidation ◽  
Kinetic Measurements ◽  
Microkinetic Model ◽  
Oxidation Of Methane ◽  
Catalytically Active

Water, which is an intrinsic part of the exhaust gas of combustion engines, strongly inhibits the methane oxidation reaction over palladium oxide-based catalysts under lean conditions and leads to severe catalyst deactivation. In this combined experimental and modeling work, we approach this challenge with kinetic measurements in flow reactors and a microkinetic model, respectively. We propose a mechanism that takes the instantaneous impact of water on the noble metal particles into account. The dual site microkinetic model is based on the mean-field approximation and consists of 39 reversible surface reactions among 23 surface species, 15 related to Pd-sites, and eight associated with the oxide. A variable number of available catalytically active sites is used to describe light-off activity tests as well as spatially resolved concentration profiles. The total oxidation of methane is studied at atmospheric pressure, with space velocities of 160,000 h−1 in the temperature range of 500–800 K for mixtures of methane in the presence of excess oxygen and up to 15% water, which are typical conditions occurring in the exhaust of lean-operated natural gas engines. The new approach presented is also of interest for modeling catalytic reactors showing a dynamic behavior of the catalytically active particles in general.

What catalysis needs from the electron microscopist

1988 ◽  
Vol 46 ◽  
pp. 694-695
Author(s):  
Alexis T. Bell
Keyword(s):  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Catalyst Deactivation ◽  
Surface Composition ◽  
Internal Surface ◽  
Active Phase ◽  
Atomic Scale ◽  
Metal Catalyst ◽  
Internal Surface Area ◽  
Porous Support

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.

The Determination of the Magnetoelectric Coupling Coefficient in Ferroelectric–Ferromagnetic Composite Based on PZT–Ferrite

2013 ◽  
Vol 58 (4) ◽  
pp. 1401-1403 ◽  
Author(s):  
J.A. Bartkowska ◽  
R. Zachariasz ◽  
D. Bochenek ◽  
J. Ilczuk
Keyword(s):  
Dielectric Permittivity ◽  
Coupling Coefficient ◽  
Mean Field ◽  
Field Approximation ◽  
Theoretical Description ◽  
Magnetoelectric Coupling ◽  
Mean Field Approximation ◽  
Dielectric Measurements ◽  
Temperature Dependences ◽  
Multiferroic Composite

Abstract In the present work, the magnetoelectric coupling coefficient, from the temperature dependences of the dielectric permittivity for the multiferroic composite was determined. The research material was ferroelectric-ferromagnetic composite on the based PZT and ferrite. We investigated the temperature dependences of the dielectric permittivity (") for the different frequency of measurement’s field. From the dielectric measurements we determined the temperature of phase transition from ferroelectric to paraelectric phase. For the theoretical description of the temperature dependence of the dielectric constant, the Hamiltonian of Alcantara, Gehring and Janssen was used. To investigate the dielectric properties of the multiferroic composite this Hamiltonian was expressed under the mean-field approximation. Based on dielectric measurements and theoretical considerations, the values of the magnetoelectric coupling coefficient were specified.

scholarly journals Oscillatory Behaviour of Ni Supported on ZrO2 in the Catalytic Partial Oxidation of Methane as Determined by Activation Procedure

Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2495
Author(s):  
Daniela Pietrogiacomi ◽  
Maria Cristina Campa ◽  
Ida Pettiti ◽  
Simonetta Tuti ◽  
Giulia Luccisano ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Partial Oxidation ◽  
Active Sites ◽  
Direct Reduction ◽  
Partial Oxidation Of Methane ◽  
Catalytic Partial Oxidation ◽  
Oxidation Of Methane ◽  
Short Contact Time ◽  
Oxidation Reduction ◽  
Ni Species

Ni/ZrO2 catalysts, active and selective for the catalytic partial oxidation of methane to syngas (CH4-CPO), were prepared by the dry impregnation of zirconium oxyhydroxide (Zhy) or monoclinic ZrO2 (Zm), calcination at 1173 K and activation by different procedures: oxidation-reduction (ox-red) or direct reduction (red). The characterization included XRD, FESEM, in situ FTIR and Raman spectroscopies, TPR, and specific surface area measurements. Catalytic activity experiments were carried out in a flow apparatus with a mixture of CH4:O2 = 2:1 in a short contact time. Compared to Zm, Zhy favoured the formation of smaller NiO particles, implying a higher number of Ni sites strongly interacting with the support. In all the activated Ni/ZrO2 catalysts, the Ni–ZrO2 interaction was strong enough to limit Ni aggregation during the catalytic runs. The catalytic activity depended on the activation procedures; the ox-red treatment yielded very active and stable catalysts, whereas the red treatment yielded catalysts with oscillating activity, ascribed to the formation of Niδ+ carbide-like species. The results suggested that Ni dispersion was not the main factor affecting the activity, and that active sites for CH4-CPO could be Ni species at the boundary of the metal particles in a specific configuration and nuclearity.

scholarly journals Hexagonal-Shaped Spin Crossover Nanoparticles Studied by Ising-Like Model Solved by Local Mean Field Approximation

2021 ◽  
Vol 7 (5) ◽  
pp. 69
Author(s):  
Catherine Cazelles ◽  
Jorge Linares ◽  
Mamadou Ndiaye ◽  
Pierre-Richard Dahoo ◽  
Kamel Boukheddaden
Keyword(s):  
Spin Crossover ◽  
Hexagonal Lattice ◽  
Mean Field ◽  
Field Approximation ◽  
Mean Field Approximation ◽  
Ligand Field ◽  
Order And Disorder ◽  
The Matrix ◽  
Local Mean ◽  
Parameter Values

The properties of spin crossover (SCO) nanoparticles were studied for five 2D hexagonal lattice structures of increasing sizes embedded in a matrix, thus affecting the thermal properties of the SCO region. These effects were modeled using the Ising-like model in the framework of local mean field approximation (LMFA). The systematic combined effect of the different types of couplings, consisting of (i) bulk short- and long-range interactions and (ii) edge and corner interactions at the surface mediated by the matrix environment, were investigated by using parameter values typical of SCO complexes. Gradual two and three hysteretic transition curves from the LS to HS states were obtained. The results were interpreted in terms of the competition between the structure-dependent order and disorder temperatures (TO.D.) of internal coupling origin and the ligand field-dependent equilibrium temperatures (Teq) of external origin.

scholarly journals Manganese vacancy-confined single-atom Ag in cryptomelane nanorods for efficient Wacker oxidation of styrene derivatives

2021 ◽  
Author(s):  
Hongling Yang ◽  
Xun Zhang ◽  
Yi Yu ◽  
Zheng Chen ◽  
Qinggang Liu ◽  
...  
Keyword(s):  
Molecular Sieve ◽  
Active Sites ◽  
Single Atom ◽  
Wacker Oxidation ◽  
Catalytically Active ◽  
Styrene Derivatives

Single-atom catalysts provide a pathway to elucidate the nature of catalytically active sites. However, keeping them stabilized during operation proves to be challenging. Herein, we employ cryptomelane-type octahedral molecular sieve...

Geometrical and Transport Properties of Disordered Fibre Networks: Analytical Results

1997 ◽  
Vol 11 (20) ◽  
pp. 867-875 ◽  
Author(s):  
A. A. Rodríaguez ◽  
E. Medina
Keyword(s):  
Probability Distribution ◽  
Transport Properties ◽  
Geometrical Structure ◽  
Mean Field ◽  
Field Approximation ◽  
Mean Field Approximation ◽  
Fracture Networks ◽  
Simplified Models ◽  
Fibre Density ◽  
Line Network

We study novel geometrical and transport properties of a 2D model of disordered fibre networks. To assess the geometrical structure we determine, analytically, the probability distribution for the number of fibre intersections and resulting segment sizes in the network as a function of fibre density and length. We also determine, numerically, the probability distribution of pore perimeters and areas. We find a non-monotonous behavior of the perimeter distribution whose main features can be explained by solving for two simplified models of the line network. Finally we formulate a mean field approximation to conduction, above the percolation threshold, using the derived results. Relevance of the results to fracture networks will be discussed.

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