Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (100) surfaces

Liu, Da‐Jiang; Evans, James W.

doi:10.1016/j.progsurf.2013.10.001

Cited by 63 publications

(268 citation statements)

References 248 publications

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“…[23][24][25][26] While the competition of phononic and (1). A tractable embedding cell for the periodic QM calculations is indicated in blue (3-layer slab formed out of a 3 × 8 multiple of the primitive surface unit cell).…”

Section: Hot or Notmentioning

confidence: 99%

“…[23][24][25][26] While the competition of phononic and + ¡ F (eV/Å) Figure 1: (color online). Schematic illustration of the QM/Me embedding scheme defined by Equation (1).…”

Section: Dedicated To My Parents Brigitte and Siegfried Meyermentioning

confidence: 99%

“…Clearly, the thermalization process is not instantaneous on the time scale of the actual adsorbate dynamics. According to the barrier of 300 meV (DFT-PBE) or even more [23,24,26] for the hollow-bridge-hollow diffusion path followed by the O adatoms, transition state theory would estimate individual thermal diffusive hops at room temperature to take place over time scales of microseconds or even longer. Instead, we observe a transient mobility over several lattice constants within 1.5 ps.…”

mentioning

confidence: 99%

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Modeling Heat Dissipation at the Nanoscale: An Embedding Approach for Chemical Reaction Dynamics on Metal Surfaces

Meyer

Reuter

2014

Angew Chem Int Ed

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Hot or not:An embedding technique for metallic systems makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. Application to O2 dissociation at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This questions the instant thermalization of reaction enthalpies generally assumed in heterogeneous catalysis modeling.Modeling Heat Dissipation at the Nanoscale:An Abstract: We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O 2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis.Exothermic surface chemical reactions may easily release several electron volts of energy. Though sizable in view of potential microscopic dissipation channels, the prevalent picture in chemical kinetics is that this energy is quasi-instantaneously thermalized, ultimately into * joerg.meyer@ch.tum.de present address: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands phononic degrees of freedom. This motivates theoretical treatments on the level of a local temperature and separates the continuous chemical motion into rare-event sequences of thermal reactions. The resulting Markovian state-to-state hopping underlies, for example, all presentday microkinetic formulations in heterogeneous catalysis. [1,2] The validation of this picture would require detailed insight into the energy-conversion process at the interface. To date this is limited at best, and if at all centered on reactions at well-defined single-crystal surfaces in ultrahigh vacuum. For a prototypical model reaction like the dissociative adsorption of O 2 molecules scanningtunneling microscopy experiments have suggested the formation of so-called "hot adatoms" on several metal surfaces. [3][4][5][6] As a consequence of the released chemical energy, this transient mobility thus intricately couples the elementary reaction steps of dissociation and diffusion.As the experimental quest to generate molecular movies of such reactions is still ongoing, theory has been challenged to elucidate the equilibration dynamics of this process. [7][8][9] Here, the bond breaking and making in highly corrugated surface potentials dictates computationally demanding quantum mechanical (QM) treatments, in par- ticular periodic boundary condition (PBC) supercell approaches to adequately describe the delocalized (surface) metallic band structure. [2] Complementing this with a...

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Section: Hot or Notmentioning

confidence: 99%

“…[23][24][25][26] While the competition of phononic and + ¡ F (eV/Å) Figure 1: (color online). Schematic illustration of the QM/Me embedding scheme defined by Equation (1).…”

Section: Dedicated To My Parents Brigitte and Siegfried Meyermentioning

confidence: 99%

mentioning

confidence: 99%

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Modeling Heat Dissipation at the Nanoscale: An Embedding Approach for Chemical Reaction Dynamics on Metal Surfaces

Meyer

Reuter

2014

Angew Chem Int Ed

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“…Theoretical approaches to various aspects of surface-mediated processes spans from concentrated mean-field models to distributed stochastic models to hybrid models; from minimalistic models (like seminal ZGB model [50]) to fairly sophisticated models with parameters calculated from first principles (direct problem, bottom-up approach) or restored from kinetic experiments (inverse problem, top-down approach) or with parametric space being itself the subject of study [3,11,25,29,31,33,35,38,49]. During recent decades impressive progress has been achieved in all fields of surface-mediated phenomena thanks to well-turned use of sophisticated ab initio models.…”

Section: Introductionmentioning

confidence: 99%

Reversible Reshaping of Supported Metal Nanoislands Under Reaction Conditions in a Minimalistic Lattice Model

Коробов

2016

J Stat Phys

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The shape of (nano)islands is among significant factors of the catalytic activity of supported catalysts. A lattice model of the reshaping under reaction conditions is suggested and studied by means of kinetic Monte Carlo simulations. It is rooted in experimental findings and is simplified as far as possible to still demonstrate reversible compact-ramified shape transitions. This simple model with complex behavior demonstrates several reshaping regimes and is considered as a possible sub-network of more realistic networks of heterogeneous catalytic reactions.

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“…In recent years, a number of groups have formulated various models to better understand the oxidation kinetics at work [34][35][36][37][38][39][40]. Of particular note, Sethuraman et al found that surface populations of WB CO ads species dominated at lower temperatures and SB CO adsorbates dominated at higher temperatures in thermally-driven adsorption/oxidation experiments.…”

Section: Introductionmentioning

confidence: 99%

Anodic Oxidation of COads Derived from Methanol on Pt Electrocatalysts Linked to the Bonding Type and Adsorption Site

Engstrom

Lim

Reimer

et al. 2014

Electrochimica Acta

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a b s t r a c tA newly formulated four-component modified Butler-Volmer model has been developed to evaluate global oxidation kinetic parameters for the various types of carbon monoxide adsorbates (CO ads ) on a nanoparticle Pt surface determined by the type of bonding as well as the local structure of the adsorption site. Partial coverages of CO ads were prepared by potentiostatic adsorption of methanol followed by potentiostatic partial oxidation at various elevated potentials and for various durations. Anodic linear sweep voltammetry was then performed, and the CO ads oxidation peaks were fitted with the model to analyze the kinetics. According to the model, preferential oxidation with respect to CO ads bonding and Pt substrate structure can be achieved dependent upon the potential and extent of oxidation. Partial oxidation at 450 mV vs. RHE for 60 min. resulted in a majority population of linearly bonded CO ads on cubic-packed Pt sites; whereas partial oxidation at 650 mV vs. RHE for 220 sec. resulted in a majority population of bridged-bonded CO ads on close-packed Pt sites.

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Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (100) surfaces

Cited by 63 publications

References 248 publications

Modeling Heat Dissipation at the Nanoscale: An Embedding Approach for Chemical Reaction Dynamics on Metal Surfaces

Modeling Heat Dissipation at the Nanoscale: An Embedding Approach for Chemical Reaction Dynamics on Metal Surfaces

Reversible Reshaping of Supported Metal Nanoislands Under Reaction Conditions in a Minimalistic Lattice Model

Anodic Oxidation of COads Derived from Methanol on Pt Electrocatalysts Linked to the Bonding Type and Adsorption Site

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