Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

Kandoi, Shampa; Greeley, Jeffrey; Evans, Steven T.; Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos

doi:10.1007/s11244-006-0001-1

Cited by 144 publications

(147 citation statements)

References 36 publications

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“…111 Even less demanding is a somewhat intermediate approach, which avoids the explicit surface vibrational calculations and predicts the entropy of surface species by scaling that of the corresponding gas-phase molecule and subtracting the loss in translational entropy. 112,113 This scaling factor is typically obtained from regression to experimental data, which clearly hampers the application of this method in a purely first-principles context.…”

Section: From Energies To Rate Constantsmentioning

confidence: 99%

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

Sabbe

Reyniers

Reuter

2012

Catal. Sci. Technol.

151

153

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Electronic structure calculations have emerged as a key contributor in modern heterogeneous catalysis research, though their application in chemical reaction engineering remains largely limited to academia. This perspective aims at encouraging the judicious use of first-principles kinetic models in industrial settings based on a critical discussion of present-day best practices, identifying existing gaps, and defining where further progress is needed.

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Section: From Energies To Rate Constantsmentioning

confidence: 99%

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

Sabbe

Reyniers

Reuter

2012

Catal. Sci. Technol.

151

153

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“…Today, DFT has reached a level of sophistication where it can be used to describe complete catalytic reactions and hence provide an insight that pinpoints to the origin of the catalytic activity and selectivity. 1,2,3,4,5,6 However, extensive DFT calculations that eventually lead to this understanding are still computationally demanding. A simplification that connects the reactivity and selectivity of a catalytic surface to one or few descriptors is therefore extremely useful.…”

Section: Abstract Density Functional Theory -Stepped Surfaces -Couplimentioning

confidence: 99%

Universal Brønsted-Evans-Polanyi Relations for C–C, C–O, C–N, N–O, N–N, and O–O Dissociation Reactions

Temel²,

et al. 2010

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It is shown that for all the essential bond forming and bond breaking reactions on metal surfaces, the reactivity of the metal surface correlates linearly with the reaction energy in a single universal relation. Such correlations provide an easy way of establishing trends in reactivity among the different transition metals. Keywords Density Functional Theory -Stepped surfaces -Coupling reactions -Bond breaking reactions -BEP relations -Scaling relationsTo bridge the gap between macroscopic properties of a catalyst, such as turn-over rates and selectivity and the microscopic properties obtained from electronic structure methods based on density functional theory (DFT), an in depth understanding of the underlying thermodynamics and kinetics of the corresponding metal surfaces is needed. Today, DFT has reached a level of sophistication where it can be used to describe complete catalytic reactions and hence provide an insight that pinpoints to the origin of the catalytic activity and selectivity. 1,2,3,4,5,6 However, extensive DFT calculations that eventually lead to this understanding are still computationally demanding. A simplification that connects the reactivity and selectivity of a catalytic surface to one or few descriptors is therefore extremely useful. Such a simplification, e.g. the Brønsted-Evans-Polanyi (BEP) relations, is able to show that the transition state energy of a reaction is linearly depending on the reaction energy. 7,8,9,10,11,12 * Corresponding author SLAC-PUB-14285 2 Herein, we investigate the transition state energies of a large number of essential bond breaking and forming reactions that play a key role in the catalytic transformation of a large fraction of base chemicals. The transition state energies investigated include C-C, C-O, C-N, N-O, N-N, and O-O coupling and have been calculated on different stepped surfaces of transition metals such as Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au. For a dissociation reaction (AB → A+B), the transition state energy (E ts ) is calculated by Equation (1), in which E ts/slab , E slab and E gas are the total energies of the slab with transition states, the clean slab, and the gas phase molecules relevant for the reactions, respectively. The dissociative adsorption energy (E diss ) is calculated by Equation (2), in which E A/slab and E B/slab are the total energies of the slab with adsorbates A and B, respectively.(1)All calculations were performed using the DACAPO plane-wave pseudo potential DFT code. 13 Ionic cores were described by ultrasoft pseudopotentials 14, and the Kohn-Sham one-electron valence states were expanded in a basis of plane wave functions with a cutoff energy up to 340 eV. For most adsorption systems, the surface Brillouin zone was sampled using a Monkhorst-Pack grid of size 4×4×1, while 2×3×1 was used for O 2 , and 8×6×1 was used for N 2 and NO as a test of the parameters. The self-consistent electron density was determined by iterative diagonalization of the Kohn-Sham Hamiltonian. A Fermi distribution for the population of...

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] This success has been made possible by the use of density functional theory and the increase in computer power. The adsorption energy and barrier height information can be combined with either a mean-field kinetic model 11 or a kinetic Monte Carlo model, 12 where interactions between surface species can be included, to obtain the catalytic activity of single sites.…”

Section: Introductionmentioning

confidence: 99%

Structure and reactivity of ruthenium nanoparticles

Gavnholt

Schiøtz

2008

Phys. Rev. B

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We present a method for obtaining detailed structural information of ruthenium nanoparticles in at least the diameter range from 1.5 to 5 nm. The method is based on an ensemble approach where a large number of low-energy structures are collected in an ensemble, from which average properties can be extracted using Boltzmann averaging. The method is used to obtain the number of catalytic active step sites present on the surface of the ruthenium particles. We find that the presence of highly catalytic active step sites does not depend significantly on the temperature within a relevant temperature range; the presence of step sites is mainly a function of the lowest energy shape of the cluster, i.e., a function of the number of atoms. By combining the structural information with estimations of the single site activities in the ammonia synthesis, we find that the optimal particle diameter is approximately 3 nm. The single site activities are estimated by using density functional theory to calculate the barrier of the rate limiting step, the dissociation of a nitrogen molecule.

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Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

Cited by 144 publications

References 36 publications

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

Universal Brønsted-Evans-Polanyi Relations for C–C, C–O, C–N, N–O, N–N, and O–O Dissociation Reactions

Structure and reactivity of ruthenium nanoparticles

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