Universality in Heterogeneous Catalysis

Nørskov, Jens K.; Bligaard, Thomas; Logadóttir, Áshildur; Bahn, Sune Rastad; Hansen, Lars Henrik; Bollinger, Mikkel; Bengaard, Hanne Skov; Hammer, Bjørk; Šljivančanin, Željko; Mavrikakis, Manos; Xu, Ye; Dahl, Søren; Jacobsen, Claus J. H.

doi:10.1006/jcat.2002.3615

Cited by 1,257 publications

(1,145 citation statements)

References 18 publications

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“…The study was focused on the stepped (211) facet of the copper face-centered cubic (fcc) crystal. This surface was chosen since stepped sites often exhibit higher activities in activating bonds than do close-packed surfaces [5]. Although the previous thermodynamic study provided insights into the likely mechanisms of CO 2 electroreduction, a more complete theoretical understanding will require the exploration of structural effects as well as the incorporation of kinetic barriers.…”

Section: Introductionmentioning

confidence: 99%

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

et al. 2011

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Polycrystalline copper electrocatalysts have been experimentally shown to be capable of reducing CO 2 into CH 4 and C 2 H 4 with relatively high selectivity, and a mechanism has recently been proposed for this reduction on the fcc(211) surface of copper, which was assumed to be the most active facet. In the current work, we use computational methods to explore the effects of the nanostructure of the copper surface and compare the effects of the fcc(111), fcc(100) and fcc(211) facets of copper on the energetics of the electroreduction of CO 2 . The calculations performed in this study generally show that the intermediates in CO 2 reduction are most stabilized by the (211) facet, followed by the (100) facet, with the (111) surface binding the adsorbates most weakly. This leads to the prediction that the (211) facet is the most active surface among the three in producing CH 4 from CO 2 , as well as the by-products H 2 and CO. HCOOH production may be mildly enhanced on the more close-packed surfaces ( (111) and (100)) as compared to the (211) facet, due to a change in mechanism from a carboxyl intermediate to a formate intermediate. The results are compared to experimental data on these same surfaces; the predicted trends in voltage requirements are consistent between the experimental and computational data.

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Section: Introductionmentioning

confidence: 99%

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

et al. 2011

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“…The accuracy is not such that detailed predictions of absolute rates of elementary reaction steps can be made, but for classes of interesting catalysts (transition metals) it is possible to create systematic data with sufficient accuracy to predict trends in reactivity. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] In the present paper, we introduce such a set of calculated reaction energies and activation energies for a large number of elementary surface reactions on a series of metal single crystal surfaces including surfaces with defects such as steps. We will also introduce a simple web application (CatApp) that can be downloaded to access these data.…”

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confidence: 99%

CatApp: A Web Application for Surface Chemistry and Heterogeneous Catalysis

et al. 2011

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We introduce a web application (CatApp) for looking up calculated reaction and activation energies for elementary coupling reactions occurring on metal surfaces. It provides access to reaction and activation energies for all reactions involving C-C, C-H, C-O, O-O, O-H, N-N, C-N, O-N, N-H splittingSolid catalysts form the backbone of the chemical industry and the hydrocarbon-based energy sector. Most catalysts and processes today are highly optimized, but there is still considerable room for improvements in reactivity and selectivity that would lower energy consumption and waste production. In addition there are tremendous challenges to catalysis science and engineering in developing a sustainable energy solutions. The ability to store solar energy as a fuel calls for new catalysts and so does the development of a sustainable chemical industry based on biomass and other non-fossil building blocks.The development of new catalysts could be accelerated significantly if we had access to systematic data for activation energies of elementary surface reactions. Once the key parameters determining the activity or selectivity of a certain process has been established though experiments or calculations, such a database would enable searches for new catalyst leads. Ideally, data would come from detailed, systematic experiments, but it is in general not possible to find such data. Electronic structure calculations provide a powerful alternative. The accuracy is not such that detailed predictions of absolute rates of elementary reaction steps can be made, but for classes of interesting catalysts (transition metals) it is possible to create systematic data with sufficient accuracy to predict trends in reactivity. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] In the present paper, we introduce such a set of calculated reaction energies and activation energies for a large number of elementary surface reactions on a series of metal single crystal surfaces including surfaces with defects such as steps. We will also introduce a simple web application (CatApp) that can be downloaded to access these data.

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“…Note that in the original product state, CH 3 and H bind to three met al surface atoms, but in our simple cluster, not all those bonds are present. This doesn't influence the transition state, but does show the bonding scheme in the product state to be more similar to the transition state than is the case.…”

Section: Changes Of Bond Orders Over the Reactionmentioning

confidence: 83%

“…Inspired by the work of Nørskov et al [3], Michaelides et al [4] analyse transition state (TST) energies using barrier decomposition analysis, decomposing the reaction barrier with respect to the of association reaction into two parts. One part depends on the adsorption energies of the product fragments.…”

Section: Introductionmentioning

confidence: 99%

“…The starting point of our method of analysis is the insight that reactions such as methane activation are quintessentially 3-body reactions, with the three interacting bodies being the molecular fragments (A = CH 3 , B = H)and the catalyst (C = Rh{111})-in our case the active atoms of the surface; in other cases it might be a reactive complex.…”

Section: Introductionmentioning

confidence: 99%

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Symmetric Transition State Analysis: An Analysis of Dissociative Methane Adsorption on Rh{111} Using Quantum Chemical Calculations

2010

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The chemical bonding aspects of the transition state (TST) of methane activation on a Rh{111} surface are analyzed. Three methods are compared: The barrier decomposition analysis of Hu et al. in which the bond between CH is assumed completely broken in the TST (Satterfield, Heterogeneous catalysis in industrial practice, 2nd ed., 1996; Chorkendorff and Niemantsverdriet, Concepts of modern catalysis and kinetics, 2003; Somorjai, Introduction to surface chemistry and catalysis, 1994); the activation strain model of Bickelhaupt in which the CH bond is assumed to be equal to the gasphase CH interaction energy (Christmann, Surface science reports, 1988; Nørs-kov and Christensen, Science, 2006; Forsberg, Chemical engineering progress, 2005); and a model in which the interaction energies between CH, and of the H atom and CH 3 with the catalyst are all given equal attention, the symmetric transition state analysis. This symmetric transition state analysis would not yield a result different from the traditional methods if all bonds were additive and decoupled. But, as our results show, that is not in general the case. The position of the maximum in non-additivity can be considered a descriptor for the position of the TST on the reaction coordinate. At the TST, we find that the three interactions are of comparable strength.

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Universality in Heterogeneous Catalysis

Cited by 1,257 publications

References 18 publications

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

CatApp: A Web Application for Surface Chemistry and Heterogeneous Catalysis

Symmetric Transition State Analysis: An Analysis of Dissociative Methane Adsorption on Rh{111} Using Quantum Chemical Calculations

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