The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis

Bligaard, Thomas; Nørskov, Jens K.; Dahl, Søren; Matthiesen, J.; Christensen, Claus H.; Sehested, Jens

doi:10.1016/j.jcat.2004.02.034

Cited by 1,505 publications

(1,409 citation statements)

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“…Similar to the possibility to control the adsorption energy of adsorbates at surfaces by altering the surface composition [18,24,37], doping bulk metal nitrides with transition metals may diminish or augment the formation of the metal nitride [49]. However, no rationale exists yet that describes how to compose metal nitrides to control the stability of the lattice nitrogen.…”

Section: Controlling the Nitrogen Vacancy Formation In Transition-metmentioning

confidence: 99%

“…This is in analogy to the Sabatier principle in heterogeneous catalysis [37] that describes the ideal catalytic activity of a material as a function of an intermediately strong bond formed between the catalyst surface and key reaction intermediates [18,24]. As a starting point, we have chosen Mo and Mn as primary metals for the development of advanced metal nitride redox materials.…”

Section: Introductionmentioning

confidence: 99%

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Rational design of metal nitride redox materials for solar-driven ammonia synthesis

2015

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Fixed nitrogen is an essential chemical building block for plant and animal protein, which makes ammonia (NH 3 ) a central component of synthetic fertilizer for the global production of food and biofuels. A global project on artificial photosynthesis may foster the development of production technologies for renewable NH 3 fertilizer, hydrogen carrier and combustion fuel. This article presents an alternative path for the production of NH 3 from nitrogen, water and solar energy. The process is based on a thermochemical redox cycle driven by concentrated solar process heat at 700–1200°C that yields NH 3 via the oxidation of a metal nitride with water. The metal nitride is recycled via solar-driven reduction of the oxidized redox material with nitrogen at atmospheric pressure. We employ electronic structure theory for the rational high-throughput design of novel metal nitride redox materials and to show how transition-metal doping controls the formation and consumption of nitrogen vacancies in metal nitrides. We confirm experimentally that iron doping of manganese nitride increases the concentration of nitrogen vacancies compared with no doping. The experiments are rationalized through the average energy of the dopant d-states, a descriptor for the theory-based design of advanced metal nitride redox materials to produce sustainable solar thermochemical ammonia.

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Section: Controlling the Nitrogen Vacancy Formation In Transition-metmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

2015

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“…This is generally fulfilled by the elements in the middle of the transition metal series and leads, for instance, to the high activity of ruthenium and cobalt for CO methanation. 2 These metals mark the transition from dissociative to molecular binding of CO for the 3d and 4d metals, respectively. According to Brodèn et al.…”

Section: Introductionmentioning

confidence: 99%

Probing C–O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

Lyon

Gruene

Fielicke

et al. 2009

The Journal of Chemical Physics

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The binding of carbon monoxide to iron, ruthenium, rhenium, and tungsten clusters is studied by means of infrared multiple photon dissociation (IR-MPD) spectroscopy. The CO stretching mode is used to probe the interaction of the CO molecule with the metal clusters and thereby the activation of the C-O bond. CO is found to adsorb molecularly to atop positions on iron clusters. On ruthenium and rhenium clusters it also binds molecularly. In the case of ruthenium, binding is predominantly to atop sites, however higher coordinated CO binding is also observed for both metals and becomes prevalent for rhenium clusters containing more than 9 atoms. Tungsten clusters exhibit a clear size dependence for molecular vs. dissociative CO binding. This behavior denotes the crossover to the purely dissociative CO binding on the earlier transition metals such as tantalum.2

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“…[3][4][5][6][7][8] The underlying principles of the descriptor-based approach are the existence of relations between the surface electronic structure, adsorption energies and activation barriers that result in volcanoshaped activity plots as function of simple descriptors, such as atomic binding energies or the d-band center. [1,6,[9][10][11][12][13][14][15][16][17] Linear scaling relations have been established between the adsorption energies of hydrogen-containing molecules such as CH x , NH x , OH x and SH x and the C, N O and S adsorption energies on transition-metal surfaces. [18] Transition-state energies have also been shown to scale linearly with adsorption energies in a similar fashion.…”

mentioning

confidence: 99%

“…[18] Transition-state energies have also been shown to scale linearly with adsorption energies in a similar fashion. [9,16,19,20] Recently, a single transition state scaling relation has been identified for a large number of C-C, C-O, C-N, N-O, N-N, and O-O coupling reactions. [21] The scaling relations provide a powerful tool for the investigation of reaction mechanisms and the prediction of potential energy surfaces.…”

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confidence: 99%

Descriptor‐Based Analysis Applied to HCN Synthesis from NH₃ and CH₄

et al. 2011

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The design of solid metal catalysts using theoretical methods has been a long-standing goal in heterogeneous catalysis. [1, 2] Recent developments in methodology and computer technology as well as the establishment of a descriptor-based approach for the analysis of reaction mechanisms and trends across the periodic table allow for the fast screening for new catalytic materials and have lead to first examples of computational discoveries of new materials. [3][4][5][6][7][8] The underlying principles of the descriptor-based approach are the existence of relations between the surface electronic structure, adsorption energies and activation barriers that result in volcanoshaped activity plots as function of simple descriptors, such as atomic binding energies or the d-band center. [1,6,[9][10][11][12][13][14][15][16][17] Linear scaling relations have been established between the adsorption energies of hydrogen-containing molecules such as CH x , NH x , OH x and SH x and the C, N O and S adsorption energies on transition-metal surfaces. [18] Transition-state energies have also been shown to scale linearly with adsorption energies in a similar fashion. [9,16,19,20] Recently, a single transition state scaling relation has been identified for a large number of C-C, C-O, C-N, N-O, N-N, and O-O coupling reactions. [21] The scaling relations provide a powerful tool for the investigation of reaction mechanisms and the prediction of potential energy surfaces. They limit the number of independent variables to a few, typically adsorption energies of key atoms. Using this information as input to a microkinetic model provides an understanding of trends in catalytic activity across the transition metals. In most cases a volcano-shaped relation between activity and the key variables, the descriptors, is observed. [16] In the present paper we will provide an example of the approach outlined above and show how one can obtain an understanding of activity/selectivity trends of a reaction with just a few new calculations. We take the synthesis of hydrogen cyanide (HCN), a versatile synthetic building block in organic chemistry, as an example. [22] For the catalytic production of HCN from methane (CH 4 ) and ammonia (NH 3 ) there exist two main processes: the Andrussow and the Degussa (BMA) process. [23][24][25] Both processes use Pt gauze catalysts and are run at temperatures up to 1573 K. The main reason for the high reaction temperature is the endothermicity (ΔH 0 = 251 kJ/mol(HCN)) of the reaction CH 4 + NH 3 → HCN + 3 H 2 , whereas the competing side reaction 2 NH 3 → N 2 + 3 H 2 is less endothermic (ΔH 0 = 46 kJ/mol(NH 3 )). Hence, NH 3 decomposition is thermodynamically favored at low temperatures. In contrast to the Degussa process where the necessary heat is supplied externally, O 2 is added to the feed of the Andrussow process and its reaction with H 2 supplies the necessary energy to drive the endothermic HCN formation.The industrially used Pt/Rh gauze catalysts reach their optimal activity only after an extended activation p...

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The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis

Cited by 1,505 publications

References 42 publications

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Probing C–O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

Descriptor‐Based Analysis Applied to HCN Synthesis from NH₃ and CH₄

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The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis

Cited by 1,505 publications

References 42 publications

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Probing C–O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

Descriptor‐Based Analysis Applied to HCN Synthesis from NH3 and CH4

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Descriptor‐Based Analysis Applied to HCN Synthesis from NH₃ and CH₄