Abstract
Electrides, i.e. salts in which electrons serve as anions, are promising materials for lowering activation energies of chemical reactions. Ab initio simulations are used to investigate the effect of the electron anions in a prototype mayenite-based electride (C12A7:e-) on the mechanism of N2 dissociation. It is found that both atomic and molecular nitrogen species chemisorb on the electride surface and become negatively charged due to the electron transfer from the substrate. However, charging alone is not sufficient to promote dissociation of N2 molecules. In the presence of Ru, N2 adsorbs with the formation of a cis-Ru2N 2 complex and the N-N bond weakens due to both the electron transfer from the substrate and interaction with Ru. This complex transforms into a more stable trans-Ru2N2 configuration, in which the N 2 molecule is dissociated, with the calculated barrier of 116 kJ mol-1 and the overall energy gain of 72 kJ mol-1. In contrast, in the case of the stoichiometric mayentie, the cis-Ru 2N2 is ∼34 kJ mol-1 more stable than the trans-Ru2N2, while the cis-trans transition has a barrier of 192 kJ mol-1. Splitting of N2 is promoted by a combination of the strong electron donating power of C12A7:e-, ability of Ru to capture N2, polarization of Ru clusters, and electrostatic interaction of negatively charged N species with the surface cations.
| Original language | English |
|---|---|
| Pages (from-to) | 2216-2219 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 136 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - 12 Feb 2014 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Enhanced N2 dissociation on Ru-loaded inorganic electride. / Kuganathan, Navaratnarajah; Hosono, Hideo; Shluger, Alexander L.; Sushko, Peter V.
In: Journal of the American Chemical Society, Vol. 136, No. 6, 12.02.2014, p. 2216-2219.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Enhanced N2 dissociation on Ru-loaded inorganic electride
AU - Kuganathan, Navaratnarajah
AU - Hosono, Hideo
AU - Shluger, Alexander L.
AU - Sushko, Peter V.
PY - 2014/2/12
Y1 - 2014/2/12
N2 - Electrides, i.e. salts in which electrons serve as anions, are promising materials for lowering activation energies of chemical reactions. Ab initio simulations are used to investigate the effect of the electron anions in a prototype mayenite-based electride (C12A7:e-) on the mechanism of N2 dissociation. It is found that both atomic and molecular nitrogen species chemisorb on the electride surface and become negatively charged due to the electron transfer from the substrate. However, charging alone is not sufficient to promote dissociation of N2 molecules. In the presence of Ru, N2 adsorbs with the formation of a cis-Ru2N 2 complex and the N-N bond weakens due to both the electron transfer from the substrate and interaction with Ru. This complex transforms into a more stable trans-Ru2N2 configuration, in which the N 2 molecule is dissociated, with the calculated barrier of 116 kJ mol-1 and the overall energy gain of 72 kJ mol-1. In contrast, in the case of the stoichiometric mayentie, the cis-Ru 2N2 is ∼34 kJ mol-1 more stable than the trans-Ru2N2, while the cis-trans transition has a barrier of 192 kJ mol-1. Splitting of N2 is promoted by a combination of the strong electron donating power of C12A7:e-, ability of Ru to capture N2, polarization of Ru clusters, and electrostatic interaction of negatively charged N species with the surface cations.
AB - Electrides, i.e. salts in which electrons serve as anions, are promising materials for lowering activation energies of chemical reactions. Ab initio simulations are used to investigate the effect of the electron anions in a prototype mayenite-based electride (C12A7:e-) on the mechanism of N2 dissociation. It is found that both atomic and molecular nitrogen species chemisorb on the electride surface and become negatively charged due to the electron transfer from the substrate. However, charging alone is not sufficient to promote dissociation of N2 molecules. In the presence of Ru, N2 adsorbs with the formation of a cis-Ru2N 2 complex and the N-N bond weakens due to both the electron transfer from the substrate and interaction with Ru. This complex transforms into a more stable trans-Ru2N2 configuration, in which the N 2 molecule is dissociated, with the calculated barrier of 116 kJ mol-1 and the overall energy gain of 72 kJ mol-1. In contrast, in the case of the stoichiometric mayentie, the cis-Ru 2N2 is ∼34 kJ mol-1 more stable than the trans-Ru2N2, while the cis-trans transition has a barrier of 192 kJ mol-1. Splitting of N2 is promoted by a combination of the strong electron donating power of C12A7:e-, ability of Ru to capture N2, polarization of Ru clusters, and electrostatic interaction of negatively charged N species with the surface cations.
UR - http://www.scopus.com/inward/record.url?scp=84894200175&partnerID=8YFLogxK
U2 - 10.1021/ja410925g
DO - 10.1021/ja410925g
M3 - Article
VL - 136
SP - 2216
EP - 2219
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 6
ER -