Abstract
The activation mechanism of NH3 in the selective catalytic reduction of NO by NH3 on a V2O7H4 cluster was investigated using a complete active space self-consistent field method. Because of the easy bond dissociation of NH4+ adsorbed on Brønsted acid sites of the V2O5 configuration, the radical species NH3+ can occur with an activation energy of only 26.7 kcal/mol. The highly active intermediate NH 3+ is stabilized by forming a very strong hydrogen bond of approximately 29.2 kcal/mol to the vanadyl oxygen. This stabilization mechanism is very similar to the low-barrier hydrogen bond in the transition state, or in an unstable intermediate state, which has been reported for some enzymatic reactions.
| Original language | English |
|---|---|
| Pages (from-to) | 12264-12266 |
| Number of pages | 3 |
| Journal | Journal of Physical Chemistry B |
| Volume | 108 |
| Issue number | 33 |
| DOIs | |
| Publication status | Published - Aug 19 2004 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry
Cite this
Selective catalytic reduction of nitric oxide by ammonia : The activation mechanism. / Kobayashi, Yuka; Tajima, Nobuo; Nakano, Haruyuki; Hirao, Kimihiko.
In: Journal of Physical Chemistry B, Vol. 108, No. 33, 19.08.2004, p. 12264-12266.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Selective catalytic reduction of nitric oxide by ammonia
T2 - The activation mechanism
AU - Kobayashi, Yuka
AU - Tajima, Nobuo
AU - Nakano, Haruyuki
AU - Hirao, Kimihiko
PY - 2004/8/19
Y1 - 2004/8/19
N2 - The activation mechanism of NH3 in the selective catalytic reduction of NO by NH3 on a V2O7H4 cluster was investigated using a complete active space self-consistent field method. Because of the easy bond dissociation of NH4+ adsorbed on Brønsted acid sites of the V2O5 configuration, the radical species NH3+ can occur with an activation energy of only 26.7 kcal/mol. The highly active intermediate NH 3+ is stabilized by forming a very strong hydrogen bond of approximately 29.2 kcal/mol to the vanadyl oxygen. This stabilization mechanism is very similar to the low-barrier hydrogen bond in the transition state, or in an unstable intermediate state, which has been reported for some enzymatic reactions.
AB - The activation mechanism of NH3 in the selective catalytic reduction of NO by NH3 on a V2O7H4 cluster was investigated using a complete active space self-consistent field method. Because of the easy bond dissociation of NH4+ adsorbed on Brønsted acid sites of the V2O5 configuration, the radical species NH3+ can occur with an activation energy of only 26.7 kcal/mol. The highly active intermediate NH 3+ is stabilized by forming a very strong hydrogen bond of approximately 29.2 kcal/mol to the vanadyl oxygen. This stabilization mechanism is very similar to the low-barrier hydrogen bond in the transition state, or in an unstable intermediate state, which has been reported for some enzymatic reactions.
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U2 - 10.1021/jp047957z
DO - 10.1021/jp047957z
M3 - Article
AN - SCOPUS:4344706376
VL - 108
SP - 12264
EP - 12266
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 33
ER -