Selective catalytic reduction of nitric oxide by ammonia: The activation mechanism

Yuka Kobayashi; Nobuo Tajima; Haruyuki Nakano; Kimihiko Hirao

doi:10.1021/jp047957z

Selective catalytic reduction of nitric oxide by ammonia: The activation mechanism

Yuka Kobayashi, Nobuo Tajima, Haruyuki Nakano, Kimihiko Hirao

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

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	https://doi.org/10.1021/jp047957z
Publication status	Published - Aug 19 2004
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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10.1021/jp047957z

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title = "Selective catalytic reduction of nitric oxide by ammonia: The activation mechanism",

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 Br{\o}nsted 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.",

author = "Yuka Kobayashi and Nobuo Tajima and Haruyuki Nakano and Kimihiko Hirao",

year = "2004",

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doi = "10.1021/jp047957z",

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journal = "Journal of Physical Chemistry B",

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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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DO - 10.1021/jp047957z

M3 - Article

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JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

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ER -

Selective catalytic reduction of nitric oxide by ammonia: The activation mechanism

Abstract

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