Abstract
Alcoholysis of amides on the CeO2 surface is investigated from density functional theory (DFT) computations, in situ FT-IR spectroscopy, and catalytic studies. The thermodynamically stable amide bonds are effectively activated by the CeO2 catalyst under mild conditions in contrast to other metal oxide catalysts. DFT calculations demonstrated that acetamide adsorbed on the CeO2 surface is attacked by lattice oxygen to give a tetrahedral intermediate in the rate-determining step of the most favorable pathway. This is consistent with the experimental finding that the activity of metal oxide catalysts increases with an increase of the base strength of the catalyst. The strong base sites of CeO2 are the most important factor for the high reactivity. Interestingly, the nucleophilic attack of lattice oxygen is further assisted by the moderately strong Ce4+ Lewis acid sites. Our computational results show that the high reactivity is ascribed to a catalytic interplay between the Lewis base and acid pair sites on the CeO2 surface.
| Original language | English |
|---|---|
| Pages (from-to) | 256-262 |
| Number of pages | 7 |
| Journal | Catalysis Today |
| Volume | 303 |
| DOIs | |
| Publication status | Published - Apr 1 2018 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
Cite this
Combined theoretical and experimental study on alcoholysis of amides on CeO2 surface : A catalytic interplay between Lewis acid and base sites. / Kamachi, Takashi; Siddiki, S. M.A.Hakim; Morita, Yoshitsugu; Rashed, Md Nurnobi; Kon, Kenichi; Toyao, Takashi; Shimizu, Ken ichi; Yoshizawa, Kazunari.
In: Catalysis Today, Vol. 303, 01.04.2018, p. 256-262.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Combined theoretical and experimental study on alcoholysis of amides on CeO2 surface
T2 - A catalytic interplay between Lewis acid and base sites
AU - Kamachi, Takashi
AU - Siddiki, S. M.A.Hakim
AU - Morita, Yoshitsugu
AU - Rashed, Md Nurnobi
AU - Kon, Kenichi
AU - Toyao, Takashi
AU - Shimizu, Ken ichi
AU - Yoshizawa, Kazunari
PY - 2018/4/1
Y1 - 2018/4/1
N2 - Alcoholysis of amides on the CeO2 surface is investigated from density functional theory (DFT) computations, in situ FT-IR spectroscopy, and catalytic studies. The thermodynamically stable amide bonds are effectively activated by the CeO2 catalyst under mild conditions in contrast to other metal oxide catalysts. DFT calculations demonstrated that acetamide adsorbed on the CeO2 surface is attacked by lattice oxygen to give a tetrahedral intermediate in the rate-determining step of the most favorable pathway. This is consistent with the experimental finding that the activity of metal oxide catalysts increases with an increase of the base strength of the catalyst. The strong base sites of CeO2 are the most important factor for the high reactivity. Interestingly, the nucleophilic attack of lattice oxygen is further assisted by the moderately strong Ce4+ Lewis acid sites. Our computational results show that the high reactivity is ascribed to a catalytic interplay between the Lewis base and acid pair sites on the CeO2 surface.
AB - Alcoholysis of amides on the CeO2 surface is investigated from density functional theory (DFT) computations, in situ FT-IR spectroscopy, and catalytic studies. The thermodynamically stable amide bonds are effectively activated by the CeO2 catalyst under mild conditions in contrast to other metal oxide catalysts. DFT calculations demonstrated that acetamide adsorbed on the CeO2 surface is attacked by lattice oxygen to give a tetrahedral intermediate in the rate-determining step of the most favorable pathway. This is consistent with the experimental finding that the activity of metal oxide catalysts increases with an increase of the base strength of the catalyst. The strong base sites of CeO2 are the most important factor for the high reactivity. Interestingly, the nucleophilic attack of lattice oxygen is further assisted by the moderately strong Ce4+ Lewis acid sites. Our computational results show that the high reactivity is ascribed to a catalytic interplay between the Lewis base and acid pair sites on the CeO2 surface.
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UR - http://www.scopus.com/inward/citedby.url?scp=85029213176&partnerID=8YFLogxK
U2 - 10.1016/j.cattod.2017.09.006
DO - 10.1016/j.cattod.2017.09.006
M3 - Article
VL - 303
SP - 256
EP - 262
JO - Catalysis Today
JF - Catalysis Today
SN - 0920-5861
ER -