Combined theoretical and experimental study on alcoholysis of amides on CeO2 surface

A catalytic interplay between Lewis acid and base sites

Takashi Kamachi, S. M.A.Hakim Siddiki, Yoshitsugu Morita, Md Nurnobi Rashed, Kenichi Kon, Takashi Toyao, Ken ichi Shimizu, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

1 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)256-262
ページ数7
ジャーナルCatalysis Today
303
DOI
出版物ステータス出版済み - 4 1 2018

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Lewis Bases
Lewis Acids
Amides
Catalysts
Acids
Oxides
Density functional theory
Metals
Oxygen
Infrared spectroscopy

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

これを引用

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.

:: Catalysis Today, 巻 303, 01.04.2018, p. 256-262.

研究成果: ジャーナルへの寄稿記事

Kamachi, Takashi ; Siddiki, S. M.A.Hakim ; Morita, Yoshitsugu ; Rashed, Md Nurnobi ; Kon, Kenichi ; Toyao, Takashi ; Shimizu, Ken ichi ; Yoshizawa, Kazunari. / Combined theoretical and experimental study on alcoholysis of amides on CeO2 surface : A catalytic interplay between Lewis acid and base sites. :: Catalysis Today. 2018 ; 巻 303. pp. 256-262.
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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.",
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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

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