Adsorption and Activation of Methane on the (110) Surface of Rutile-type Metal Dioxides

研究成果: ジャーナルへの寄稿記事

4 引用 (Scopus)

抄録

Methane strongly adsorbs on the (110) surface of IrO 2 , a rutile-type metal dioxide. Its C-H bond is facilely dissociated even below room temperature, as predicted in a few theoretical works and actually observed in a recent experimental study. Thence, three questions are posed and answered in this paper: First, why does methane adsorb on the IrO 2 surface so strongly? Second, why is the surface so active for the C-H bond breaking reaction? Third, is there any other rutile-type metal dioxide that is more active than IrO 2 ? A second-order perturbation theoretic approach is successfully applied to the analysis of the electronic structure of methane, which is found to be significantly distorted on the surface. Regarding the first point, it is clarified that an attractive orbital interaction between the surface Ir 5d z2 orbital and the distorted methane's highest occupied molecular orbital leads to the strong adsorption. As for the second point, the bond strength between the surface metal atom and the CH 3 fragment generated after the C-H bond scission of methane is correlated well with the activation barrier. A substantial bonding interaction between CH 3 's nonbonding orbital and the dz 2 orbital hints at the strong Ir-CH 3 bond and hence high catalytic activity ensues. Last but not least, β-PtO 2 , a distorted rutile-type dioxide, is identified as a more active catalyst than IrO 2 . Here again, a perturbation theoretic line of explanation is found to be of tremendous help. This paper is at the intersection of theoretical, catalytic, inorganic, and physical chemistry. Also, it should serve as a model for the design and study of metal-oxide catalysts for the C-H bond activation of methane.

元の言語英語
ページ(範囲)15359-15381
ページ数23
ジャーナルJournal of Physical Chemistry C
122
発行部数27
DOI
出版物ステータス出版済み - 7 12 2018

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Methane
dioxides
rutile
methane
Metals
Chemical activation
activation
Adsorption
adsorption
metals
orbitals
methylidyne
inorganic chemistry
chemistry
Physical chemistry
catalysts
perturbation
Catalysts
physical chemistry
Molecular orbitals

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

これを引用

Adsorption and Activation of Methane on the (110) Surface of Rutile-type Metal Dioxides. / Tsuji, Yuta; Yoshizawa, Kazunari.

:: Journal of Physical Chemistry C, 巻 122, 番号 27, 12.07.2018, p. 15359-15381.

研究成果: ジャーナルへの寄稿記事

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abstract = "Methane strongly adsorbs on the (110) surface of IrO 2 , a rutile-type metal dioxide. Its C-H bond is facilely dissociated even below room temperature, as predicted in a few theoretical works and actually observed in a recent experimental study. Thence, three questions are posed and answered in this paper: First, why does methane adsorb on the IrO 2 surface so strongly? Second, why is the surface so active for the C-H bond breaking reaction? Third, is there any other rutile-type metal dioxide that is more active than IrO 2 ? A second-order perturbation theoretic approach is successfully applied to the analysis of the electronic structure of methane, which is found to be significantly distorted on the surface. Regarding the first point, it is clarified that an attractive orbital interaction between the surface Ir 5d z2 orbital and the distorted methane's highest occupied molecular orbital leads to the strong adsorption. As for the second point, the bond strength between the surface metal atom and the CH 3 fragment generated after the C-H bond scission of methane is correlated well with the activation barrier. A substantial bonding interaction between CH 3 's nonbonding orbital and the dz 2 orbital hints at the strong Ir-CH 3 bond and hence high catalytic activity ensues. Last but not least, β-PtO 2 , a distorted rutile-type dioxide, is identified as a more active catalyst than IrO 2 . Here again, a perturbation theoretic line of explanation is found to be of tremendous help. This paper is at the intersection of theoretical, catalytic, inorganic, and physical chemistry. Also, it should serve as a model for the design and study of metal-oxide catalysts for the C-H bond activation of methane.",
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