Potential for C-H activation in CH4 utilizing a cumfi-type zeolite as a catalyst

Atsushi Itadani, Hiroyuki Sugiyama, Masashi Tanaka, Takahiro Ohkubo, Takashi Yumura, Hisayoshi Kobayashi, Yasushige Kuroda

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Abstract

We have found that a copper ion-exchanged MFI (Mobil Five)-type zeolite, having an ion exchange capacity of 112% (CuMFI-112), exhibits a specific interaction with CH4, even at room temperature. The observed properties are very remarkable compared with those found in the adsorbed amount of sodium ion-exchanged MFI and in the interaction with the sodium ion in MFI as well as in the adsorbed amounts for other types of copper ion-exchanged zeolites. The specificity of Cu+ in MFI is clearly evident. The most remarkable feature of the present system is the distinct appearance of infrared bands (IR) at 2661 and 2619 cm-1 due to adsorbed CH4 at 300 K and the change in the X-ray absorption fine structure spectra of CuMFI before and after CH4 adsorption at 300 K, indicating the existence of substantial and specific interaction in this system. In addition, calculations based on the density functional theory were carried out by utilizing a Cu-AlSi91O151H66 cluster model, which is made up of a 10-membered ring of CuMFI. As a result, the calculations gave absorption bands that can be explained reasonably by the observed novel IR bands, indicating the existence of two types of η2(H, H)-type interactions between Cu+ and CH4: (1) hydrogen interacted with a Cu cation coordinating to two oxygen atoms near an intersection of straight and sinusoidal channels, and (2) hydrogen interacted with a Cu cation located above a 5-membered ring on a wall of a straight channel. The nature of such bonding can be described by the formation of Cu-C bonds, which causes the deformation the Td structure of CH4. Such interaction results in a weakening of the C-H bond and thus a lower frequency shift of the C-H bond interacting with Cu+.

Original languageEnglish
Pages (from-to)7213-7222
Number of pages10
JournalJournal of Physical Chemistry C
Volume113
Issue number17
DOIs
Publication statusPublished - Apr 30 2009

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ASJC Scopus subject areas

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

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