Combined experimental and computational approaches to elucidate the structures of silver clusters inside the ZSM-5 cavity

Takashi Yumura, Akira Oda, Hiroe Torigoe, Atsushi Itadani, Yasushige Kuroda, Takashi Wakasugi, Hisayoshi Kobayashi

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Abstract

A combination of experimental and computational analyses suggested the presence of Ag3 or Ag4 clusters inside a nanometer-sized cavity in Ag-ZSM-5 zeolites, which were formed from H-ZSM-5 using the conventional ion-exchange method in an aqueous silver nitrate solution. During the experimental analyses, we investigated the structural and absorption properties of Ag-ZSM-5 through UV-vis diffuse reflectance and X-ray absorption fine structure (XAFS) measurements. The results from the extended XAFS (EXAFS) analysis indicated that clusters contained in the ZSM-5 cavity have Ag-Ag separations of approximately 2.6 Å. The UV-vis measurements indicated that the clusters located in the cavity present three prominent absorption bands centered at approximately 255, 287, and 331 nm for the sample treated at 473 K. The Ag-ZSM-5 treated at 573 or 673 K presents new UV-vis bands at approximately 303 and 319 nm. The experimental results regarding the structural and absorption properties of Ag-ZSM-5 could be well-reproduced by DFT calculations when a model large enough to represent a 10-membered ring of ZSM-5 was used. DFT optimization indicated that the ZSM-5 cavity can accommodate a triangular Ag3 cluster and a butterfly Ag4 cluster whose Ag-Ag separations range from 2.7 to 2.9 Å. According to time-dependent DFT calculations, these clusters have electronic transitions from a completely symmetric 5s-based orbital to a 5s-based orbital with one node. The electronic excitations between the 5s-based orbitals are modulated by the ZSM-5 encapsulation through the resulting deformation of the cluster and interactions between the cluster and framework oxygen atoms. The electronic transitions between the 5s-based orbitals that appropriately explain the UV-vis absorption properties would become fingerprints for identifying the shapes and sizes of clusters inside a zeolite cavity. Our multidisciplinary analyses conclusively determined the origin of the absorption peaks in Ag-ZSM-5 and successfully obtained atomistic information about the states of silver clusters inside a ZSM-5 cavity. The findings of this study will provide useful information for elucidating the structures of active sites in Ag-ZSM-5 and their important role in catalytic reactions such as C-H bond activation in hydrocarbons.

Original languageEnglish
Pages (from-to)23874-23887
Number of pages14
JournalJournal of Physical Chemistry C
Volume118
Issue number41
DOIs
Publication statusPublished - Oct 16 2014

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Silver
Discrete Fourier transforms
Zeolites
silver
X ray absorption
cavities
Silver Nitrate
Hydrocarbons
Encapsulation
Absorption spectra
Nitrates
Ion exchange
orbitals
Chemical activation
Oxygen
Atoms
fine structure
electronics
silver nitrates
zeolites

ASJC Scopus subject areas

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

Cite this

Combined experimental and computational approaches to elucidate the structures of silver clusters inside the ZSM-5 cavity. / Yumura, Takashi; Oda, Akira; Torigoe, Hiroe; Itadani, Atsushi; Kuroda, Yasushige; Wakasugi, Takashi; Kobayashi, Hisayoshi.

In: Journal of Physical Chemistry C, Vol. 118, No. 41, 16.10.2014, p. 23874-23887.

Research output: Contribution to journalArticle

Yumura, Takashi ; Oda, Akira ; Torigoe, Hiroe ; Itadani, Atsushi ; Kuroda, Yasushige ; Wakasugi, Takashi ; Kobayashi, Hisayoshi. / Combined experimental and computational approaches to elucidate the structures of silver clusters inside the ZSM-5 cavity. In: Journal of Physical Chemistry C. 2014 ; Vol. 118, No. 41. pp. 23874-23887.
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AU - Kuroda, Yasushige

AU - Wakasugi, Takashi

AU - Kobayashi, Hisayoshi

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