TY - JOUR
T1 - Why do zeolites induce an unprecedented electronic state on exchanged metal ions?
AU - Oda, Akira
AU - Ohkubo, Takahiro
AU - Yumura, Takashi
AU - Kobayashi, Hisayoshi
AU - Kuroda, Yasushige
N1 - Funding Information:
Dr. A. O. acknowledges financial support from Japan Society for the Promotion of Science (Research Fellowship for Young Scientists, DC1 & PD) and from Japan Science and Technology Agency (Precursory Research for Embryonic Science and Technology). Financial supports for the present work were also provided by Japan Society of Promotion Science (Grants-in-Aid for Scientific Research: No. 17GS0206, 21655021 and 16H04118).
Publisher Copyright:
© the Owner Societies 2017.
PY - 2017
Y1 - 2017
N2 - Understanding the exact position and the detailed role of the Al array in zeolites is essential for elucidating the origin of unique properties that can be derived from the metal-ion exchanged in zeolite samples and for designing zeolite materials with high efficiency in catalytic and adsorption processes. In this work, we investigate, for the first time, the important role of the Al array in the reactivity observed on the metal-ion exchanged in zeolites on the basis of the calculation method by utilizing the spontaneous heterolytic cleavage of H2 observed experimentally on the Zn2+-ion exchanged in MFI-type zeolites (Zn2+-MFI) as the model reaction. In the case of calculation, two main types of models for considering the Al positions in MFI-type zeolites were adopted: in the first type, the Al atoms with appropriate distances are aligned in the circumferential direction of the straight channel (abbreviated as a circumferentially arrayed Al-Al site); in the second type, the nearest neighbouring Al atoms with appropriate distances are directed toward the straight channel axis (abbreviated as a channel directionally arrayed Al-Al site). Results indicated that the Al-array direction governs the reactivity of Zn2+-MFI. The former type of array well explains the experimental fact that spontaneous and irreversible heterolysis of H2 takes place on Zn2+-MFI, even at room temperature, whereas the latter type of array is less reactive; high activation energy is required for the heterolytic cleavage of H2 (ca. >70 kJ mol-1). A detailed analysis of the geometric and electronic structures of a series of Zn2+-MFI models with various Al-array directions clarified the following facts: the circumferentially arrayed Al-Al site induces an inevitable environment around the Zn2+ site, with the simultaneous existence of both a Lewis acid point (coordinatively unsaturated and distorted Zn2+) and a Lewis base point (the lattice oxygen atom juxtaposed with exchanged Zn2+, which participates in the activation of H2: OjL). It is the circumferentially arrayed Al-Al atoms that confer acidic and basic nature on the metal ion and the lattice oxygen atom (OjL), and ultimately trigger the heterolytic dissociation of H2, even at 300 K.
AB - Understanding the exact position and the detailed role of the Al array in zeolites is essential for elucidating the origin of unique properties that can be derived from the metal-ion exchanged in zeolite samples and for designing zeolite materials with high efficiency in catalytic and adsorption processes. In this work, we investigate, for the first time, the important role of the Al array in the reactivity observed on the metal-ion exchanged in zeolites on the basis of the calculation method by utilizing the spontaneous heterolytic cleavage of H2 observed experimentally on the Zn2+-ion exchanged in MFI-type zeolites (Zn2+-MFI) as the model reaction. In the case of calculation, two main types of models for considering the Al positions in MFI-type zeolites were adopted: in the first type, the Al atoms with appropriate distances are aligned in the circumferential direction of the straight channel (abbreviated as a circumferentially arrayed Al-Al site); in the second type, the nearest neighbouring Al atoms with appropriate distances are directed toward the straight channel axis (abbreviated as a channel directionally arrayed Al-Al site). Results indicated that the Al-array direction governs the reactivity of Zn2+-MFI. The former type of array well explains the experimental fact that spontaneous and irreversible heterolysis of H2 takes place on Zn2+-MFI, even at room temperature, whereas the latter type of array is less reactive; high activation energy is required for the heterolytic cleavage of H2 (ca. >70 kJ mol-1). A detailed analysis of the geometric and electronic structures of a series of Zn2+-MFI models with various Al-array directions clarified the following facts: the circumferentially arrayed Al-Al site induces an inevitable environment around the Zn2+ site, with the simultaneous existence of both a Lewis acid point (coordinatively unsaturated and distorted Zn2+) and a Lewis base point (the lattice oxygen atom juxtaposed with exchanged Zn2+, which participates in the activation of H2: OjL). It is the circumferentially arrayed Al-Al atoms that confer acidic and basic nature on the metal ion and the lattice oxygen atom (OjL), and ultimately trigger the heterolytic dissociation of H2, even at 300 K.
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U2 - 10.1039/c7cp02669b
DO - 10.1039/c7cp02669b
M3 - Article
C2 - 28880028
AN - SCOPUS:85029865900
VL - 19
SP - 25105
EP - 25114
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 36
ER -