Abstract
Recent interest in Cu-exchanged zeolite catalysts for methane hydroxylation has been broadened to small-pore Cu-zeolites such as Cu-SSZ-13 (Cu-CHA), Cu-SSZ-16 (Cu-AFX), and Cu-SSZ-39 (Cu-AEI), which were reported to produce more methanol per copper atom than the medium-pore Cu-ZSM-5 (Cu-MFI) and large-pore Cu-mordenite (Cu-MOR) zeolites do. To elucidate the nature of such fascinating catalytic activities, theoretical investigations based on density functional theory (DFT) were performed on the direct conversion of methane to methanol by [Cu2(μ-O)]2+-exchanged AEI, CHA, AFX, and MFI zeolites in periodic systems. DFT computational results show that the important activation energies for C-H bond dissociation by [Cu2(μ-O)]2+-AEI, -CHA, and -AFX zeolites are lower than those for [Cu2(μ-O)]2+-MFI zeolite. Moreover, the rate-determining methanol desorption and N2O decomposition by [2Cu]2+-AEI zeolite are also found to require low barriers, which renders [Cu2(μ-O)]2+-AEI zeolite highly active for the direct conversion of methane to methanol. Molecular orbital analyses show that AEI, CHA, AFX, and MFI zeolites exert similar confinement effects that stabilize the transition state for C-H bond cleavage. In addition, a decrease in the Cu-O-Cu angle, due to a change in the zeolite ring structure, lowers the acceptor orbital energy of [Cu2(μ-O)]2+-zeolite, which further stabilizes the transition state. We conclude that these two factors play important roles in the activation of methane.
| Original language | English |
|---|---|
| Pages (from-to) | 3741-3751 |
| Number of pages | 11 |
| Journal | ACS Catalysis |
| Volume | 7 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Jun 2 2017 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
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Roles of Zeolite Confinement and Cu-O-Cu Angle on the Direct Conversion of Methane to Methanol by [Cu2(μ-O)]2+-Exchanged AEI, CHA, AFX, and MFI Zeolites. / Mahyuddin, M. Haris; Staykov, Aleksandar; Shiota, Yoshihito; Miyanishi, Mayuko; Yoshizawa, Kazunari.
In: ACS Catalysis, Vol. 7, No. 6, 02.06.2017, p. 3741-3751.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Roles of Zeolite Confinement and Cu-O-Cu Angle on the Direct Conversion of Methane to Methanol by [Cu2(μ-O)]2+-Exchanged AEI, CHA, AFX, and MFI Zeolites
AU - Mahyuddin, M. Haris
AU - Staykov, Aleksandar
AU - Shiota, Yoshihito
AU - Miyanishi, Mayuko
AU - Yoshizawa, Kazunari
PY - 2017/6/2
Y1 - 2017/6/2
N2 - Recent interest in Cu-exchanged zeolite catalysts for methane hydroxylation has been broadened to small-pore Cu-zeolites such as Cu-SSZ-13 (Cu-CHA), Cu-SSZ-16 (Cu-AFX), and Cu-SSZ-39 (Cu-AEI), which were reported to produce more methanol per copper atom than the medium-pore Cu-ZSM-5 (Cu-MFI) and large-pore Cu-mordenite (Cu-MOR) zeolites do. To elucidate the nature of such fascinating catalytic activities, theoretical investigations based on density functional theory (DFT) were performed on the direct conversion of methane to methanol by [Cu2(μ-O)]2+-exchanged AEI, CHA, AFX, and MFI zeolites in periodic systems. DFT computational results show that the important activation energies for C-H bond dissociation by [Cu2(μ-O)]2+-AEI, -CHA, and -AFX zeolites are lower than those for [Cu2(μ-O)]2+-MFI zeolite. Moreover, the rate-determining methanol desorption and N2O decomposition by [2Cu]2+-AEI zeolite are also found to require low barriers, which renders [Cu2(μ-O)]2+-AEI zeolite highly active for the direct conversion of methane to methanol. Molecular orbital analyses show that AEI, CHA, AFX, and MFI zeolites exert similar confinement effects that stabilize the transition state for C-H bond cleavage. In addition, a decrease in the Cu-O-Cu angle, due to a change in the zeolite ring structure, lowers the acceptor orbital energy of [Cu2(μ-O)]2+-zeolite, which further stabilizes the transition state. We conclude that these two factors play important roles in the activation of methane.
AB - Recent interest in Cu-exchanged zeolite catalysts for methane hydroxylation has been broadened to small-pore Cu-zeolites such as Cu-SSZ-13 (Cu-CHA), Cu-SSZ-16 (Cu-AFX), and Cu-SSZ-39 (Cu-AEI), which were reported to produce more methanol per copper atom than the medium-pore Cu-ZSM-5 (Cu-MFI) and large-pore Cu-mordenite (Cu-MOR) zeolites do. To elucidate the nature of such fascinating catalytic activities, theoretical investigations based on density functional theory (DFT) were performed on the direct conversion of methane to methanol by [Cu2(μ-O)]2+-exchanged AEI, CHA, AFX, and MFI zeolites in periodic systems. DFT computational results show that the important activation energies for C-H bond dissociation by [Cu2(μ-O)]2+-AEI, -CHA, and -AFX zeolites are lower than those for [Cu2(μ-O)]2+-MFI zeolite. Moreover, the rate-determining methanol desorption and N2O decomposition by [2Cu]2+-AEI zeolite are also found to require low barriers, which renders [Cu2(μ-O)]2+-AEI zeolite highly active for the direct conversion of methane to methanol. Molecular orbital analyses show that AEI, CHA, AFX, and MFI zeolites exert similar confinement effects that stabilize the transition state for C-H bond cleavage. In addition, a decrease in the Cu-O-Cu angle, due to a change in the zeolite ring structure, lowers the acceptor orbital energy of [Cu2(μ-O)]2+-zeolite, which further stabilizes the transition state. We conclude that these two factors play important roles in the activation of methane.
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U2 - 10.1021/acscatal.7b00588
DO - 10.1021/acscatal.7b00588
M3 - Article
AN - SCOPUS:85020911972
VL - 7
SP - 3741
EP - 3751
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 6
ER -