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Issue 26, 2020
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Barrierless methane-to-methanol conversion: the unique mechanism of AlO+

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Abstract

The kinetics of AlO+ + CH4 are studied from 300–500 K using a selected-ion flow tube. At all temperatures the reaction proceeds near the Langevin–Gioumousis–Stevenson collision rate with two product channels: hydrogen atom abstraction (AlOH+ + CH3, 86 ± 5%) and methanol formation (Al+ + CH3OH, 14 ± 5%). Density functional calculations show the key Al–CH3OH+ intermediate is formed barrierlessly via a mechanism unique to aluminum, avoiding the rate-limiting step common to other MO+. The reaction of Al2O3+ + CH4 follows a similar mechanism to that for AlO+ through to the key intermediate; however, the conversion to methanol occurs only for AlO+ due to favorable energetics attributed to a weaker Al+–CH3OH bond. Importantly, that bond strength may be tuned independent of competing product channels by altering the acidity of the Al with electron-withdrawing or donating groups, indicating a key design criteria to develop a real world Al-atom catalyst.

Graphical abstract: Barrierless methane-to-methanol conversion: the unique mechanism of AlO+

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Article information


Submitted
29 Apr 2020
Accepted
11 Jun 2020
First published
24 Jun 2020

Phys. Chem. Chem. Phys., 2020,22, 14544-14550
Article type
Paper

Barrierless methane-to-methanol conversion: the unique mechanism of AlO+

B. C. Sweeny, D. C. McDonald, S. G. Ard, A. A. Viggiano and N. S. Shuman, Phys. Chem. Chem. Phys., 2020, 22, 14544
DOI: 10.1039/D0CP02316G

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