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

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.