Efficient Selective Oxidation of Aromatic Alkanes by Double Cobalt Active Sites over Oxygen Vacancy‐rich Mesoporous Co3O4

Abstract The development of efficient catalyst for selective oxidation of hydrocarbon to functional compounds remains a challenge. Herein, mesoporous Co 3 O 4 (mCo 3 O 4 ‐350) showed excellent catalytic activity for selective oxidation of aromatic‐alkanes, especially for oxidation of ethylbenzene with a conversion of 42 % and selectivity of 90 % for acetophenone at 120 °C. Notably, mCo 3 O 4 presented a unique catalytic path of direct oxidation of aromatic‐alkanes to aromatic ketones rather than the conventional stepwise oxidation to alcohols and then to ketones. Density functional theory calculations revealed that oxygen vacancies in mCo 3 O 4 activate around Co atoms, causing electronic state change from Co 3+ ( O h) →Co 2+ ( O h) . Co 2+ ( O h) has great attraction to ethylbenzene, and weak interaction with O 2 , which provide insufficient O 2 for gradual oxidation of phenylethanol to acetophenone. Combined with high energy barrier for forming phenylethanol, the direct oxidation path from ethylbenzene to acetophenone is kinetically favorable on mCo 3 O 4 , sharply contrasted to non‐selective oxidation of ethylbenzene on commercial Co 3 O 4 .