Enhanced Light Alkane Oxidation under Impurity-Containing Conditions by Low-Coordinated Co-O Structures Boosting C-H Bond Activation

Anthropogenic light alkanes pose significant environmental and health hazards; however, achieving their efficient catalytic oxidation, particularly under industrial conditions with impurities, remains a huge challenge. Tuning the coordinated structure of metal atoms is a promising strategy for improving their low-temperature efficiency for stable C-H bond activation. Herein, we propose a one-step method for precisely modulating the coordination structures of Co atoms in a Co₃O₄ catalyst by controlling the diverse nucleation rates of Co(OH)_x species. The Co₃O₄-L catalyst with the lowest Co-O bonding exhibits exceptional catalytic performance, achieving complete oxidation of 1000 ppm propane and methane at just 179 and 290 °C, respectively. This performance is far superior to that of known catalysts, which typically require over 250 and 350 °C for 90% conversion of propane and methane, respectively. Additionally, Co₃O₄-L demonstrates excellent activity and stability in the presence of multiple organic components, as well as SO₂ and H₂O. The promoted electron-pair interactions between σ/σ* C-H orbitals and d orbitals of low-coordinated Co²⁺ species by sufficient low saturation sites strengthens the adsorption and activation of light alkanes and facilitates the cleavage of the C-H bond, ultimately reducing the reaction energy barrier. The high stability and antitoxicity are due to the abundant surface dangling bond-induced structural stability and rapid oxygen replenishment, which is facilitated by high electron transport capacity. This study establishes a solid foundation for further exploration of effective catalytic platforms for light alkanes under impurity-containing conditions.