Ultralow-loading single-atom cobalt on graphitic carbon nitrogen with robust Co-N pairs for aerobic cyclohexane oxidation

Selectively aerobic oxidation of cyclohexane using the homogeneous catalysts is an industrially important process, suffering from the difficult catalyst separation, low conversion and selectivity. Herein, a series of single-atom Co catalysts, possessing the ultralow Co loading of below 1.0 wt.%., supported on mesoporous graphitic carbon nitrogen (Co/g-C3N4-w) were prepared by a simple adsorption method and applied into the cyclohexane oxidation. Characterization results demonstrate that the confinement effect of the voids in g-C3N4 facilitates the formation of the single-atom Co, which is stabilized by bonding with the pyridinic nitrogen of g-C3N4 and accompanied by the electron transfer from Co to g-C3N4. The catalytic performance presents an increasing trend with the increment of the Co loading, and the superior value with the conversion of 23.8% and selectivity of 95.6% is obtained over Co/g-C3N4-0.9. Kinetic study, density functional theory (DFT) calculations, and characterizations reveal that the decreased activation energy of cyclohexane oxidation over Co/g-C3N4-w can be attributed to the favorable dissociation activation of O-2 molecules and decomposition of cyclohexylhydroperoxide (CHHP) intermediate on the coordination unsaturated single-atom Co as well as the enhanced adsorption of cyclohexane on the electron-rich g-C3N4 surface, boosting the cyclohexane oxidation following the surface catalytic mechanism. Distinctively, robust Co-N structures and hydrophobic nature of g-C3N4 contribute to the high stability of Co/g-C3N4-0.9 for cyclohexane oxidation.

Automated summary

In this study, a series of ultralow loading single-atom Co catalysts supported on mesoporous graphitic carbon nitrogen (Co/g-C3N4-w) were prepared and applied in the aerobic oxidation of cyclohexane. The catalytic performance was found to improve with the increase of Co loading, with Co/g-C3N4-0.9 exhibiting the highest conversion (23.8%) and selectivity (95.6%). The enhanced catalytic activity can be attributed to the favorable dissociation activation of O2 molecules and decomposition of cyclohexylhydroperoxide (CHHP) intermediate on the single-atom Co, as well as the enhanced adsorption of cyclohexane on the g-C3N4 surface.