Defect-mediated hydroxylation of multi-walled carbon nanotubes as metal-free catalysts to enhance catalytic performance for oxidative dehydrogenation of ethylbenzene using CO2

The fabrication and hydroxylation of surface defects on multi-walled carbon nanotubes (MWCNTs) are performed through a single or combined method involving hydrothermal, ultrasonic and ball-milling treatments. These treatments cannot change the tubular morphology of the graphite structure in MWCNTs but they can alter the surface defect structure on MWCNTs. Surface defects on MWCNTs can promote the hydroxylation of the MWCNTs to produce hydroxyl groups. However, these defects are difficult to hydroxylate when occupied by other functional groups, such as carboxyl groups, even though the hydroxylation processes are the same. After hydroxylation, the MWCNTs with surface defects can be employed as metal-free catalysts for the oxidative dehydrogenation of ethylbenzene using CO2 as soft oxidants. The inherent disorder or artificial skeleton defects on MWCNTs cannot directly act as catalytic active sites, but they can be hydroxylated to enhance the catalytic activity of the MWCNTs. For the same type of MWCNT defects formed after hydroxylation, the catalytic activity is closely related to the defect density. If the disorder or skeleton defects cause a higher defect density on the hydroxylated MWCNTs, the MWCNTs will exhibit a higher catalytic activity. Due to the different structures and positions of the MWCNT defect carbons, the artificial skeleton defects on MWCNTs more efficiently promote the hydroxylation of MWCNTs compared to the disorder defects, decreasing their defect density and enhancing their catalytic activity. Therefore, MWCNTs-BOH36 with skeleton defects has a catalytic activity that is twice as high as that of MWCNTs-CS-120 with disorder defects.