Protecting Mg-sites from hydration by embedding magnesium-aluminium layered double hydroxide in halloysite and using as pickering catalysts in Baeyer-Villiger oxidation

A facile strategy was developed via thermal treatment to get hierarchically structured magnesium-aluminium layered double hydroxide (MgAl-LDH) selectively loaded on the inner and external surfaces of halloysite nanotubes, respectively. The loaded MgAl-LDH was found to have active centers for Baeyer-Villiger (B V) oxidation that was protected from hydration by embedding in halloysite lumens. The B V oxidation of cyclohexanone was observed to have better performance by using the halloysite impregnated MgAl-LDH (MgAl-LDH@Hal) as catalysts than that of external surface modified MgAl-LDH (MgAl-LDH@Hal600). A conversion 57.0% of cyclohexanone was achieved, and the yield of ε-caprolactone was 22.0% when the MgAl-LDH@Hal was used as catalysts. Density Functional Theory (DFT) calculations as well as high-resolution of X-ray photoelectron spectrum (XPS) measurements revealed the charge depletion occurred in the Mg-sites of sample MgAl-LDH@Hal in comparison with MgAl-LDH@Hal600, which benefited the activation of H ₂O ₂ oxidants, and thus assisting the B V reaction. The prepared composites were able to work as phase-transfer catalysts as Pickering emulsions in oxidation of cyclohexanone.