Applicability of core-shell SiO2 microspheres with a high TiO2 loading as stationary phase for HPLC

Due to its high chemical stability, sufficient rigidity and zwitterionic ion exchange properties, TiO2 can be considered as an alternative stationary phase material to SiO2 for high performance liquid chromatography. TiO2 stationary phase is usually prepared by coating TiO2 onto SiO2 support by sol-gel method. However, in the traditional coating method, in order to overcome the rapid hydrolysis rate of tetrabutyl orthotitanate, only a very low concentration of tetrabutyl orthotitanate can be used, resulting in a low loading of TiO2 on the support. TiO2 core-shell spheres with a good monodispersity were prepared using 0.25 mol L−1 tetrabutyl orthotitanate. The specific surface area, pore volume, pore diameter and TiO2 loading of the TiO2 core-shell spheres were 66 m2 g−1, 0.15 cm3 g−1, 9.8 nm and 57%, respectively. The core-shell spheres were derivatized with n-octadecyltrichlorosilane and then packed into a stainless steel column to test the separation performance for neutral, basic and acidic samples in liquid chromatography. A baseline separation of polyaromatic hydrocarbons was achieved, showing a column efficiency for fluorene of 118075 plates m−1. The prepared stationary phase was also used to separate acidic and basic mixtures, and column efficiencies of 54500 and 25836 plates m−1 were obtained for N,N-dinitroaniline and p-chlorophenol, respectively. The relative standard deviations of the retention times of polyaromatic hydrocarbons for run-to-run, day-to-day and column-to-column repeatability were all below 5.1%. This work demonstrated that TiO2 can be coated in the pores of the shell of SiO2 core-shell spheres with high TiO2 loading using a high concentration of tetrabutyl orthotitanate as the titania source. The experimental results show that the TiO2 coated core-shell spheres can be a good alternative stationary phase for liquid chromatography.