Solid Phase Adsorption of Crystal Violet Lactone on Silica Nanoparticles to Probe Mechanochemical Surface Modification

Abstract

The solid phase adsorption of crystal violet lactone (CVL) on five types of Stober silica nanopowders with BET specific surface areas in the range of 50-800 m2/g under dry milling conditions was described for the first time. The hydrogen bonding between surface silanol and the carboxylate of the ring-opened triphenylmethane dye (CVL+) led to the formation of monolayers of CVL+ in a flat-laid configuration. The lambda max of CVL+ in diffusive reflection visible spectra was influenced by the particle size of silica powders, suggesting that the microenvironmental polarity of adsorbed CVL+ is considerably reduced along with the decrease of the particle size. The solid phase adsorption of CVL obeyed Langmuir adsorption isotherms to give a saturated amount of CVL+ for every silica nanoparticle. The surface concentration of CVL+ on nanoparticles at the saturation was estimated to be 0.31 mg/m2 on average, disclosing that about 52% of the surface can be covered by CVL+ under the assumption that the BET-specific surface areas are equivalent to the real surfaces active for the CVL adsorption. The generation of the blue color of CVL provided a convenient means to estimate qualitative and quantitative analysis of the surface coverage with surface-active reagents, which conceal surface silanols. Subsequently, silica nanoparticles were milled with a surface modifier, followed by milling with CVL to observe the intensity of the blue color in order to disclose that the surface coverage with oligo- and polyethylene glycols as well as with nonionic surfactants by dry milling was specifically determined by the number of repeating oxyethylene units. Although the surface-active reagents were easily desorbed in water, the desorption was notably suppressed by milling with CVL, suggesting that the surface-modified particles with the surface-active reagents are covered with ultrathin films of CVL.