Engineering the surface of hybrid organic–inorganic films with orthogonal grafting of oxide nanoparticles

Superparamagnetic iron oxide nanoparticles of magnetite have been grafted on the surface of a hybrid organic–inorganic film prepared using an organically modified alkoxide, 3-glycidoxypropyltrimethoxysilane, as precursor. A solventless synthesis of the hybrid films at high pH has been employed and the surface chemistry of the deposited films has been processed by controlling the aging time of the sol. The films have been characterized by FTIR, Raman and UV spectroscopy and grazing incidence X-ray diffraction. Films prepared with fresh sols have shown a mixed presence of epoxides and hydroxyls on the surface, which enabled the successful grafting of the iron oxide nanoparticles. Films from aged sols, which contain only hydroxyls, have failed to bind the iron particles but have instead shown the capability of grafting ceria nanoparticles. This method has, therefore, allowed a direct grafting of nanoparticles on the hybrid surface without any post-synthetic functionalization step. Moreover, the phase transition induced in iron oxide nanoparticles by means of a laser beam has been exploited to pattern the film surface creating different domains of magnetite and hematite.