Silanization of 3D-Printed Silica Fibers and Monoliths

Surface functionalization of complex three-dimensional (3D) porous architectures has not been widely investigated despite their potential in different application domains. In this work, silanization was performed in silica 3D-printed porous structures, and the homogeneity of functional groups within the architecture was investigated by comparing the extent of the functionalization in the walls and core of the monolith. A silica ink was used for direct ink writing (DIW) to shape fibers and monoliths with different architectures and stacking designs. The surfaces of the fibers and monoliths were functionalized with 3-aminopropyl(triethoxysilane) (APTES) using different reaction conditions. The nature of the functional groups on the surface and the presence of RSiO_1.5 bonds were identified by solid-state ¹³C-NMR, ²⁹Si-NMR, and by ξ-potential measurements. Elemental analysis was used to quantify the concentration of bonded APTES in the core and walls of the monolith. The availability and hydrolytic stability of the introduced amine group on fibers were evaluated using the adsorption of PdCl₄^2- ions within the pH range of 2-5. The study found that geometries with interfiber distances above 250 μm are homogeneously functionalized with amine groups. As the interfiber distance of the monolith decreases, a significantly lower density of amine groups is detected in the core of the monolith. The determination of the homogeneity of 3D-printed monoliths makes this work relevant as it provides the limits of functionalization carried out in stirred batch reactors for geometrically defined structures produced from a 3D-printing process.