3D Printing of Ordered Mesoporous Silica Using Light-Induced Sol-Gel Chemistry

Mesoporous ceramic materials used in applications such as catalysis, filtration, or sensing, are usually hierarchically structured. Thereby, their structural hierarchy is often inherently related to the manufacturing methods and cannot be independently locally designed along all length scales. This study combines light-based additive manufacturing and bottom-up light-induced self-assembly (LISA) sol-gel chemistry to engineer hierarchically structured porous silica from the nanoscale to the macroscopic object geometry. A LISA-based printing solution that enables printing of ordered mesoporous silica with geometrically complex shapes by using a commercially available digital light processing (DLP)-based 3D printer is presented. This approach exploits the self-assembly process of block copolymer mesopore templates, such as Pluronic P123, and hydrolysis and condensation of silica precursors upon irradiation in the 3D printer to shape mesoporous silica objects. Furthermore, different resins are added to the LISA solution to print 3D silica-resin objects. Mesoporous silica objects up to 10 mm in size, consisting of ordered mesopores with diameters around 5 nm and having high specific surface areas of approximate to 400 m2 g-1 are successfully printed with a fast and easy post-processing. 3D printing of mesoporous silica objects achieved by using light-induced self-assembly (LISA) sol-gel chemistry in a digital light processing (DLP)-based 3D printer is presented in this study. Different resins are added to the LISA solution to print 3D silica-resin objects, which become mesoporous silica after calcination. Thus, structure formation at three length scales is controlled in one process. image