Customizable heterogeneous catalysts: From 3D printed designs to mesoporous materials

This dissertation describes the author’s efforts in developing new heterogeneous catalytic systems. The work is focused on controlling the structure of heterogeneous catalysts at the macroscale (using 3D printing methods) and at the nanoscale (using Mesoporous Silica Nanoparticles). The first chapter consists of a general introduction to 3D printing and its applications in chemistry laboratories and heterogeneous catalysis. The second chapter presents the 3D printing process of materials with active functional groups using a commercial stereolithographic 3D printer. Controlling the composition of the 3D printable resin, different organic/inorganic catalytic groups were incorporated into the 3D architectures. The active sites, part of the 3D structure, did not require any post-printing treatment for activation and they were used directly after printing. The incorporated functionalities were accessible and catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions. As a proof of concept, custom-made catalysts were printed and used for studying the kinetics of a heterogeneously catalyzed reaction in a conventional solution spectrophotometer. In addition, we used 3D printed millifluidic devices containing catalytic sites on their walls to promote azide-alkyne cycloadditions. We showed that 3D printing allows controlling the morphology of the active materials, resulting in enhancing catalytic activity upon increasing complexity of the 3D architectures. The third chapter presents a study of the effect of macroscopic catalyst morphology on the performance of batch reactions. A series of catalytically active magnetic stir-bar compartments (SBC) with different architectures were 3D printed and used to promote the hydrolysis of sucrose. Fixing the surface area and the number of accessible catalytic sites of the 3D printed SBC allowed exploring the effect of subtle changes in morphology on the