Catalytically Active Light Printed Microstructures

Abstract Light‐induced additive manufacturing (3D printing) has revolutionized manufacturing and its integration into the fabrication of catalysts holds key potential to enable facile access to optimized catalyst geometries and designs. Herein – for the first time – micro‐ and macro‐sized photocatalytically active 3D printed objects are introduced via a dual‐function photoresin using a ruthenium(II) complex containing monomer as both a photoinitiator for the 3D printing process and as the active photocatalyst within the printed structure. The approach leverages the spatial and temporal control afforded by light‐induced 3D printing techniques during both one‐ and two‐photon printing to precisely position the photocatalyst within intricate geometries using a pentaerythritol triacrylate (PETA) based resin. The successful incorporation of ruthenium(II) complexes is demonstrated via time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS) into desired sections of 3D‐printed objects. The one‐ and two‐photon fabricated architectures show photocatalytic activity in the C─H arylation of activated aryl bromides. The potential of tailored catalytically active 3D objects is exemplified by one of the microscale designs. This design, utilizing only 1% of the volume of a macroscale structure fabricated from the same resin, achieved 75% of the photocatalytic performance.