Finch Alicia K, Gillhuber Sebastian, Frisch Hendrik, Roesky Peter W, Barner-Kowollik Christopher
School of Chemistry and Physics, Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD, 4000, Australia.
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany.
Adv Mater. 2025 Aug;37(34):e2506663. doi: 10.1002/adma.202506663. Epub 2025 Jun 6.
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.
光诱导增材制造（3D打印）彻底改变了制造业，将其集成到催化剂制造中具有关键潜力，能够轻松获得优化的催化剂几何形状和设计。在此，首次通过一种双功能光致抗蚀剂引入了微米级和宏观尺寸的具有光催化活性的3D打印物体，该光致抗蚀剂使用含钌（II）配合物的单体作为3D打印过程的光引发剂以及打印结构内的活性光催化剂。该方法利用了光诱导3D打印技术在单光子和双光子打印过程中提供的空间和时间控制，使用基于季戊四醇三丙烯酸酯（PETA）的树脂将光催化剂精确地定位在复杂的几何形状中。通过飞行时间二次离子质谱（ToF-SIMS）证明了钌（II）配合物成功地掺入到3D打印物体的所需部分中。单光子和双光子制造的结构在活化芳基溴的C─H芳基化反应中表现出光催化活性。一种微观设计体现了定制的具有催化活性的3D物体的潜力。这种设计仅使用了由相同树脂制造的宏观结构体积的1%，却实现了75%的光催化性能。
