Porphyrinic Zirconium Metal–Organic Frameworks (MOFs) as Heterogeneous Photocatalysts for PET‐RAFT Polymerization and Stereolithography
| Autor: | Kenward Jung, Nathaniel Corrigan, Xiaobing Shi, Kang Liang, Liwen Zhang, Cyrille Boyer, Rashin Namivandi-Zangeneh, Zhiheng Zhang, Rhiannon P. Kuchel |
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| Rok vydání: | 2021 |
| Předmět: |
Green chemistry
Materials science Dispersity chemistry.chemical_element 3D printing 010402 general chemistry 01 natural sciences Catalysis law.invention chemistry.chemical_compound law Reversible addition−fragmentation chain-transfer polymerization Stereolithography chemistry.chemical_classification Zirconium 010405 organic chemistry business.industry fungi Chain transfer General Chemistry Polymer General Medicine 0104 chemical sciences Monomer Photopolymer Polymerization chemistry Chemical engineering Metal-organic framework business |
| Zdroj: | Angewandte Chemie. 133:5549-5556 |
| ISSN: | 1521-3757 0044-8249 |
| Popis: | In this study, porphyrinic zirconium (Zr) MOFs were investigated as heterogeneous photocatalysts for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of various monomers under a broad range of wavelengths, producing polymers with high monomer conversions, narrow molecular weight distributions, low dispersity and good chain-end fidelity. Screening of various porphyrinic Zr-MOFs (Zn) containing Zn-metalled porphyrinic ligands demonstrated that MOF-525 (Zn) with the smallest size had the best photocatalytic activity in PET-RAFT polymerization, due to enhanced dispersion and light penetration. Oxygen tolerance and temporal control were also demonstrated during MOF catalysed PET-RAFT. Results suggested that the polymerization rates were significantly affected by changing the size and surface area of MOFs, and the heterogeneous MOF photocatalysts could be easily separated and recycled for up to five independent PET-RAFT polymerizations without an obvious decrease in efficiency. Finally, the MOF photocatalysts were utilized to create three-dimensional polymeric objects with high resolution via visible light mediated stereolithography in an open-air environment. |
| Databáze: | OpenAIRE |
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