4.8 Article

Rapid Generation of Hierarchically Porous Metal-Organic Frameworks through Laser Photolysis

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 28, Pages 11349-11354

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202003636

Keywords

hierarchical pores; linker photolysis; metal-organic frameworks

Funding

  1. Center for Gas Separations, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0001015]
  2. Robert A. Welch Foundation through a Welch Endowed Chair [A-0030]
  3. Qatar National Research Fund [NPRP9-377-1-080]

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Hierarchically porous metal-organic frameworks (HP-MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP-MOFs with remarkable application potential in multiple fields. Recently, new methods such as linker labilization for the construction of HP-MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate photolabile linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing-cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP-MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.

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