4.7 Article

Synthesis of Mixed-Metal MIL-68 under Mild Conditions by Controlling Nucleation Using a Microfluidic System

Journal

CRYSTAL GROWTH & DESIGN
Volume 22, Issue 7, Pages 4139-4145

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.2c00140

Keywords

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Funding

  1. Japan Science and Technology Agency PRESTO [JPMJPR17NA]
  2. Japan Society for the Promotion of Science KAKENHI [20H02577, 20H04646, 20H04680, 19K22222, 21K20544]

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By controlling nucleation using microfluidic synthesis and metal mixing, MIL-68 containing trivalent metal ions was rapidly synthesized without HF addition, resulting in a product with high crystallinity.
Metal-organic frameworks that contain trivalent metal ions as nodes (M3+-MOFs) exhibit potential for various applications due to their exceptional thermal and chemical stability; however, M3+-MOF synthesis requires extreme reaction conditions such as high temperatures, long reaction times, and hydrogen fluoride (HF) addition. Here, we rapidly synthesized MIL-68 containing trivalent metal ions without any HF addition by controlling nucleation using microfluidic synthesis and metal mixing. Al3+ addition during the initial reaction between Fe3+ and the ligand yielded 1D chain-based secondary building units, consequently forming MIL-68. Compared to the products obtained using bulk and microwave-assisted syntheses, the product obtained via microfluidic synthesis exhibited high crystallinity. Thus, the combination of microfluidic systems and metal mixing is a novel approach in synthesizing industrially applicable M3+-MOFs.

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