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» MOFの溶媒熱合成

MOFの溶媒熱合成

2000
無機化学における有機金属骨格のソルボサーマル合成用テフロンライニングオートクレーブ。.

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Solvothermal synthesis is the most common 方法 for producing high-quality, crystalline Metal-Organic Frameworks. The process involves heating a solution of the metal salt and organic linker in a sealed vessel, such as a Teflon-lined autoclave. The elevated temperature and プレッシャー facilitate the dissolution of precursors and promote the crystallization of the thermodynamically stable MOF product over several hours or days.

Solvothermal synthesis is a subset of hydrothermal synthesis where the solvent is not necessarily water. For MOFs, high-boiling point organic solvents like N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), or N-methyl-2-pyrrolidone (NMP) are frequently used. The reaction is carried out in a sealed container, which allows the temperature to be raised above the solvent’s boiling point at atmospheric pressure, creating autogenous pressure inside the vessel.

The key advantages of this method are manifold. The increased temperature enhances the solubility of the reactants, ensuring a homogeneous reaction medium. It also provides the necessary activation energy for the formation of the metal-ligand coordination bonds and the subsequent nucleation and growth of the crystalline framework. The slow cooling process that often follows the heating period allows for the growth of large, well-defined single crystals, which are essential for determining the MOF’s structure via X-ray crystallography. Furthermore, the solvent molecules can act as templates or structure-directing agents, influencing which crystalline phase is formed. Modulators, such as monocarboxylic acids (e.g., acetic acid or formic acid), are often added to the reaction mixture to compete with the linker for coordination sites on the metal cluster, thereby slowing down the crystallization rate and improving the quality and size of the resulting crystals.

UNESCO Nomenclature: 2203
無機化学

タイプ

化学プロセス

混乱

実質的な

使用法

広く普及している

前駆物質

  • development of the autoclave for high-pressure reactions
  • hydrothermal synthesis of zeolites and other inorganic materials
  • principles of solution-based crystal growth
  • understanding of chemical kinetics and thermodynamics

アプリケーション

  • large-scale production of commercial mofs like basolite c300 (hkust-1)
  • synthesis of novel MOF structures for research
  • growth of large single crystals for X-ray diffraction analysis
  • preparation of phase-pure MOF powders
  • synthesis of MOFs that are not accessible at ambient conditions

特許:

NA

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Related to: solvothermal synthesis, hydrothermal synthesis, crystallization, autoclave, single crystal, modulator, dmf, coordination chemistry, materials synthesis, nucleation.

歴史的背景

MOFの溶媒熱合成

1986
1991
1995
2000
2004
1986
1990
1994
1997
2002
2015-09-14

(日付が不明または関連性がない場合、例えば「流体力学」などでは、その注目すべき出現時期の概算値が提示されます。)

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