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. 2023 Apr 17;62(17):e202218252.
doi: 10.1002/anie.202218252. Epub 2023 Mar 16.

Ionothermal Synthesis of Metal-Organic Frameworks Using Low-Melting Metal Salt Precursors

Tyler J Azbell  1 , Tristan A Pitt  1 , Melissa M Bollmeyer  1 , Christina Cong  1   2 , Kyle M Lancaster  1 , Phillip J Milner  1
Affiliations

Ionothermal Synthesis of Metal-Organic Frameworks Using Low-Melting Metal Salt Precursors

Tyler J Azbell et al. Angew Chem Int Ed Engl. .

Abstract

Metal-organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes with myriad potential applications in chemical separations, catalysis, and drug delivery. A major barrier to the application of MOFs is their poor scalability, as most frameworks are prepared under highly dilute solvothermal conditions using toxic organic solvents. Herein, we demonstrate that combining a range of linkers with low-melting metal halide (hydrate) salts leads directly to high-quality MOFs without added solvent. Frameworks prepared under these ionothermal conditions possess porosities comparable to those prepared under traditional solvothermal conditions. In addition, we report the ionothermal syntheses of two frameworks that cannot be prepared directly under solvothermal conditions. Overall, the user-friendly method reported herein should be broadly applicable to the discovery and synthesis of stable metal-organic materials.

Keywords: Conductivity; Ionothermal; Metal-Organic Framework; Porosity; Sustainability.

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Figures

Figure 1.
Figure 1.
(a) Ionothermal synthesis of M2Cl2(btdd) (M = Co, Ni). (b) Structures of M2Cl2(btdd) (M = Co, Ni). Gray, white, red, green, blue, purple, and black spheres represent carbon, hydrogen, oxygen, chlorine, nitrogen, cobalt, and nickel, respectively. (c) PXRD patterns of M2Cl2(btdd) (M = Co, Ni) synthesized under solvothermal (ST) and ionothermal (IT) conditions. The experimental PXRD patterns were baseline corrected. (d) SEM images of M2Cl2(btdd) (M = Co, Ni) prepared under ionothermal conditions.
Figure 2.
Figure 2.
(a) Ionothermal synthesis of Zn5Cl4(btdd)3. (b) Structure of Zn5Cl4(btdd)3. (c) SEM image of Zn5Cl4(btdd)3 prepared under ionothermal conditions. (d) PXRD patterns of Zn5Cl4(btdd)3 synthesized under solvothermal (ST) and ionothermal (IT) conditions. The experimental PXRD patterns were baseline corrected.
Figure 3.
Figure 3.
(a) Ionothermal synthesis of Ni3(btp)2. (b) Structure of Ni3(btp)2. Gray, white, blue, and black spheres correspond to carbon, hydrogen, nitrogen, and nickel, respectively. (c) SEM image of Ni3(btp)2 prepared under ionothermal conditions. (d) PXRD patterns of Ni3(btp)2 synthesized under solvothermal (ST) and ionothermal (IT) conditions. The experimental PXRD patterns were baseline corrected.
Figure 4.
Figure 4.
(a) Ionothermal synthesis of Ni(bdp). (b) Structure of Ni(bdp). Gray, white, blue, and black spheres correspond to carbon, hydrogen, nitrogen, and nickel, respectively. (c) SEM image of Ni(bdp) prepared under ionothermal conditions. (d) PXRD patterns of Ni(bdp) synthesized under solvothermal (ST) and ionothermal (IT) conditions. The experimental PXRD patterns were baseline corrected.
Figure 5.
Figure 5.
(a) Ionothermal synthesis of Co2(dobdc) and Ni2(m-dobdc). (b) Structures of Co2(dobdc) and Ni2(m-dobdc). Gray, white, red, purple, and black spheres correspond to carbon, hydrogen, oxygen, cobalt, and nickel, respectively. (c) PXRD patterns of Co2(dobdc) and Ni2(m-dobdc) synthesized under solvothermal (ST) and ionothermal (IT) conditions. The experimental PXRD patterns were baseline corrected. (d) SEM images of Co2(dobdc) and Ni2(m-dobdc) prepared under ionothermal conditions.
Figure 6.
Figure 6.
(a) Ionothermal synthesis of Fe2X2(dobdc) and Fe2X2(m-dobdc) (X = Cl, OH). (b) Structures of Fe2X2(dobdc) and Fe2X2(m-dobdc) (X = Cl, OH). Gray, white, red, orange, and green spheres correspond to carbon, hydrogen, oxygen, iron, and chlorine, respectively. (c) PXRD patterns of Fe2X2(dobdc) and Fe2X2(m-dobdc) (X = Cl, OH) synthesized under solvothermal (ST) and ionothermal (IT) conditions. The experimental PXRD patterns were baseline corrected. (d) SEM images of Fe2X2(dobdc) and Fe2X2(m-dobdc) (X = Cl, OH) prepared under ionothermal conditions.
Figure 7.
Figure 7.
Mössbauer profiles of the Fe(III) MOFs Fe2X2(m-dobdc) and Fe2X2(dobdc) (X = Cl, OH). The Mössbauer profile of the Fe(II) MOF Fe2(dobdc) is included for comparison.
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