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Interfacing and Growth Pathways of Metal−Organic Frameworks with Morphological Evolution
Summary:
The authors from Yonsei University developed hybrid metal-organic frameworks (MOFs) with controlled anisotropic growth characteristics, achieving precise construction of complex structures in the application of MOF-on-MOF heterostructure synthesis.
Background:
1. To address the challenge of controlling anisotropic growth between MOFs with mismatched lattices, previous researchers developed MOF-on-MOF heterostructures via epitaxial growth or ternary assembly, yet struggled with precise regulation of high-mismatch systems and complex structure construction.
2. The authors proposed an innovative strategy guided by lattice matching degree, realizing selective growth via favorable/unfavorable crystal planes and successfully preparing complex hybrid MOFs with H-shaped cavities.
Research Content:
1. Synthesis
The authors synthesized template MOFs (In-MIL-68B, In-MIL-53C, In-MIL-53D, In-MIL-68B−Br) via solvothermal method, then conducted sequential MOF-on-MOF growth at 100 °C in DMF, with reaction times ranging from 10 to 20 minutes.
2. Characterizations:
1) BET and pore size: Not explicitly provided; key lattice parameters include In-MIL-68B (a=21.77 Å, b=37.71 Å, c=7.23 Å), In-MIL-53C (open form: a=18.63 Å, b=18.17 Å, c=7.11 Å).
2) SEM/TEM tests: In-MIL-68B@In-MIL-53C is semitubular (width 1.13±0.10 μm, length 1.57±0.08 μm); In-MIL-68B@In-MIL-53D is flower-shaped; the final complex MOF has five segments with H-shaped cavities.
3) Other tests: PXRD confirmed phase coexistence; ¹H NMR showed final BDC²⁻:NDC²⁻ ratio of 31:69; elemental mapping verified Br incorporation.
3. Application
The research focused on structural regulation of MOF heterostructures, laying a foundation for applications in catalysis, separation, and sensing.
4. Mechanism
Lattice matching degree dominates growth pathways: In-MIL-53C (19.5% mismatch) grows via {110} plane; In-MIL-53D (41.2% mismatch) switches to {010} plane (1.0% mismatch). Growth follows "seeding-merging-growth" sequence with concurrent template etching and linker reincorporation.
Outlook:
This research clarifies the lattice matching regulation mechanism for MOF-on-MOF growth, achieves complex structure construction, and provides a theoretical/practical basis for functional hybrid MOF design.
Interfacing and Growth Pathways of Metal−Organic Frameworks with Morphological Evolution
Authors: Goeun Choi, Eunji Kim, Sojin Oh, Sujeong Lee, Moonhyun Oh
DOI: 10.1021/acsnano.5c17654
Link: https://pubs.acs.org/doi/10.1021/acsnano.5c17654
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