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An In Situ One-Pot Synthetic Approach towards Multivariate Zirconium MOFs
Summary:
The authors from Texas A&M University and Guilin University of Electronic Technology developed a series of multivariate Zr-MOFs (UiO-66 derivatives) incorporating tetratopic porphyrin (TCPP) ligands, achieving high chemical stability and tunable multifunctionality for catalysis and sensing applications.
Background:
1. To incorporate multiple functionalities into chemically robust MOFs, previous researchers used mixed-ligand strategies, but these were limited to ligands of identical geometry/connectivity and often yielded phase separation or poor stability.
2. The authors proposed a one-pot, thermodynamically controlled synthesis that integrates TCPP ligands of different symmetry into UiO-66 without forming separate domains, obtaining 49 phase-pure multivariate MOFs.
Research Content:
1. Synthesis:
ZrCl₄, BDC (or derivatives), TCPP (or metallated TCPP), and benzoic acid modulator were dissolved in DMF and solvothermally treated (105–135 °C, 10–20 h) to yield porphyrin⊂UiO-66 powders.
2. Characterizations:
1) BET: UiO-66 ~1100 m² g⁻¹; NiTCPP⊂UiO-66 ~800 m² g⁻¹; micropores (7–12 Å) retained.
2) SEM: octahedral micro-crystals 200–500 nm; EDS mapping shows uniform Ni/Zr distribution.
3) PXRD confirms fcu topology; ¹H NMR gives NiTCPP:BDC ≈ 0.28:3.73; TGA > 400 °C decomposition; chemical stability tested in 6 M HCl & 10 mM NaOH (12 h) without leaching or phase change.
3. Application:
FeTCPPCl⊂UiO-66 oxidizes ABTS (H₂O₂, 25 °C) with UV–vis A₄₁₈ nm increase, reaching 0.4 AU in 20 min, outperforming PCN-222/PPF-5 controls.
4. Mechanism:
Competitive coordination of TCPP during UiO-66 nucleation creates defects that accommodate tetratopic linkers; high Zr₆ cluster connectivity prevents framework collapse; porphyrin carboxylates bridge clusters, locking TCPP inside micropores and suppressing leaching.
Outlook:
The one-pot multivariate strategy breaks the topology constraint of mixed-ligand MOFs, furnishing stable Zr-MOFs with programmable functionality for catalysis, sensing, and separation under harsh conditions.
An In Situ One-Pot Synthetic Approach towards Multivariate Zirconium MOFs
Authors: Yujia Sun, Lixian Sun, Dawei Feng, Hong-Cai Zhou
DOI: 10.1002/anie.201602274
Link: https://onlinelibrary.wiley.com/doi/10.1002/anie.201602274
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