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A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
Summary:
The authors from the University of Oslo, Versailles Saint-Quentin, and the University of Torino developed a new zirconium-based inorganic building brick, Zr₆O₄(OH)₄(CO₂)₁₂, forming metal-organic frameworks (MOFs) with exceptional thermal and chemical stability, achieving high surface areas up to 4170 m²/g and potential applications in gas storage, catalysis, and separation.
Background:
1. To address the poor thermal and chemical stability of conventional MOFs, previous researchers explored various metal clusters and linkers, achieving moderate success, yet most MOFs still decompose below 400 °C and degrade in polar solvents.
2. The authors proposed using a 12-connected Zr₆-oxo cluster as an inorganic node and linear dicarboxylate linkers, obtaining UiO-66/67/68 series MOFs that retain crystallinity above 540 °C and resist boiling water and organic solvents.
Research Content:
1. Synthesis:
The authors synthesized UiO-66 (Zr-BDC), UiO-67 (Zr-BPDC), and UiO-68 (Zr-TPDC) via solvothermal reaction of ZrCl₄ with the corresponding dicarboxylic acids in DMF at 120 °C for 24 h under static conditions.
2. Characterizations:
1) BET: Langmuir surface areas of 1187 m²/g (UiO-66), 3000 m²/g (UiO-67), and 4170 m²/g (UiO-68); microporous with triangular windows of 6–10 Å.
2) SEM: 1–2 µm intergrown cubic crystals.
3) TGA-MS: onset decomposition at 540 °C under N₂, releasing benzene fragments; PXRD shows no change after 300 °C calcination or 24 h stirring in H₂O, DMF, acetone, benzene; mechanical pressing up to 10 000 kg cm⁻² leaves pattern intact.
4) EXAFS & IR: reversible μ₃-OH removal at 250–300 °C, Zr coordination drops from 8 to 7 without framework collapse; full re-hydration restores original structure.
3. Application:
The materials were tested for N₂ adsorption, solvent resistance, and mechanical compression, demonstrating ultra-high surface area together with unprecedented thermal/chemical robustness, making them promising for harsh-condition separations, catalysis, and gas storage.
4. Mechanism:
The exceptional stability arises from the strong Zr–O(carboxylate) bonding and the flexible Zr₆-oxo core that reversibly de/hydroxylates without breaking the carboxylate bridges, thus preserving the cubic-close-packed framework topology.
Outlook:
This work establishes the Zr₆O₄(OH)₄(CO₂)₁₂ cluster as a universally stable 12-connected node for isoreticular MOF expansion, pushing MOF thermal stability to the limit of organic linker degradation and opening avenues for carborane-linker-based even more robust frameworks.
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
Authors: Jasmina Hafizovic Cavka, Søren Jakobsen, Unni Olsbye, Nathalie Guillou, Carlo Lamberti, Silvia Bordiga, Karl Petter Lillerud
DOI: 10.1021/ja8057953
Link: https://pubs.acs.org/doi/10.1021/ja8057953
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