Abstract
A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-26 (St Andrews porous material-26), has been prepared using the 4,4′,4“-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoate (TMTB) tritopic linker with formic acid as a modulating agent. In the as-prepared form STA-26 possesses Im (Formula presented.) m symmetry compared with the Pm (Formula presented.) m symmetry of the non-interpenetrated analogue, NU-1200, prepared using benzoic acid as a modulator. Upon removal of residual solvent there is a shift between the interpenetrating lattices and a resultant symmetry change to Cmcm which is fully reversible. This is observed by X-ray diffraction and 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr 6 nodes leaving coordinatively unsaturated Zr 4+ sites, as shown by IR spectroscopy using CO and CD 3CN as probe molecules. Nitrogen adsorption at 77 K together with grand canonical Monte Carlo simulations confirms a microporous, fully interpenetrated, structure with pore volume 0.53 cm 3 g −1 while CO 2 adsorption at 196 K reaches 300 cm 3 STP g −1 at 1 bar. While the pore volume is smaller than that of its non-interpenetrated mesoporous analogue, interpenetration makes the structure more stable to moisture adsorption and introduces shape selectivity in adsorption.
Original language | English |
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Pages (from-to) | 6115-6126 |
Number of pages | 12 |
Journal | Chemistry - A European Journal |
Volume | 24 |
Issue number | 23 |
Early online date | 31 Jan 2018 |
DOIs | |
Publication status | Published - 20 Apr 2018 |
Keywords
- hafnium
- metal-organic frameworks
- modulators
- reversible lattice shift
- zirconium
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry
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Dive into the research topics of 'Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift'. Together they form a unique fingerprint.Profiles
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Tina Düren
- Department of Chemical Engineering - Head of Department
- Centre for Sustainable Chemical Technologies (CSCT)
- EPSRC Centre for Doctoral Training in Statistical Applied Mathematics (SAMBa)
- Centre for Integrated Materials, Processes & Structures (IMPS) - Centre Director
- Institute of Sustainability and Climate Change
Person: Research & Teaching, Core staff, Affiliate staff
Equipment
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Balena High Performance Computing (HPC) System
Facility/equipment: Equipment
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High Performance Computing (HPC) Facility
Chapman, S. (Manager)
University of BathFacility/equipment: Facility