2024 - Sustainable Industrial Processing Summit
SIPS 2024 Volume 4. Kanatzidis Intl. Symp / Solid State Chemistry and Materials
| Editors: | F. Kongoli, M.A. Alario-Franco, I. Chung, M. Delferro, O. Farha, H. Kageyama, F. Marquis, A. Navrotsky, A. Tressaud, P. Trikalitis |
| Publisher: | Flogen Star OUTREACH |
| Publication Year: | 2024 |
| Pages: | 222 pages |
| ISBN: | 978-1-998384-10-5 (CD) |
| ISSN: | 2291-1227 (Metals and Materials Processing in a Clean Environment Series) |
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ULTRAPOROUS MOFs BASED ON 18-CONNECTED TERNARY, TRIGONAL PRISMATIC SUPERPOLYHEDRA
Pantelis Trikalitis1;1UNIVERSITY OF CRETE, Heraklion, Greece;
Type of Paper: Invited
Id Paper: 201
Topic: 52
Abstract:
The chemistry of metal organic frameworks (MOFs) continues to expand rapidly providing materials with diverse structures and properties. The reticular chemistry approach, where well defined structural building blocks are combined together forming crystalline open framework solids, has greatly accelerated the discovery of new and important materials. However, its full potential toward the rational design of MOFs relies on the availability of highly connected building blocks because these are greatly reducing the number of possible structures. Towards this, building blocks with connectivity greater than twelve are highly desirable but extremely rare. We report here the discovery of novel 18-connected, trigonal prismatic, ternary building blocks (tbb) and their assembly into unique MOFs, denoted as Fe-tbb-MOF-x (x: 1, 2, 3) with hierarchical micro- and mesoporosity.1 The remarkable tbb is an 18-c super-trigonal prism, with three points of extension at each corner, consisting of triangular (3-c) and rectangular (4-c) carboxylate-based organic linkers and trigonal prismatic [Fe3(μ3-Ο)(-COO)6]+ clusters. The tbb’s are linked together by an 18-c cluster made of 4-c ligands and a crystallographically distinct Fe3(μ3-Ο) trimer, forming overall a 3-D (3,4,4,6,6)-c five nodal net. The hierarchical, highly porous nature of Fe-tbb-MOF-x (x: 1, 2, 3) was confirmed by recording detailed sorption isotherms of Ar, CH4 and CO2 at 87, 112 and 195 K respectively, revealing an ultrahigh BET area (4263 - 4847 m2 g-1) and pore volume (1.95 - 2.29 cm3 g-1). Because of the observed ultrahigh porosities, the H2 and CH4 storage properties of Fe-tbb-MOF-x were investigated, revealing well-balanced high gravimetric and volumetric deliverable capacities for cryo-adsorptive H2 storage (11.6 wt%/41.4 g L-1, 77 K/100 bar – 160 K/5 bar), as well as CH4 storage at near ambient temperatures (367 mg g-1/160 cm3(STP)cm-3, 5-100 bar at 298 K), placing these materials among the top performing MOFs. The present work opens new directions to apply reticular chemistry for the construction of novel MOFs with tunable porosities, based on contracted or expanded tbb analogues.