Date
Abstract
Flexible metal−organic materials (FMOMs) with stepped isotherms can offer enhanced working capacity in storage applications such as adsorbed natural gas (ANG) storage. Unfortunately, whereas >1000 FMOMs are known, only a handful exhibit methane uptake of >150 cm3 /cm3 at 65 atm and 298 K, conditions relevant to ANG. Here, we report a double-walled 2-fold interpenetrated diamondoid (dia) network, X-dia-6-Ni, [Ni2L4(μ-H2O)]n, comprising a new azo linker ligand, L− (L− = (E)-3-(pyridin-4-yldiazenyl)- benzoate) and 8-connected dinuclear molecular building blocks. X-dia-6-Ni exhibited gas (CO2, N2, CH4) and liquid (C8 hydrocarbons)-induced reversible transformations between its activated narrow-pore β phase and γ, a large-pore phase with ca. 33% increase in unit cell volume. Single-crystal X-ray diffraction (SCXRD) studies of the as-synthesized phase α, β, and γ revealed that structural transformations were enabled by twisting of the azo moiety and/or deformation of the MBB. Further insight into these transformations was gained from variable temperature powder XRD and in situ variable pressure powder XRD. Low-temperature N2 and CO2 sorption revealed stepped Type F−II isotherms with saturation uptakes of 422 and 401 cm3 /g, respectively. X-dia-6-Ni exhibited uptake of 200 cm3 /cm3 (65 atm, 298 K) and a high CH4 working capacity of 166 cm3 /cm3 (5−65 bar, 298 K, 33 cycles), the third highest value yet reported for an FMOM and the highest value for an FMOM with a Type F−II isotherm
Supervisor
Description
Publisher
American Chemical Society
Citation
Journal of the American Chemical Society 2024, 146 (27), 18387-18395
Collections
Chemical Sciences
Bernal Institute
Show all metadata
Files
Thumbnail Image
Li_2024_Reversible.pdf
Adobe PDF, 3.79 MB
Keywords
metal-organic framework, porous materials, single crystal, gas-storage, Chemical sciences
ULRR Identifiers
https://doi.org/10.34961/researchrepository-ul.26841586
 https://hdl.handle.net/10344/13756
Funding code
Funding Information
We gratefully acknowledge Science Foundation Ireland (SFIAwards 16/IA/4624), the Irish Research Council (IRCLA/2019/167), the European ResearchCouncil (ADG 885695) and the National Natural Science Foundation of China (22371146). S.J.N. and M.V. acknowledge the Luxembourg national supercomputer MeluXina and the Irish Centre for High-End Computing (ICHEC) for the provision of computational facilities and support. S.J.N. is grateful for the support by Enterprise Ireland and the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie actions (grant agreement no. 847402, project ID: MF20210297).
Sustainable Development Goals
External Link
Type
Article
Rights
https://creativecommons.org/licenses/by-nc-sa/4.0/
License