Reversible Phase Transformations in a Double-Walled Diamondoid Coordination Network with a Stepped Isotherm for Methane

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Xia Li - , University of Limerick (Author)
  • Debobroto Sensharma - , University of Limerick (Author)
  • Leigh Loots - , University of Stellenbosch (Author)
  • Shubo Geng - , Nankai University (Author)
  • Sousa Javan Nikkhah - , University of Limerick (Author)
  • En Lin - , Nankai University (Author)
  • Volodymyr Bon - , Chair of Inorganic Chemistry I (Author)
  • Wansheng Liu - , Nankai University (Author)
  • Zhifang Wang - , Nankai University (Author)
  • Tao He - , University of Limerick (Author)
  • Soumya Mukherjee - , University of Limerick (Author)
  • Matthias Vandichel - , University of Limerick (Author)
  • Stefan Kaskel - , Chair of Inorganic Chemistry I (Author)
  • Leonard J. Barbour - , University of Stellenbosch (Author)
  • Zhenjie Zhang - , Nankai University (Author)
  • Michael J. Zaworotko - , University of Limerick (Author)

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.

Details

Original languageEnglish
Pages (from-to)18387-18395
Number of pages9
JournalJournal of the American Chemical Society
Volume146
Issue number27
Publication statusPublished - 10 Jul 2024
Peer-reviewedYes

External IDs

PubMed 38904843