Supercritical CO2 utilization for the crystallization of 2D metal-organic frameworks using tert-butylpyridine additive

Núria Portolés-Gil, Sarah Gowing, Oriol Vallcorba, Concepción Domingo*, Ana M. López-Periago*, José A. Ayllón*

*Corresponding author for this work

Research output: Contribution to journalArticleResearchpeer-review

11 Citations (Scopus)


© 2018 Elsevier Ltd Recently, the study of the synthesis of metal-organic frameworks (MOFs) in the presence of supercritical CO2 (scCO2) has become a burgeoning direction in materials science. MOFs crystallization in scCO2 is often carried out in the presence of other solvents, such as ionic or organic liquids, to increase reagents solubility in the reaction media. In this work, a totally new and cleaner way is followed, utilizing small amounts of an ancillary ligand to increase metal solubility, which result in a more efficient use of scCO2. The precipitation of 2D MOFs, based in the combination of different trifluoroacetates of transition metals (M(tfa)2, MII = CuII or ZnII), and a bidentate pyridine derivative (dpy), was studied. MOFs of the type [M(tfa)2(dpy)x]∝ were precipitated using scCO2 as the solvent medium and the ligand tert-butylpyridine (t-bpy) as additive. The targeted 2D MOFs were precipitated after a short reaction time (ca. 3 h) operating under relatively soft supercritical conditions (20 MPa and 333 K). This new synthetic approach is thought as a generic method that can be used to modify metal precursors in systems in which the reaction is too slow or incomplete in neat scCO2. Moreover, the increase of metal centre solubility allowed the in situ deposition of MOF crystals grafted on modified substrates.
Original languageEnglish
Pages (from-to)444-453
JournalJournal of CO2 Utilization
Publication statusPublished - 1 Mar 2018


  • Metal-organic frameworks
  • Supercritical CO 2
  • Surface grafting
  • Tert-butylpyridine additive


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