Quasicontinuous Cooperative Adsorption Mechanism in Crystalline Nanoporous Materials

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

  • Bartosz Mazur - , Wrocław University of Science and Technology (Autor:in)
  • Filip Formalik - , Wrocław University of Science and Technology, Northwestern University (Autor:in)
  • Kornel Roztocki - , Adam Mickiewicz University in Poznań (Autor:in)
  • Volodymyr Bon - , Professur für Anorganische Chemie (I) (AC1) (Autor:in)
  • Stefan Kaskel - , Professur für Anorganische Chemie (I) (AC1) (Autor:in)
  • Alexander V. Neimark - , Rutgers - The State University of New Jersey, New Brunswick (Autor:in)
  • Lucyna Firlej - , Wrocław University of Science and Technology, Université de Montpellier (Autor:in)
  • Bogdan Kuchta - , Wrocław University of Science and Technology, Aix-Marseille Université (Autor:in)

Abstract

The hase behavior of confined fluids adsorbed in nanopores differs significantly from their bulk counterparts and depends on the chemical and structural properties of the confining structures. In general, phase transitions in nanoconfined fluids are reflected in stepwise adsorption isotherms with a pronounced hysteresis. Here, we show experimental evidence and an in silico interpretation of the reversible stepwise adsorption isotherm which is observed when methane is adsorbed in the rigid, crystalline metal-organic framework IRMOF-1 (MOF-5). In a very narrow range of pressures, the adsorbed fluid undergoes a structural and highly cooperative reconstruction and transition between low-density and high-density nanophases, as a result of the competition between the fluid-framework and fluid-fluid interactions. This mechanism evolves with temperature: below 110 K, a reversible stepwise isotherm is observed, which is a result of the bimodal distribution of the coexisting nanophases. This temperature may be considered as a critical temperature of methane confined to nanopores of IRMOF-1. Above 110 K, as the entropy contribution increases, the isotherm shape transforms to a common continuous S-shaped form that is characteristic to a gradual densification of the adsorbed phase as the pressure increases.

Details

OriginalspracheEnglisch
Seiten (von - bis)6961-6965
Seitenumfang5
FachzeitschriftJournal of Physical Chemistry Letters
Jahrgang13
Ausgabenummer30
PublikationsstatusVeröffentlicht - 4 Aug. 2022
Peer-Review-StatusJa

Externe IDs

PubMed 35877384