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Adsorption Isotherms II01:25

Adsorption Isotherms II

Brunauer, Emmett, and Teller (BET) introduced a theory in 1938 that modified Langmuir's assumptions to explain multilayer physical adsorption. This theory is applicable to Type II isotherms and provides a more realistic picture of adsorption processes. The BET theory assumes a uniform solid surface with localized adsorption sites, where adsorption at one site doesn't affect adsorption at neighboring sites. This theory also allows for the possibility of additional molecules being adsorbed on top...
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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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A Three-Dimensional Covalent Organic Framework Enables Guest-Triggered Reversible Disorder-Order Structural

Bang Hou1, Jiayang Liu2, Xiaoliang Wang1,3

  • 1Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.

Journal of the American Chemical Society
|June 29, 2026
PubMed
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This study introduces a flexible covalent organic framework (COF) with amine linkages that shows remarkable SO2 adsorption. This COF design enables dynamic gas uptake and structural integrity, crucial for gas separation technologies.

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Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Covalent organic frameworks (COFs) offer tunable properties for gas adsorption but achieving controlled flexibility and high crystallinity is challenging.
  • Dynamic gas adsorption requires materials that can adapt their structure upon guest interaction without losing integrity.

Purpose of the Study:

  • To develop a three-dimensional COF with controlled framework flexibility for dynamic gas adsorption.
  • To investigate the structure-property relationships governing gas sorption behavior in COFs with different linkage types.

Main Methods:

  • Single-crystal-to-single-crystal transformation of an imine-linked COF to an amine-linked COF via postsynthetic reduction.
  • Powder X-ray diffraction (PXRD) to analyze structural changes during guest adsorption-desorption.
  • Gas sorption measurements (SO2, N2) at various temperatures and pressures.
  • Computational modeling to understand framework deformation mechanisms.

Main Results:

  • The amine-linked COF (39-a) exhibits reversible pore-opening behavior with polar molecules, unlike its rigid imine-linked counterpart (39-i).
  • 39-a achieves exceptionally high SO2 uptake (10.4 mmol g-1 at 298 K, 1 bar), one of the highest for COFs under ambient conditions.
  • SO2 adsorption induces a reversible disorder-order-disorder transformation in 39-a, driven by host-guest interactions and facilitated by flexible amine linkages.
  • Framework compression is accommodated through cooperative folding and torsional distortion, preserving structural integrity.

Conclusions:

  • Linkage-controlled structural adaptation is a viable strategy for designing COFs with dynamic gas adsorption capabilities.
  • The amine-linked COF demonstrates robust and selective SO2 adsorption, suitable for challenging environments.
  • This work provides insights into host-guest interactions and framework dynamics in COFs for advanced gas separation applications.