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Disentangling Adsorption and Absorption in Microporous Polymers.

Máté Füredi1,2, Andrei Kolesnikov3, Anqi Wang4

  • 1Department of Chemical Engineering, University College London, London, WC1E 7JE, UK.

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|August 8, 2025
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Summary
This summary is machine-generated.

This study introduces ellipsometry to distinguish vapor adsorption and absorption in polymers of intrinsic microporosity (PIMs). This method overcomes limitations of traditional techniques, enabling better understanding of PIMs for advanced applications.

Keywords:
adsorptionellipsometric porosimetrymicroporous materialspolymersthin films

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Physical Chemistry

Background:

  • Polymers of intrinsic microporosity (PIMs) exhibit both vapor adsorption (nanopore filling) and absorption (polymer swelling).
  • Distinguishing between adsorption and absorption is crucial for understanding PIMs' performance in gas separation, water purification, and energy storage.
  • Traditional gravimetric and volumetric methods struggle to differentiate these processes due to increased sorbent mass.

Purpose of the Study:

  • To develop and validate an in situ ellipsometry-based method for simultaneously measuring and deconvoluting vapor adsorption and absorption in PIMs.
  • To investigate the contributions of adsorption and absorption in diverse PIMs exposed to various vapors.
  • To apply nanopore confinement and polymer swelling models to interpret the experimental data.

Main Methods:

  • Utilized in situ ellipsometry to monitor real-time changes in thin-film PIM sorbents.
  • Developed concurrent optical modeling to analyze ellipsometric data.
  • Quantified adsorption and absorption contributions using classical physisorption and Flory-like polymer swelling theories.

Main Results:

  • Demonstrated ellipsometry's sensitivity to thickness and optical density changes in PIMs.
  • Successfully disentangled adsorption and absorption contributions for four distinct PIMs with varying chemistries.
  • Provided experimental isotherms for both adsorption and absorption processes.

Conclusions:

  • In situ ellipsometry offers a powerful alternative for characterizing PIM-vapor interactions, overcoming limitations of conventional methods.
  • The study provides a deeper understanding of sub-nanometer-scale processes in PIMs, crucial for optimizing their use in emerging technologies.
  • Accurate differentiation of adsorption and absorption is key to tailoring PIMs for specific applications like separations and energy storage.