Decoding gas-solid interaction effects on adsorption isotherm shape: II. Polar adsorptives

S. Hadi Madani, Mark J. Biggs, Francisco Rodríguez-Reinoso, Phillip Pendleton

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

A unique set of 6 polar adsorptives of relatively large dipole moment and of increasing kinetic diameter were used to probe pore volumes available and their mechanism of adsorption on a well-characterised microporous carbon. Multiple adsorption isotherm measurements were made and repeatable results with relatively small standard deviations in amount adsorbed at low relative pressures were obtained. Inconsistencies were observed between calculated Gurvitsch volumes. Sources of these were analysed and identified as contributions from one or more of: (a) molecular sieve effects; (b) molecular packing effects, and; (c) 2D molecular structure formation due to hydrogen bonding. These inconsistencies were further studied by comparison with pore volumes derived via the Dubinin-Radushkevich (DR) equation. Qualitative analyses of the micropore filling processes were proposed, and substantiated by complementary DR analyses. Although most of the isotherms showed Type I character, recasting the relative pressure axis in logarithmic format highlighted clear differences as contributions from fluid-fluid and fluid-solid interactions during pore filling. Overall, the adsorptives were classified into three groups: (a) polar adsorptives with primarily specific interactions adsorbing as a condensation process over a relatively narrow relative pressure range in a medium and late pressure range (iso-PrOH, MeOH, 2-methyl, 2-butanol, H2O); (b) polar adsorptives with potential for non-specific interactions adsorbing as a condensation process over a relatively narrow pressure range in a medium pressure range (pyridine, iso-PrOH, 2-methyl, 2-butanol); and, (c) halogenated adsorptives adsorbing with an S-shaped uptake extending over a broad relative pressure (dichloromethane).

Original languageEnglish
Pages (from-to)232-240
Number of pages9
JournalMicroporous and Mesoporous Materials
Volume278
Early online date29 Nov 2018
DOIs
Publication statusPublished - Apr 2019

Keywords

  • Adsorbate
  • Adsorbent
  • Adsorption
  • Mechanism
  • Polarity
  • Polarizability
  • Specific interaction

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials

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