Low temperature pyrolysis of thin film composite polyphosphazene membranes for hot gas separation

F. Radmanesh, A. Tena, E. J.R. Sudhölter, N. E. Benes*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

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Highly selective thin-film composite membranes for hot hydrogen sieving are prepared via the pyrolysis of thin cyclomatric polyphenoxy phosphazene films that are prepared via a non-conventional interfacial polymerization of hexachlorocyclotriphosphazene with 1,3,5-trihydroxybenzene or m-dihydroxybenzene. The presence of the cyclic phosphazene ring within the weakly branched polymer films gives rise to a distinct thermal degradation evolution, with an onset temperature of around 200 °C. For the trihydroxybenzene derived material, the hydrogen permselectivity of the films shows a maximum pyrolysis temperature of around 450 °C. At this temperature a compact atomic structure is obtained that comprises mostly disordered carbon and accommodates P–O–C and P–O–P bonds. During thermal treatment, these films reveal molecular sieving with permselectivities exceeding 100 for H2/N2, H2/CH4, and H2/CO2, and a hydrogen permeance of 2 × 10−10 to 1.5 × 10−8 mol/m2/s/Pa (0.6-44.8GPU), at 200 °C. At ambient temperatures, thin films are very effective barriers for small gas molecules. Because of the inexpensive facile synthesis and low- temperature pyrolysis, the polyphosphazene films have the potential for use in high-temperature industrial gas separations, as well as for use as barriers such as liners in high- pressure hydrogen storage vessels at ambient temperature.

Original languageEnglish
Article number100379
Number of pages8
JournalMaterials Today Nano
Publication statusPublished - 2023


  • Carbon Molecular Sieve
  • Cyclic Phosphazene
  • Gas barriers
  • Interfacial polymerization
  • Thin film composite membranes


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