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Title: Tightening polybenzimidazole (PBI) nanostructure via chemical cross-linking for membrane H2/CO2 separation

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/C7TA03874G· OSTI ID:1398377

Membranes that permeate H2 and reject CO2 at temperatures above 150 °C are of great interest for low-cost H2 purification and pre-combustion CO2 capture. One of the leading polymers for this separation is poly[2,2'-(m-phenylene)-5,5'-bisbenzimidazole] (PBI), which has good thermal stability and high H2/CO2 selectivity. This study, for the first time, demonstrates that H2/CO2 selectivity can be significantly enhanced by chemical cross-linking of PBI in solid state, in distinct contrast with the literature where cross-linking PBI in solutions decreased H2/CO2 selectivity. We prepared a series of cross-linked PBIs by immersing PBI thin films in terephthaloyl chloride solutions for varying times to achieve different degrees of cross-linking, and then systematically investigated the effect of cross-linking on physical properties including gel content, thermal stability, cross-linking density, fractional free volume (FFV) and inter-chain spacing. Gas sorption and pure- and mixed-gas permeation properties were determined at temperatures ranging from 35 to 200 °C. Cross-linking decreased CO2 sorption and significantly increased H2/CO2 selectivity with a slight decrease in H2 permeability. For example, after cross-linking of PBI, the H2/CO2 selectivity increased from 15 to 23 while the H2 permeability decreased from 45 to 39 Barrers at 200 °C. As a result, the performance of this cross-linked PBI surpasses the Robeson's upper bound estimated at 200 °C, indicating its promise for H2 purification and CO2 capture.

Research Organization:
Univ. at Buffalo, NY (United States)
Sponsoring Organization:
USDOE Office of Fossil Energy (FE); National Science Foundation (NSF)
Grant/Contract Number:
FE0026463; 1554236
OSTI ID:
1398377
Alternate ID(s):
OSTI ID: 1659663
Journal Information:
Journal of Materials Chemistry. A, Vol. 5, Issue 37; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

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Cited By (3)

Sorption‐Enhanced Mixed Matrix Membranes with Facilitated Hydrogen Transport for Hydrogen Purification and CO 2 Capture journal July 2019
Effects of tertiary amines and quaternary ammonium halides in polysulfone on membrane gas separation properties journal September 2018
Novel high performance poly( p -phenylene benzobisimidazole) (PBDI) membranes fabricated by interfacial polymerization for H 2 separation journal January 2019