Tailoring sub-3.3 Å ultramicropores in advanced carbon molecular sieve membranes for blue hydrogen production

Hu, Leiqing; Bui, Vinh T.; Krishnamurthy, Ajay; Fan, Shouhong; Guo, Wenji; Pal, Sankhajit; Chen, Xiaoyi; Zhang, Gengyi; Ding, Yifu; Singh, Rajinder P.; Lupion, Monica; Lin, Haiqing

doi:10.1126/sciadv.abl8160

Tailoring sub-3.3 Å ultramicropores in advanced carbon molecular sieve membranes for blue hydrogen production

Journal Article · Tue Mar 08 23:00:00 EST 2022 · Science Advances

DOI:https://doi.org/10.1126/sciadv.abl8160· OSTI ID:1864405

^[1]; Bui, Vinh T. ^[2]; ^[3]; ^[4]; ^[2]; Pal, Sankhajit ^[2]; ^[2]; Zhang, Gengyi ^[2]; ^[4]; Singh, Rajinder P. ^[5]; ^[2]; ^[2]

Univ. at Buffalo, State Univ. of New York (SUNY), Buffalo, NY (United States); University at Buffalo, SUNY
Univ. at Buffalo, State Univ. of New York (SUNY), Buffalo, NY (United States)
Theiss Research, La Jolla, CA (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Univ. of Colorado, Boulder, CO (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Carbon molecular sieve (CMS) membranes prepared by carbonization of polymers containing strongly size-sieving ultramicropores are attractive for high-temperature gas separations. However, polymers need to be carbonized at extremely high temperatures (900° to 1200°C) to achieve sub-3.3 Å ultramicroporous channels for H₂/CO₂ separation, which makes them brittle and impractical for industrial applications. Here, we demonstrate that polymers can be first doped with thermolabile cross-linkers before low-temperature carbonization to retain the polymer processability and achieve superior H₂/CO₂ separation properties. Specifically, polybenzimidazole (PBI) is cross-linked with pyrophosphoric acid (PPA) via H bonding and proton transfer before carbonization at ≤600°C. The synergistic PPA doping and subsequent carbonization of PBI increase H₂ permeability from 27 to 140 Barrer and H₂/CO₂ selectivity from 15 to 58 at 150°C, superior to state-of-the-art polymeric materials and surpassing Robeson’s upper bound. This study provides a facile and effective way to tailor subnanopore size and porosity in CMS membranes with desirable molecular sieving ability.

View Accepted Manuscript (DOE)

Research Organization:: State Univ. of New York (SUNY), Buffalo, NY (United States)

Sponsoring Organization:: USDOE Pittsburgh Energy Technology Center (PET)

Grant/Contract Number:: FE0031636

OSTI ID:: 1864405

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 10 Vol. 8; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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