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Overcoming humidity-induced swelling of graphene oxide-based hydrogen membranes using charge-compensating nanodiamonds

Nature Energy volume 6, pages 1176–1187 (2021)Cite this article

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Abstract

Graphene oxide (GO) can form ultrapermeable and ultraselective membranes that are promising for various gas separation applications, including hydrogen purification. However, GO films lose their attractive separation properties in humid conditions. Here we show that incorporating positively charged nanodiamonds (ND+s) into GO nanolaminates leads to humidity-resistant, yet high-performing, membranes. While native GO membranes fail at a single run, the GO/ND+ composite retains up to roughly 90% of GO’s H2 selectivity against CO2 after several cycles under an aggressive humidity test. The addition of negatively charged ND to GO brought no such stabilization, suggesting that charge compensation acts as the main mechanism conferring humidity resistance, where ND+s neutralize the negative charge GO sheets. We observed a similar but inferior stabilization effect when positively charged polyhedral oligomeric silsesquioxane replaces ND+. The demonstrated material platform offers a solution for separating H2 gas from its usually humid mixtures generated from fossil fuel sources or water splitting.

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Fig. 1: Schematic illustration of GO and GOαND+/− laminate membranes.
Fig. 2: Morphological evaluation of GO sheets, GO–ND+ complexes and laminate membranes.
Fig. 3: Separation performance stability of GO-based membranes under humid feed.
Fig. 4: Charge evaluation of precursors and structural analysis of membranes.
Fig. 5: Gas transport properties of GO-based membranes.
Fig. 6: Photographs of GO and GO30ND+ membranes immersed in water.
Fig. 7: Humidity stability of ND+-incorporated GO membranes.
Fig. 8: Filler comparison and performance stability of GO membranes for other applications.

Data availability

The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

We acknowledge S. Kawaguchi for his supervision in synchrotron-based XRD measurements conducted at BL02B2 of SPring-8 with the approval of JASRI (proposal number 2019B1362). We also thank H. Tochio and S. Hirase (Kyoto University) for their support with the Raman microspectroscopy and gas adsorption measurements, respectively. We thank J. Xue and X. Sun (ShanghaiTech University) for their assistance in Kelvin probe force microscopy analysis. E.S. gratefully acknowledges the Japan Science and Technology Agency (JST) for funding under the JST-Mirai program (grant number JPMJMI17E3). A.P.I. and H.E.K. acknowledge the Japan Society for the Promotion of Science (JSPS) for funding under the JSPS International Fellowship program. R.I. acknowledges Quantum Leap Flagship Program (MEXT Q-LEAP, grant number JPMXS0120330644), MEXT, and Precursory Research for Embryonic Science and Technology (PRESTO, grant number JPMJPR18G1), JST. B.K.C. acknowledges funding from Ministry of Science and Technology, Taiwan (grant number 110-2222-E-008-003-MY3). T.L. acknowledges the National Natural Science Foundation, China, for funding under the General Program (grant number 22075181). M.S. acknowledges JSPS for KAKENHI funding (grant numbers 20H00453 and 18K19297).

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Authors and Affiliations

  1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Kyoto, Japan

    Guoji Huang, Behnam Ghalei, Ali Pournaghshband Isfahani, H. Enis Karahan, Detao Qin, Masahiko Tsujimoto, Daisuke Yamaguchi, Kunihisa Sugimoto & Easan Sivaniah

  2. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto, Japan

    Guoji Huang, Behnam Ghalei, Ali Pournaghshband Isfahani, H. Enis Karahan, Daiki Terada, Detao Qin, Daisuke Yamaguchi, Masahiro Shirakawa & Easan Sivaniah

  3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, China

    Conger Li & Tao Li

  4. Division of Diffraction and Scattering, Japan Synchrotron Radiation Research Institute (JASRI), Sayo-Cho, Sayo-gun, Hyogo, Japan

    Kunihisa Sugimoto

  5. Institute for Quantum Life Science, National Institutes for Quantum Science and Technology, Chiba, Japan

    Ryuji Igarashi

  6. Department of Chemical and Materials Engineering, National Central University, Taoyuan City, Taiwan, Republic of China

    Bor Kae Chang

  7. R&D Center for Membrane Technology, Chung Yuan Christian University, Taoyuan City, Taiwan, Republic of China

    Bor Kae Chang

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  1. Guoji Huang
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Contributions

Conceptualization was done by G.H. and B.G. Methodology was developed by G.H., B.G., A.P.I. and H.E.K. Investigations were carried out by G.H., A.P.I., D.T., H.E.K., M.T., C.L., D.Q., B.K.C., T.L., D.Y. and K.S. Validation was done by A.P.I., B.G. and H.E.K. Software was developed by B.K.C. and T.L. Formal analysis was carried out by G.H., B.G., A.P.I., H.E.K., D.Q., D.Y., K.S., R.I. and M.S. Data curation was done by G.H. and B.G. The original draft was written and prepared by E.S., B.G., G.H., A.P.I. and H.E.K. Review and editing of the paper was done by H.E.K., B.G. and E.S. Visualization was done by B.G., G.H. and H.E.K. Project administration was done by G.H. and B.G. Funding was acquired by E.S. Resources were supplied by E.S., B.G., R.I., M.S., B.K.C. and T.L. Supervision was carried out by B.G. and E.S. All authors have read and agreed to the published version of the paper.

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Correspondence to Behnam Ghalei or Easan Sivaniah.

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The results of this publication have been filed for a patent application by Kyoto University. G.H., B.G. and E.S. are listed as inventors within the patent.

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Peer review information Nature Energy thanks Miao Yu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 The lateral size analysis of GO sheets.

SEM images and corresponding size distributions of a, d. SGO, b, e. GO, and c, f. LGO. The average lateral sizes of SGO, GO, and LGO samples were calculated as 0.2, 3, and 10 µm, respectively.

Source data

Extended Data Fig. 2 Size distribution of ND+ and other nanoparticles used for comparison.

TEM images of ND+ particles, the scale bar indicates 5 nm in the TEM image. Hydrodynamic particle size distribution of b. ND+, c. ND−, d. POSS−, and e. POSS+ particles based on dynamic light scattering (DLS) measurements. All measurements were performed at 25 °C using aqueous dispersions of 5 mg mL−1.

Source data

Extended Data Fig. 3 Digital pictures and microscopy images of GOαND+ composite membranes on AAO support.

The photos of a. GO-only, b. GO10ND+, c. GO20ND+, and d. GO30ND+ membranes. 2D and 3D height surface AFM images of e. GO-only, f. GO10ND+, g. GO20ND+, and h. GO30ND+ membranes; the scan area is 10 μm × 10 μm. Surface SEM images of i. GO, j. GO10ND+, k. GO20ND+, and l. GO30ND+ membranes. The surface morphology of membranes gradually became rougher when the ND+ particles are added. The rough microstructure without any severe agglomeration of ND+ particles confirmed the uniform dispersion of ND+ particles, even at a relatively high loading of 30 wt.%.

Source data

Extended Data Fig. 4 Spectroscopic and nanomechanical analyses of GO, ND+, and GOαND+ membranes.

a. FTIR analysis: GO exhibited typical peaks corresponding to C−O (alkoxy/alkoxide, 1046 cm−1), C−O (carboxyl, 1410 cm−1), C=C (aromatic, 1627 cm−1), C=O (carboxyl/carbonyl, 1726 cm−1), and −OH (3300 cm−1). The bands of ND+ at 1720 cm−1 and 1000−1350 cm−1 are corresponding to the stretching of C=O and C−O or C−O−C vibrations, respectively, which is in agreement with the literature70. The carbonyl band at 1725 cm−1 broadened and shifted to lower frequencies at 1636 cm−1 by incorporating ND+ particles, indicating the hydrogen bonding between GO and ND+s. b, c, d. High-resolution XPS analysis: The deconvolutions of C−C region indicate the presence of both sp2- and sp3-hybridized species in both GO and ND+. Since ND+ particles are poor in O functionalities, the relative abundance (intensity) of the total signals of O−C=O, C=O, and O−C−O species is lower in GO30ND+ membranes compared to GO membranes. No nitrogen peak was found in the structure of GO membranes, whereas the GO30ND+ membrane exhibited 1.5% nitrogen due to the presence of ND+, detected at 399.1 eV (C−NH−C) and 401.1 eV (C3−N) (see Supplementary Table 2). e. Nanoindentation-based mechanical testing of the laminate membranes. (Error bars represent the standard error of 20 indents.) f. Raman spectra of ND+, GO, and GOαND+ complexes on silicon wafer substrates. The D and G bands at around 1343 cm−1 and 1589 cm−1 are characteristic of defective and sp2-hybridized (graphenic) sites of GO structure. ND+ particles show distinct bands of diamond, disordered (amorphous) sp3 carbon, and G-band of graphene-like carbon (GLC) with sp2 hybridization71. The ID/IG for GO and GOαND+ membranes range from 0.78 to 0.86. D and G bands of GOαND+ samples are slightly broader than those of native GO, likely because of the superimpositions of ND+s peaks72. By adding ND+s, the G peak slightly shifted and reached lower ~1585 cm−1 for GO30ND+, partly because of the combination of GO’s G-band with the GLC band of ND+s73.

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Unprocessed microscopy images.

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Huang, G., Ghalei, B., Pournaghshband Isfahani, A. et al. Overcoming humidity-induced swelling of graphene oxide-based hydrogen membranes using charge-compensating nanodiamonds. Nat Energy 6, 1176–1187 (2021). https://doi.org/10.1038/s41560-021-00946-y

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