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SCIENCE CHINA Materials, Volume 62, Issue 7: 925-935(2019) https://doi.org/10.1007/s40843-018-9401-1

Cation-diffusion controlled formation of thin graphene oxide composite membranes for efficient ethanol dehydration

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  • ReceivedDec 12, 2018
  • AcceptedJan 29, 2019
  • PublishedFeb 26, 2019

Abstract

Structural manipulation of graphene oxide (GO) building blocks has been widely researched. Concerning GO membranes for separation applications, the validity and maintenance of their microscopic structures in the chemical environment are pivotal for effective separation at the molecular scale. Cationic interactions with both aromatic rings and oxygenated functional groups of GO make metal ions intriguing for physically and chemically structural reinforcement. By filtrating GO suspension through the substrate loaded with cations, stacking of GO nanosheets and diffusion of cations steadily evolve simultaneously in an aqueous environment without flocculation. Thus, thin and homogeneous GO membrane is obtained. Divalent and monovalent cations were studied regarding their interactions with GO, and the performance of correspondingly functionalized membranes was evaluated. The divalent cation-stabilized membranes have favorable stability in the separation of water/ethanol. This facile fabrication and functionalization method may also be applicable for structure construction of other two-dimensional materials.


Funded by

the National Natural Science Foundation of China(21476107,21490585,21776125,51861135203)

the Innovative Research Team Program by the Ministry of Education of China(IRT17R54)

and the Topnotch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)


Acknowledgment

This work was financially supported by the National Natural Science Foundation of China (21476107, 21490585, 21776125 and 51861135203), the Innovative Research Team Program by the Ministry of Education of China (IRT17R54) and the Topnotch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Jin W had the idea of controlling the assembly of graphene oxide membranes using cation-diffusion. Guan K and Jin W designed the experiments. Guan K engineered GO-based membranes and performed the performance evaluation. Liu Q conducted the theoretical simulations. Guan K, Zhou G, Liu G and Ji Y took part in the characterizations of membrane samples. Guan K, Liu G and Jin W analyzed the data and discussed the results. Guan K wrote the paper with support from Liu G and Jin W.


Author information

Kecheng Guan is now a PhD candidate at the State Key Laboratory of Materials-oriented Chemical Engineering, Nanjing Tech University. His current research focuses on the development of graphene-based materials for membrane separation processes.


Wanqin Jin is a professor of chemical engineering at Nanjing Tech University, and a Fellow of the Royal Society of Chemistry. He received his PhD degree from Nanjing University of Technology in 1999. He was a research associate at the Institute of Materials Research & Engineering of Singapore (2001), an Alexander von Humboldt Research Fellow (2001–2013), and visiting professor at Arizona State University (2007) and Hiroshima University (2011, JSPS invitation fellowship). His current research focuses on membrane materials and processes. He now serves as an Editor of Journal of Membrane Science.


Supplement

Supplementary information

Supplementary results are available in the online version of the paper.


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  • Figure 1

    Illustration of filtrating GO aqueous suspension through cations-loaded filter substrate (left) and cation-diffusion controlled GO depositing process (right).

  • Figure 2

    (a) XPS K 2p scan of different hPAN samples; (b) respective narrow scan of different cations-loaded hPAN samples.

  • Figure 3

    Simulation snapshots of (a) Ca2+, (b) Mg2+, (c) Li+ and (d) Na+ above GO nanosheet after system optimization; (e) digital image of GO suspensions with different cations added (GO concentration: 0.1 mg mL−1, cation concentration: 2 mmol L−1); (f) illustration of interactions between oxygenated functional groups of GO and divalent cation; XPS C 1s spectra of (g) GO and (h) CaGO membranes.

  • Figure 4

    (a) XPS Ca 2p spectra at different etching depths; (b) Ca/C atomic ratio at different etching depths (inset image indicates the depth direction etched from membrane surface).

  • Figure 5

    SEM (a) cross-section and (b) surface images of CaGO membrane; EDS mapping of (c) C and Ca element of CaGO membrane; AFM images of (d) GO and (e) CaGO membranes; (f) displacement-height curves of GO and CaGO membrane surfaces (displacement is indicated by red arrows in AFM images).

  • Figure 6

    Pervaporation performance of pristine GO membrane and cation-stabilized GO membranes with a feed solution of 10 wt% water/ethanol at 70°C. The inset image is the XRD pattern of corresponding membranes.

  • Figure 7

    Pervaporation performance of (a) GO-0.1 and (b) CaGO-0.1 membranes at different operation temperatures; (c) digital photo of GO-0.4 and CaGO-0.4 membranes after pervaporation test.

  • Figure 8

    Pervaporation performances (a) under different operation temperatures and (b) with different feed water contents.

  • Figure 9

    Two-stage long-term pervaporation performance of CaGO membrane.

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