Graphene Oxide Nanofiltration Membranes Stabilized by Cationic

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Graphene Oxide Nanofiltration Membranes Stabilized by Cationic Porphyrin for High Salt Rejection Xiao-Ling Xu,† Fu-Wen Lin,† Yong Du,‡ Xi Zhang,‡ Jian Wu,*,† and Zhi-Kang Xu*,‡,§ †

Department of Chemistry and ‡MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China § Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University, Nanjing 201123, China S Supporting Information *

ABSTRACT: Swelling has great influences on the structure stability and separation performance of graphene oxide laminate membranes (GOLMs) for water desalination and purification. Herein, we report cross-linked GOLMs from GO assembled with cationic tetrakis(1-methyl-pyridinium-4-yl)porphyrin (TMPyP) by a vacuum-assisted strategy. The concave nonoxide regions (G regions) of GO are used as cross-linking sites for the first time to precisely control the channel size for water permeation and salt ion retention. Channels around 1 nm are constructed by modulating the assembly ratio of TMPyP/GO, and these cross-linked GOLMs show high salt rejection. KEYWORDS: graphene oxide, membrane, intercalation, nanofiltration, salt rejection

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of its low energy cost and simple operation process.13,14 Typical NF membranes have pore size around 1 nm for efficient retention of divalent salts and organic molecules from water.13,14 Generally, GOLMs are relatively effective (rejection >85%) in NF process for rejecting large organic molecules, while ineffective (rejection MgSO4 > MgCl2 > NaCl. This also indicates that the performance of GOLMs intercalated by TMPyP is influenced by both steric hindrance and Donnan effects. The permeate fluxes are quite low for the GO membranes with relatively high salt rejection, which is the main limitation for their practical applications.29 Nonetheless, they are advantageous in the accurate separation and the separation systems with oxidizing agent, because of their well-defined structure and excellent chlorine resistance.1,3 The low fluxes are mainly caused by the low porosity of membrane, the long channel of water permeation, and the slow transport of water in GO region.8,9,30 In future research, this problem can be solved by some

Figure 4. GOLM performance: (a) with different VTMPyP‑SS/VGO‑SS (GOLM-50), (b) with different thicknesses (GOLM-6/30, Test salt: Na2SO4), (c) for different salt solutions (GOLM-100−6/30). Test conditions: salt concentration = 2000 mg/L, 0.8 MPa, cross-flow rate = 25 L/h.

as GOLM-VGO‑SS-VTMPyP‑SS/VGO‑SS. Figure 3a, b shows that the etched pores with around 200 nm in diameter can be totally covered after the process of membrane fabricating (Figure S6). The antiswelling property of GOLMs in water is investigated through comparatively exploring the d-spacing of GOLMs in both dry and wet states by XRD characterization (Figure 3c, d). The H value, which can be calculated by 2θ peak at 5−12°, indicates GOLMs with compact structure at a certain level. In the dry state, GOLMs possess the highly compact structure. Figure 3c shows that the H value of GOLMs gradually increases as VTMPyP‑SS/VGO‑SS raises from 0/30 to 30/30 (0.98−1.12 nm). D

DOI: 10.1021/acsami.6b03693 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Letter

ACS Applied Materials & Interfaces

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methods, such as screening a suitable base membrane, declining the membrane thickness, increasing the surface defects of GO sheet, and decreasing the area of GO regions. In summary, TMPyP is verified to prior assembly in the concave G region of GO sheet, and the cross-linked GOLMs can be easily fabricated from TMPyP/GO complexes by a vacuum-assisted strategy. Intercalating TMPyP into GO sheets not only enhances the antiswelling property of GOLMs in water, but also hardly increases the d-spacing of GOLMs by controlling the flattened TMPyP to assembly in the concave G region. We fabricate GOLMs with precisely channel size around 1 nm, hence these GOLMs show high salt rejection under the optimized fabrication condition (GOLM-100-6/30 for Na2SO4; rejection ratio, 87.7%; permeation flux, 9.3 L/m2· h). This work provides an example of using plane TMPyP for tuning the structures and performances of GOLMs, and the approach can be extended to other 2D molecules for fabricating GOLMs with controllable channel size.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b03693. Experimental details, absorbance spectra and fluorescence spectra versus the titration volume of TPPS-SS, digital photographs of the mixed solutions, SEM images and XRD patterns of GOLMs with different VTMPyP‑SS/ VGO‑SS, the NF test of GOLMs intercalated by TPPS with different VTPPS‑SS/VGO‑SSor by TMPyP with different thicknesses (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is primarily funded by the National Natural Science Foundation of China (Grant 21534009). We thank PhD. Yan Lv for her discussion at the beginning of the nanofiltration tests.

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REFERENCES

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DOI: 10.1021/acsami.6b03693 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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DOI: 10.1021/acsami.6b03693 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX