Enhanced Stability of Laminated Graphene Oxide Membranes for Nanofiltration via Interstitial Amide Bonding.

Laminated graphene oxide (GO) has promising use as a membrane because of its high permeance, chemical and mechanical stability, as well as the molecular sieving effect of its interlayers. However, the hydrophilic surface of GO, which is highly decorated with oxygen groups, easily induces delamination of stacked GO films in aqueous media, thereby limiting the practical application. To stabilize GO films in aqueous media, we functionalized a polymer support with branched polyethylene-imine (BPEI). BPEI adsorbed intercalated into the stacked GO sheets via diffusion during filtration. The GO/BPEI membrane obtained exhibits high stability during sonication (>1 h duration, 40 kHz frequency) in water within a broad pH range (2-12). In contrast, the GO film spontaneously delaminated upon sonication. Furthermore, BPEI treatment did not affect the filtration performance of the GO film, as evidenced by the high rejection rates (>90%) for the dye molecules methylene blue, rose bengal, and brilliant blue and by their permeation rates of ca. 124, 34.8, 12.2, and 5.1%, respectively, relative to those of a typical GO membrane.

[1]  Jiachun Feng,et al.  Realizing Ultrahigh Modulus and High Strength of Macroscopic Graphene Oxide Papers Through Crosslinking of Mussel‐Inspired Polymers , 2013, Advanced materials.

[2]  D. Dikin,et al.  Graphene Oxide Sheets Chemically Cross-Linked by Polyallylamine , 2009 .

[3]  Alfred Benninghoven Chemical Analysis of Inorganic and Organic Surfaces and Thin Films by Static Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS) , 1994 .

[4]  D. Bhattacharyya,et al.  Large-area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide , 2016, Nature Communications.

[5]  Renbi Bai,et al.  MEMBRANE FOULING AND CLEANING IN MICROFILTRATION OF ACTIVATED SLUDGE WASTEWATER , 2003 .

[6]  Chao Gao,et al.  High-flux graphene oxide nanofiltration membrane intercalated by carbon nanotubes. , 2015, ACS applied materials & interfaces.

[7]  Xi Zhang,et al.  Graphene Oxide Nanofiltration Membranes Stabilized by Cationic Porphyrin for High Salt Rejection. , 2016, ACS applied materials & interfaces.

[8]  Dan Li,et al.  Controllable corrugation of chemically converted graphene sheets in water and potential application for nanofiltration. , 2011, Chemical communications.

[9]  S. Stankovich,et al.  Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy , 2009 .

[10]  Chao Gao,et al.  Ultrathin Graphene Nanofiltration Membrane for Water Purification , 2013 .

[11]  Kazuomi Suzuki,et al.  Hydrolytic stability of methacrylamide in acidic aqueous solution. , 2004, Biomaterials.

[12]  Z. Jia,et al.  Covalently crosslinked graphene oxide membranes by esterification reactions for ions separation , 2015 .

[13]  Weiwei Cai,et al.  Graphene oxide papers modified by divalent ions-enhancing mechanical properties via chemical cross-linking. , 2008, ACS nano.

[14]  Baoxia Mi,et al.  Enabling graphene oxide nanosheets as water separation membranes. , 2013, Environmental science & technology.

[15]  Miao Yu,et al.  Ultrathin, Molecular-Sieving Graphene Oxide Membranes for Selective Hydrogen Separation , 2013, Science.

[16]  Hee‐Tae Jung,et al.  Intercalation of Gas Molecules in Graphene Oxide Interlayer: The Role of Water , 2014 .

[17]  Michael S Strano,et al.  Understanding the pH-dependent behavior of graphene oxide aqueous solutions: a comparative experimental and molecular dynamics simulation study. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[18]  A. Ciesielski,et al.  Graphene via sonication assisted liquid-phase exfoliation. , 2014, Chemical Society reviews.

[19]  Daeok Kim,et al.  Sonication-free dispersion of large-area graphene oxide sheets using internal pressure from release of intercalated carbon dioxide , 2015 .

[20]  Yulong Ying,et al.  Salt concentration, pH and pressure controlled separation of small molecules through lamellar graphene oxide membranes. , 2013, Chemical communications.

[21]  J. Zhao,et al.  Enhanced water permeation through sodium alginate membranes by incorporating graphene oxides , 2014 .

[22]  Baoxia Mi,et al.  Graphene Oxide Membranes for Ionic and Molecular Sieving , 2014, Science.

[23]  G. P. Simon,et al.  Graphene‐Directed Supramolecular Assembly of Multifunctional Polymer Hydrogel Membranes , 2015 .

[24]  Jia-Qi Hu,et al.  Graphene Oxide Membranes with Strong Stability in Aqueous Solutions and Controllable Lamellar Spacing. , 2016, ACS applied materials & interfaces.

[25]  Long Chen,et al.  Stitching graphene oxide sheets into a membrane at a liquid/liquid interface. , 2014, Chemical communications.

[26]  S. Stankovich,et al.  Preparation and characterization of graphene oxide paper , 2007, Nature.

[27]  S. Sampath,et al.  Graphene and graphene oxide as effective adsorbents toward anionic and cationic dyes. , 2011, Journal of colloid and interface science.

[28]  Bao-hang Han,et al.  Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors. , 2013, Nanoscale.

[29]  Jianli Zou,et al.  Diffusion driven layer-by-layer assembly of graphene oxide nanosheets into porous three-dimensional macrostructures , 2014, Nature Communications.

[30]  P. Garstecki,et al.  Polyethyleneimine coating renders polycarbonate resistant to organic solvents. , 2012, Lab on a chip.

[31]  Quan-hong Yang,et al.  On the origin of the stability of graphene oxide membranes in water. , 2015, Nature chemistry.

[32]  Marianne Nyström,et al.  Drawbacks of applying nanofiltration and how to avoid them: A review , 2008 .

[33]  Juin-Yih Lai,et al.  Cross-Linking with Diamine Monomers To Prepare Composite Graphene Oxide-Framework Membranes with Varying d-Spacing , 2014 .

[34]  L. Brinson,et al.  Bio‐Inspired Borate Cross‐Linking in Ultra‐Stiff Graphene Oxide Thin Films , 2011, Advanced materials.

[35]  Sheng-Zhen Zu,et al.  The effect of interlayer adhesion on the mechanical behaviors of macroscopic graphene oxide papers. , 2011, ACS nano.

[36]  Jae-Young Choi,et al.  Selective Gas Transport Through Few-Layered Graphene and Graphene Oxide Membranes , 2013, Science.