Self‐Assembly of Thiourea‐Crosslinked Graphene Oxide Framework Membranes toward Separation of Small Molecules

The poor mechanical strength of graphene oxide (GO) membranes, caused by the weak interlamellar interactions, poses a critical challenge for any practical application. In addition, intrinsic but large-sized 2D channels of stacked GO membranes lead to low selectivity for small molecules. To address the mechanical strength and 2D channel size control, thiourea covalent-linked graphene oxide framework (TU-GOF) membranes on porous ceramics are developed through a facile hydrothermal self-assembly synthesis. With this strategy, thiourea-bridged GO laminates periodically through the dehydration condensation reactions via NH2 and/or SH with OCOH as well as the nucleophilic addition reactions of NH2 to COC, leading to narrowed and structurally well-defined 2D channels due to the small dimension of the covalent TU-link and the deoxygenated processes. The resultant TU-GOF/ceramic composite membranes feature excellent sieving capabilities for small species, leading to high hydrogen permselectivities and nearly complete rejections for methanol and small ions in gas, solvent, and saline water separations. Moreover, the covalent bonding formed at the GO/support and GO/GO interfaces endows the composite membrane with significantly enhanced stability.

[1]  M. Pumera,et al.  Monothiolation and Reduction of Graphene Oxide via One-Pot Synthesis: Hybrid Catalyst for Oxygen Reduction. , 2015, ACS nano.

[2]  Juin-Yih Lai,et al.  Pressure-assisted self-assembly technique for fabricating composite membranes consisting of highly ordered selective laminate layers of amphiphilic graphene oxide , 2014 .

[3]  Yuhan Sun,et al.  Strict molecular sieving over electrodeposited 2D-interspacing-narrowed graphene oxide membranes , 2017, Nature Communications.

[4]  I. Grigorieva,et al.  Unimpeded Permeation of Water Through Helium-Leak–Tight Graphene-Based Membranes , 2011, Science.

[5]  V. Khabashesku,et al.  Sidewall Covalent Functionalization of Single Wall Carbon Nanotubes Through Reactions of Fluoronanotubes with Urea, Guanidine, and Thiourea , 2008 .

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

[7]  K. B. Yoon,et al.  Orientation‐Controlled Monolayer Assembly of Zeolite Crystals on Glass and Mica by Covalent Linkage of Surface‐Bound Epoxide and Amine Groups , 2000 .

[8]  A. D. Todd,et al.  Harnessing the chemistry of graphene oxide. , 2014, Chemical Society reviews.

[9]  Yuhan Sun,et al.  Sharp molecular-sieving of alcohol-water mixtures over phenyldiboronic acid pillared graphene oxide framework (GOF) hybrid membrane. , 2015, Chemical communications.

[10]  T. Miyata,et al.  Dehydration of an ethanol/water azeotrope through alginate-DNA membranes cross-linked with metal ions by pervaporation. , 2015, Carbohydrate polymers.

[11]  Jie Shen,et al.  Subnanometer Two-Dimensional Graphene Oxide Channels for Ultrafast Gas Sieving. , 2016, ACS nano.

[12]  Wanqin Jin,et al.  Two-Dimensional-Material Membranes: A New Family of High-Performance Separation Membranes. , 2016, Angewandte Chemie.

[13]  G. Shi,et al.  Graphene Oxide Membranes with Tunable Semipermeability in Organic Solvents , 2015, Advanced materials.

[14]  D. R. Paul,et al.  Free-standing graphene oxide thin films assembled by a pressurized ultrafiltration method for dehydration of ethanol , 2014 .

[15]  Berrin Tansel,et al.  Significance of hydrated radius and hydration shells on ionic permeability during nanofiltration in dead end and cross flow modes , 2006 .

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

[17]  Quan-hong Yang,et al.  Self‐Assembled Free‐Standing Graphite Oxide Membrane , 2009 .

[18]  A. Huang,et al.  Amine-modified Mg-MOF-74/CPO-27-Mg membrane with enhanced H-2/CO2 separation , 2015 .

[19]  Miao Zhu,et al.  Selective ion penetration of graphene oxide membranes. , 2013, ACS nano.

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

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

[22]  Jie Shen,et al.  Membranes with fast and selective gas-transport channels of laminar graphene oxide for efficient CO2 capture. , 2014, Angewandte Chemie.

[23]  N. Widjojo,et al.  Development of flat-sheet membranes for C1–C4 alcohols dehydration via pervaporation from sulfonated polyphenylsulfone (sPPSU) , 2012 .

[24]  Wenge Chen,et al.  A novel fabrication of graphene by chemical reaction with a green reductant , 2016 .

[25]  Yu Zhang,et al.  Nanometric Graphene Oxide Framework Membranes with Enhanced Heavy Metal Removal via Nanofiltration. , 2015, Environmental science & technology.

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

[27]  X. Lou,et al.  Enhancing lithium–sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide , 2014, Nature Communications.

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

[29]  A. Talyzin,et al.  Effect of synthesis method on solvation and exfoliation of graphite oxide , 2013 .

[30]  J. Xue,et al.  Sulphur-functionalized graphene towards high performance supercapacitor , 2015 .

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

[32]  I. V. Grigorieva,et al.  Precise and Ultrafast Molecular Sieving Through Graphene Oxide Membranes , 2014, Science.

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

[34]  Huanting Wang,et al.  Facile Fabrication of Freestanding Ultrathin Reduced Graphene Oxide Membranes for Water Purification , 2015, Advanced materials.

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

[36]  Kang Li,et al.  Graphene oxide membranes on ceramic hollow fibers – Microstructural stability and nanofiltration performance , 2015 .

[37]  Jie Shen,et al.  A graphene oxide membrane with highly selective molecular separation of aqueous organic solution. , 2014, Angewandte Chemie.

[38]  Yongfeng Li,et al.  Reduction of graphene oxide by thiourea. , 2011, Journal of nanoscience and nanotechnology.

[39]  Mercedes Villegas,et al.  Sorption and pervaporation of methanol/water mixtures with poly(3-hydroxybutyrate) membranes , 2015 .

[40]  Lei Shi,et al.  Efficient dehydration of the organic solvents through graphene oxide (GO)/ceramic composite membranes , 2014 .

[41]  Taner Yildirim,et al.  Graphene oxide framework materials: theoretical predictions and experimental results. , 2010, Angewandte Chemie.

[42]  T. Yildirim,et al.  Porous graphene oxide frameworks: Synthesis and gas sorption properties , 2011 .

[43]  Miao Zhu,et al.  Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions. , 2014, ACS nano.

[44]  S. C. Mojumdar,et al.  Thermal and FTIR spectral studies in various proportions of urea thiourea mixed crystal , 2011 .