Facile Fabrication of Graphene Membranes with Readily Tunable Structures.

Advanced membranes that combine mechanical robustness with fast permeation are crucial to many applications such as water purification, ions selectivity, and gas separation. Graphene sheets offer a promising opportunity to fabricate thin, high-flux, and pressure-endurable membranes because of their unique 2D morphology, oxidizable surface, and electrical conductivity. We herein report a highly effective yet simple approach to the fabrication of graphene membranes featuring controllable oxidation degrees and thus tunable structures and properties. The graphene sheets comprise a single or a few layers with a lateral dimension of 50-100 nm; their C/O ratios can be manipulated from 4.1 for graphene with a low degree of oxidation (low-oxidation graphene) to 2.5 for medium-oxidation graphene to 1.3 for high-oxidation graphene, by controlling the proportion of phosphoric acid during the 60 min fabrication. Fabricated by simple vacuum filtration, the membranes exhibited various water flux from 200.0 to 20.0 L/m(2)·h·bar at 3 bar of pressure and mechanical robustness (Young's modulus can be up to 20 GPa and tensile strength to 100 MPa). When these membranes were used as electrodes for supercapacitors, specific capacitances of 58.8 F/g and 23.5 F/cm(3) were recorded for the low-oxidation graphene membrane at 1 A/g by a two-electrode configuration; the capacity values retained ∼95% after 800 cycles; the high capacitance would be caused by moderate wettability and high electrical conductivity.

[1]  Biao Zhang,et al.  Self-assembled reduced graphene oxide/carbon nanotube thin films as electrodes for supercapacitors , 2012 .

[2]  Afriyanti Sumboja,et al.  Large Areal Mass, Flexible and Free‐Standing Reduced Graphene Oxide/Manganese Dioxide Paper for Asymmetric Supercapacitor Device , 2013, Advanced materials.

[3]  R. Stoltenberg,et al.  Evaluation of solution-processed reduced graphene oxide films as transparent conductors. , 2008, ACS nano.

[4]  T. Pradeep,et al.  Reduced graphene oxide-metal/metal oxide composites: facile synthesis and application in water purification. , 2011, Journal of hazardous materials.

[5]  A. Biswas,et al.  Graphene oxide-based hydrogels to make metal nanoparticle-containing reduced graphene oxide-based functional hybrid hydrogels. , 2012, ACS applied materials & interfaces.

[6]  Huixin Shi,et al.  Highly wrinkled cross-linked graphene oxide membranes for biological and charge-storage applications. , 2012, Small.

[7]  Xi Shen,et al.  Wrinkling in Graphene Sheets and Graphene Oxide Papers , 2014 .

[8]  Xu Wang,et al.  Creep and recovery of polystyrene composites filled with graphene additives , 2014 .

[9]  J. Byun,et al.  Preparation of highly stacked graphene papers via site-selective functionalization of graphene oxide , 2013 .

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

[11]  Xiaoming Tao,et al.  A Transparent, Flexible, Low‐Temperature, and Solution‐Processible Graphene Composite Electrode , 2010 .

[12]  Xiaoming Yang,et al.  Well-dispersed chitosan/graphene oxide nanocomposites. , 2010, ACS applied materials & interfaces.

[13]  Bobby G. Sumpter,et al.  Tunable water desalination across graphene oxide framework membranes. , 2014, Physical chemistry chemical physics : PCCP.

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

[15]  Xiaohui Wu,et al.  Preparation of butadiene–styrene–vinyl pyridine rubber–graphene oxide hybrids through co-coagulation process and in situ interface tailoring , 2012 .

[16]  Chi Cheng,et al.  Liquid-Mediated Dense Integration of Graphene Materials for Compact Capacitive Energy Storage , 2013, Science.

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

[18]  Liqun Zhang,et al.  Supramolecular ionic liquid based on graphene oxide. , 2012, Physical chemistry chemical physics : PCCP.

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

[20]  Reginald E. Rogers,et al.  Binder free graphene-single-wall carbon nanotube hybrid papers for the removal of polyaromatic compounds from aqueous systems , 2013 .

[21]  R. Verdejo,et al.  Graphene filled polymer nanocomposites , 2011 .

[22]  Zhiping Xu,et al.  Understanding water permeation in graphene oxide membranes. , 2014, ACS applied materials & interfaces.

[23]  G. Wallace,et al.  Advancement in liquid exfoliation of graphite through simultaneously oxidizing and ultrasonicating , 2014 .

[24]  Porous Graphene Materials for Advanced Electrochemical Energy Storage and Conversion Devices , 2014 .

[25]  Yulong Ying,et al.  Graphene oxide nanosheet: an emerging star material for novel separation membranes , 2014 .

[26]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

[27]  Jang-Kyo Kim,et al.  Fabrication of highly-aligned, conductive, and strong graphene papers using ultralarge graphene oxide sheets. , 2012, ACS nano.

[28]  H. Dai,et al.  Solvothermal reduction of chemically exfoliated graphene sheets. , 2009, Journal of the American Chemical Society.

[29]  Y. Shao-horn,et al.  Thin films of carbon nanotubes and chemically reduced graphenes for electrochemical micro-capacitors , 2011 .

[30]  Superhydrophobic Graphene‐Based Materials: Surface Construction and Functional Applications , 2013 .

[31]  L. Brinson,et al.  High‐Nanofiller‐Content Graphene Oxide–Polymer Nanocomposites via Vacuum‐Assisted Self‐Assembly , 2010 .

[32]  D. Yan,et al.  Toward effective and tunable interphases in graphene oxide/epoxy composites by grafting different chain lengths of polyetheramine onto graphene oxide , 2014 .

[33]  R. Ruoff,et al.  Hydrogen bond networks in graphene oxide composite paper: structure and mechanical properties. , 2010, ACS nano.

[34]  Benjamin Collins Brodie,et al.  On the Atomic Weight of Graphite , 1859 .

[35]  I. Calizo,et al.  A highly practical route for large-area, single layer graphene from liquid carbon sources such as benzene and methanol , 2011 .

[36]  Reginald E. Rogers,et al.  Free-standing carbon nanotube/graphene hybrid papers as next generation adsorbents. , 2014, Nanoscale.

[37]  Hongbing Lu,et al.  Superhydrophobic Graphene‐Based Materials: Surface Construction and Functional Applications , 2013, Advanced materials.

[38]  Li Wang,et al.  Graphene-based polyaniline nanocomposites: preparation, properties and applications , 2014 .

[39]  M. Pumera,et al.  Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. , 2014, Chemical Society reviews.