Clay-supported graphene materials: application to hydrogen storage.

The present work refers to clay-graphene nanomaterials prepared by a green way using caramel from sucrose and two types of natural clays (montmorillonite and sepiolite) as precursors, with the aim of evaluating their potential use in hydrogen storage. The impregnation of the clay substrates by caramel in aqueous media, followed by a thermal treatment in the absence of oxygen of these clay-caramel intermediates gives rise to graphene-like materials, which remain strongly bound to the silicate support. The nature of the resulting materials was characterized by different techniques such as XRD, Raman spectroscopy and TEM, as well as by adsorption isotherms of N2, CO2 and H2O. These carbon-clay nanocomposites can act as adsorbents for hydrogen storage, achieving, at 298 K and 20 MPa, over 0.1 wt% of hydrogen adsorption excess related to the total mass of the system, and a maximum value close to 0.4 wt% of hydrogen specifically related to the carbon mass. The very high isosteric heat for hydrogen sorption determined from adsorption isotherms at different temperatures (14.5 kJ mol(-1)) fits well with the theoretical values available for hydrogen storage on materials that show a strong stabilization of the H2 molecule upon adsorption.

[1]  B. Sernelius,et al.  Repulsive van der Waals forces due to hydrogen exposure on bilayer graphene , 2012, 1201.1132.

[2]  R. Ruoff,et al.  Graphene and Graphene Oxide: Synthesis, Properties, and Applications , 2010, Advanced materials.

[3]  T. Pinnavaia,et al.  On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum , 1984 .

[4]  T. Kyotani,et al.  Templated Nanocarbons for Energy Storage , 2012, Advanced materials.

[5]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[6]  Shaojun Guo,et al.  Graphene nanosheet: synthesis, molecular engineering, thin film, hybrids, and energy and analytical applications. , 2011, Chemical Society reviews.

[7]  A. Gu,et al.  How to accurately determine the uptake of hydrogen in carbonaceous materials , 2004 .

[8]  M. Darder,et al.  Caramel–clay nanocomposites , 2005 .

[9]  R. Piner,et al.  Synthesis of graphene-like nanosheets and their hydrogen adsorption capacity , 2010 .

[10]  M. Darder,et al.  Multifunctional materials based on graphene-like/sepiolite nanocomposites , 2010 .

[11]  Eduardo Ruiz-Hitzky,et al.  Graphene-clay based nanomaterials for clean energy storage , 2014 .

[12]  D. Petridis,et al.  Aqueous and gaseous adsorption from montmorillonite-carbon composites and from derived carbons. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[13]  Christopher S. Johnson,et al.  Carbons for Lithium Battery Applications Prepared Using Sepiolite as an Inorganic Template , 1999 .

[14]  Chen-Chia Huang,et al.  Hydrogen storage performance in palladium-doped graphene/carbon composites , 2013 .

[15]  T. Kyotani,et al.  Formation of a flexible graphite film from poly(acrylonitrile) using a layered clay film as template , 1994 .

[16]  D. Petridis,et al.  High Surface Area Montmorillonite−Carbon Composites and Derived Carbons , 2004 .

[17]  M. Darder,et al.  Supported Graphene from Natural Resources: Easy Preparation and Applications , 2011, Advanced materials.

[18]  S. Stankovich,et al.  Graphene-based composite materials , 2006, Nature.

[19]  T. Kyotani,et al.  Formation of highly orientated graphite from polyacrylonitrile by using a two-dimensional space between montmorillonite lamellae , 1988, Nature.

[20]  Dolores Lozano-Castelló,et al.  Pillared carbons consisting of silsesquioxane bridged graphene layers for hydrogen storage materials , 2012 .

[21]  J. A. Schwarz,et al.  Pore Structure of Carbon−Mineral Nanocomposites and Derived Carbons Obtained by Template Carbonization , 1996 .

[22]  P. Luckham,et al.  The colloidal and rheological properties of bentonite suspensions , 1999 .

[23]  F. Švec,et al.  Nanoporous polymers for hydrogen storage. , 2009, Small.

[24]  E. Ruiz-Hitzky.  Molecular access to intracrystalline tunnelsof sepiolite , 2001 .

[25]  A. Govindaraj,et al.  Uptake of H2 and CO2 by Graphene , 2008 .

[26]  R. T. Yang,et al.  Hydrogen storage on platinum nanoparticles doped on superactivated carbon , 2007 .

[27]  G. Sandí,et al.  New Carbon Electrodes for Secondary Lithium Batteries , 1996 .

[28]  S. Ramaprabhu,et al.  Investigation of Spillover Mechanism in Palladium Decorated Hydrogen Exfoliated Functionalized Graphene , 2011 .

[29]  D. Cazorla-Amorós,et al.  Characterization of Activated Carbon Fibers by CO 2 Adsorption , 1996 .

[30]  Ying Ying Wang,et al.  Raman spectroscopy and imaging of graphene , 2008, 0810.2836.

[31]  S. Mallakpour,et al.  Preparation and characterization of new organoclays using natural amino acids and Cloisite Na , 2011 .

[32]  T. Kyotani,et al.  Formation of graphite thin film from polyfurfuryl alcohol and polyvinyl acetate carbons prepared between the lamellae of montmorillonite , 1991 .

[33]  Dolores Lozano-Castelló,et al.  Hydrogen storage on chemically activated carbons and carbon nanomaterials at high pressures , 2007 .

[34]  M. Darder,et al.  Relevance of polymer– and biopolymer–clay nanocomposites in electrochemical and electroanalytical applications , 2006 .

[35]  V. Tozzini,et al.  Prospects for hydrogen storage in graphene. , 2012, Physical chemistry chemical physics : PCCP.

[36]  James M. Tour,et al.  Growth of graphene from food, insects, and waste. , 2011, ACS nano.

[37]  S. Bhatia,et al.  Optimum conditions for adsorptive storage. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[38]  Diego Cazorla-Amorós,et al.  Hydrogen Storage in Activated Carbons and Activated Carbon Fibers , 2002 .

[39]  P. Aranda,et al.  Templated Synthesis of Carbon Nanofibers from Polyacrylonitrile Using Sepiolite , 2004 .

[40]  A. Züttel,et al.  Hydrogen adsorption in carbonaceous materials–: How to determine the storage capacity accurately , 2002 .

[41]  D. Cazorla-Amorós,et al.  Scale-up activation of carbon fibres for hydrogen storage , 2010 .

[42]  M. Darder,et al.  Functionalized carbon-silicates from caramel-sepiolite nanocomposites. , 2007, Angewandte Chemie.

[43]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.