Theoretical insight into hydrogen adsorption onto graphene: a first-principles B3LYP-D3 study.

This work investigates hydrogen adsorption onto various graphene flakes such as coronene and coronene-like as suitable models of graphene within the framework of the DFT-B3LYP method. The non-local van der Waals (vdW) density functional (B3LYP-D3) method is used for both structural geometry optimization and total energy estimations. Calculations were carried out for a hydrogen molecule above a coronene surface with both conventional and vdW corrected DFT to investigate how these approaches perform in the case of hydrogen adsorption on a graphene surface. Our first-principles results within the B3LYP-D3/def2-TZVPP model show that hydrogen physisorbs on a coronene surface with an adsorption energy of -5.013 (kJ mol(-1)) which is in good agreement with the experimental value. The influence of the basis set and graphene flake size were also evaluated and the results indicate that these slightly affect the adsorption properties. We found also that it is crucial to use non-local dispersion interactions to get accurate results for hydrogen adsorption on a graphene surface. Furthermore, the co-adsorption of H2 molecules onto the graphene surface was investigated. The results obtained at the B3LYP-D3/def2-TZVP level show that H2 molecules can be physisorbed on both sides of the graphene layer with adsorption properties similar to those for a single surface. Finally, we showed that H2 molecules might be bound to the graphene surface via a bilayer adsorption scheme with weak adsorption energy. Charge population and electron density analysis confirm the weak binding nature of the system under consideration.

[1]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[2]  Y. Gogotsi,et al.  Tailoring of nanoscale porosity in carbide-derived carbons for hydrogen storage. , 2005, Journal of the American Chemical Society.

[3]  Stuart A. Rice,et al.  Graphite and Its Crystal Compounds , 1961 .

[4]  V. Sidis,et al.  DFT investigation of the adsorption of atomic hydrogen on a cluster-model graphite surface , 1999 .

[5]  G. W. C. Kaye,et al.  Tables of Physical and Chemical Constants , 2018 .

[6]  M. Ganji,et al.  B36N36 fullerene-like nanocages: A novel material for drug delivery , 2010 .

[7]  D. Bhattacharyya,et al.  Interaction of Nucleobases with Wrinkled Graphene Surface: Dispersion Corrected DFT and AFM Studies , 2012 .

[8]  Thomas Frauenheim,et al.  Hydrogen bonding and stacking interactions of nucleic acid base pairs: A density-functional-theory based treatment , 2001 .

[9]  G. DiLabio,et al.  Extension of the B3LYP–dispersion-correcting potential approach to the accurate treatment of both inter- and intra-molecular interactions , 2013, Theoretical Chemistry Accounts.

[10]  Andreas Züttel,et al.  Materials for hydrogen storage , 2003 .

[11]  H. V. Swygenhoven,et al.  Deformation in nanocrystalline metals , 2006 .

[12]  A. Datta,et al.  Pattern formation due to fluorination on graphene fragments: structures, hopping behavior, and magnetic properties. , 2013, The journal of physical chemistry. A.

[13]  J. Tse,et al.  Graphene nanostructures as tunable storage media for molecular hydrogen. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[14]  Reversible Hydrogen Storage by Controlled Buckling of Graphene Layers , 2011, 1101.1178.

[15]  S. Han,et al.  ADSORPTION PROPERTIES OF HYDROGEN ON (10, 0) SINGLE-WALLED CARBON NANOTUBE THROUGH DENSITY FUNCTIONAL THEORY , 2004 .

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

[17]  Ž. Šljivančanin,et al.  Extended atomic hydrogen dimer configurations on the graphite(0001) surface. , 2009, The Journal of chemical physics.

[18]  Jörg Fink,et al.  Hydrogen storage in different carbon nanostructures , 2002 .

[19]  Julian Tirado-Rives,et al.  Performance of B3LYP Density Functional Methods for a Large Set of Organic Molecules. , 2008, Journal of chemical theory and computation.

[20]  T Yildirim,et al.  Titanium-decorated carbon nanotubes as a potential high-capacity hydrogen storage medium. , 2005, Physical review letters.

[21]  Yixuan Wang,et al.  Interaction between glycine/glycine radicals and intrinsic/boron-doped (8,0) single-walled carbon nanotubes: a density functional theory study. , 2008, The journal of physical chemistry. B.

[22]  A. Datta,et al.  Computational design of high hydrogen adsorption efficiency in molecular sulflower , 2007 .

[23]  S. Grimme,et al.  A geometrical correction for the inter- and intra-molecular basis set superposition error in Hartree-Fock and density functional theory calculations for large systems. , 2012, The Journal of chemical physics.

[24]  F. Marinelli,et al.  Density functional theory investigation of H adsorption and H2 recombination on the basal plane and in the bulk of graphite: Connection between slab and cluster model , 2002 .

[25]  Y. Miyamoto,et al.  Ab Initio Investigation of Physisorption of Molecular Hydrogen on Planar and Curved Graphenes , 2001 .

[26]  Permeation of low-Z atoms through carbon sheets: Density functional theory study on energy barriers and deformation effects , 2012, 1201.4014.

[27]  G. Seifert,et al.  Hydrogen storage by physisorption on nanostructured graphite platelets , 2004 .

[28]  D. Teillet-Billy,et al.  Double H atom adsorption on a cluster model of a graphite surface , 2006 .

[29]  A. Datta.  Modelling doped (Ni, Pd, Pt) sulfur-nitrolic systems as new motifs for storage of hydrogen. , 2009, Physical chemistry chemical physics : PCCP.

[30]  J. Kysar,et al.  Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene , 2008, Science.

[31]  Michael Hietschold,et al.  Incorporation and manipulation of coronene in an organic template structure. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[32]  D. Mathematics,et al.  Structure and energetics of hydrogen chemisorbed on a single graphene layer to produce graphane , 2011, 1103.2619.

[33]  J. Alper.  Water Splitting Goes Au Naturel , 2003, Science.

[34]  J. Bertrán,et al.  Influence of the Side Chain in the Structure and Fragmentation of Amino Acids Radical Cations. , 2007, Journal of chemical theory and computation.

[35]  A. Datta,et al.  Do cation···π interactions always need to be 1:1? , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[36]  A. Schäfer,et al.  Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr , 1994 .

[37]  D. Bethune,et al.  Storage of hydrogen in single-walled carbon nanotubes , 1997, Nature.

[38]  A. Züttel,et al.  Hydrogen-storage materials for mobile applications , 2001, Nature.

[39]  Siegmar Roth,et al.  Hydrogen adsorption in different carbon nanostructures , 2005 .

[40]  M. Bowers,et al.  Mn+(H2)n and Zn+(H2)n Clusters: Influence of 3d and 4s Orbitals on Metal−Ligand Bonding , 1997 .

[41]  X. Sha,et al.  First-principles study of the structural and energetic properties of H atoms on a graphite (0001) surface , 2002 .

[42]  X. Sha,et al.  Adsorption of hydrogen and deuterium atoms on the (0001) graphite surface , 2002 .

[43]  F. Peeters,et al.  Electric Field Activated Hydrogen Dissociative Adsorption to Nitrogen-Doped Graphene , 2010 .

[44]  J. S. Arellano,et al.  Density functional study of adsorption of molecular hydrogen on graphene layers , 2000 .

[45]  Ronghu Wu,et al.  IRMPD spectra of Gly.NH4 + and proton-bound betaine dimer: evidence for the smallest gas phase zwitterionic structures. , 2008, Journal of mass spectrometry : JMS.

[46]  N. Russo,et al.  The performance of density functional based methods in the description of selected biological systems and processes. , 2012, Physical chemistry chemical physics : PCCP.

[47]  F. Peeters,et al.  The electric field as a novel switch for uptake/release of hydrogen for storage in nitrogen doped graphene. , 2011, Physical chemistry chemical physics : PCCP.

[48]  Yoshiyuki Kawazoe,et al.  Clustering of Ti on a C60 surface and its effect on hydrogen storage. , 2005, Journal of the American Chemical Society.

[49]  D. Henwood,et al.  Ab initio investigation of molecular hydrogen physisorption on graphene and carbon nanotubes , 2007 .

[50]  V. Dryza,et al.  Spectroscopic study of the benchmark Mn+-H2 complex. , 2009, The journal of physical chemistry. A.

[51]  Sanjeev S. Seahra,et al.  2175 Å and 3.4 Micron Absorption Bands and Carbon Depletion in the Diffuse Interstellar Medium , 1999 .

[52]  J. Reimers,et al.  Hydrogen bonding and reactivity of water to azines in their S1 (n,π*) electronic excited states in the gas phase and in solution. , 2012, Physical chemistry chemical physics : PCCP.

[53]  M. Ganji,et al.  Adsorption of H2S molecules by cucurbit[7]uril: an ab initio vdW-DF study , 2013 .

[54]  Ferdi Schüth,et al.  Improved Hydrogen Storage Properties of Ti‐Doped Sodium Alanate Using Titanium Nanoparticles as Doping Agents , 2003 .

[55]  Andreas Züttel,et al.  Hydrogen storage in carbon nanostructures , 2002 .

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

[57]  H. Nakanishi,et al.  First principles studies for the dissociative adsorption of H2 on graphene , 2003 .

[58]  F. Peeters,et al.  High-capacity hydrogen storage in Al-adsorbed graphene , 2010 .