Applied Surface Science 296 (2014) 204208

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Prediction of hydrogen storage on Y-decorated graphene: A density functional theory study

Wenbo Liu a, , Yang Liu a , Rongguo Wang b
a b

School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150080, PR China National Key Laboratory for Advanced Composites in Special Environment, Harbin Institute of Technology, Harbin 150080, PR China

a r t i c l e

i n f o

a b s t r a c t
Yttrium decorated graphene has been investigated as a potential carrier for high density hydrogen storage. The adsorption energy and optimized geometry for yttrium on pristine and boron doped graphene have been studied by DFT calculations. The clustering and stability of isolated yttrium atoms on graphene has also been considered. For yttrium decorated boron doped graphene, each yttrium can attach six hydrogen molecules with average adsorption energy of 0.568 eV per hydrogen molecule and the hydrogen storage capacity of this material is 5.78 wt.%, indicating yttrium decorated boron doped graphene as a promising hydrogen storage candidate. 2014 Elsevier B.V. All rights reserved.

Article history: Received 2 December 2013 Received in revised form 13 January 2014 Accepted 14 January 2014 Available online 25 January 2014 Keywords: Hydrogen storage capacity Yttrium decorated graphene Boron substitution

1. Introduction Hydrogen, a renewable and clean energy source, is widely accepted as an ideal substitution of fossil fuels [1]. The safety of transportation and efciency of storage are serious bottlenecks which block the application of hydrogen [2]. The storage capacity and binding energy between hydrogen molecules and the storage media are two basic requirements that must be met. According to U.S. Department of Energy (DOE), the storage capacity of a promising candidate should be at least 5.5 wt.%. The binding energy should be in the range of 0.2 and 0.7 eV per H2 , which is suitable for both hydrogen adsorption and desorption of hydrogen molecules [3]. Many researches have been devoted to synthesize hydrogen storage candidates and predict the hydrogen storage capacities of these materials, such as metal-organic frameworks, organic polymer network, and carbon nano materials. Graphene [4], an atomic layer of carbon, has aroused extensive investigation due to its unique electronic structure and mechanical properties [5]. Compared to other materials of carbon family, graphene has an extremely high specic surface area which is an advantage for storage of atoms or molecules. However, it has been proved that pristine graphene binds weakly with hydrogen molecules, and the binding energy between them is about 0.15 eV per H2 molecule. Doping or coating foreign atoms is an effective way to change

Corresponding author at: No. 2, Yikuang Street, Nan Gang district, Harbin, Hei Longjiang Province 150080, China. Tel.: +86 0451 86402399; fax: +86 0451 86402399. E-mail address: liuwenbo@hit.edu.cn (W. Liu). 0169-4332/$ see front matter 2014 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2014.01.087

the electronic structure of graphene and the binding mechanism between hydrogen and the storage systems [6]. Alkali atoms such as Li decorated graphene gives an excellent performance on hydrogen storage [7]. Although Li/graphene can reach a high hydrogen storage capacity, the interaction between Li atom and hydrogen molecules is pure physisorption, which leads to a poor binding energy at room temperature [8]. Ti coating is another option [911]. Liu and coworkers calculated the hydrogen storage capacity of Ti/graphene [11]. Results showed that each Ti atom could capture four hydrogen molecules with a moderate binding energy. However, the large cohesive energy of bulk Ti makes neighboring metal atoms aggregate and the clustering of Ti nally cause a signicant degradation of hydrogen storage capability. Recently, Ca has been proved to been an excellent adatom to enhance the storage capability of graphene sheet. The interaction between Ca atom and hydrogen molecule is Kubas-type binding, which contains both charge transfer and hybridization [1215]. The d-orbital state of Ca plays an important role in the enhancement of the binding energy. The works mentioned above are on one basic hypothesis that hydrogen molecules are the only gas molecules which are attached on the hydrogen storage material. However, in realistic conditions, other gas molecules like oxygen will be inevitably incorporated into hydrogen storage medium during the process of hydrogen adsorption. With the purpose of coming closer to realistic conditions, the group of A. Sigal studied the effect of oxygen on the hydrogen storage capacity of metal decorated graphene [16,17]. Yttrium, a rare earth element, has been incorporated into metal borides and showed promising potential to be used as hydrogen storage devices [18]. Because the electron conguration of Y is 4d1 5s2 , one may hypothesize that Y/graphene may bind with

W. Liu et al. / Applied Surface Science 296 (2014) 204208

205

hydrogen molecules as Kubas-type and be an excellent hydrogen storage candidate. In this paper, we carried out rst-principles calculations based on DFT to investigate the hydrogen storage capacity of Y decorated pristine graphene and B-doped graphene. Stability and the clustering of metal decorating on the system have also been considered. 2. Simulation details Numerical calculations were performed within spin-polarized DFT using DMol3 package which has already been applied successfully to graphene in various instances [19]. The exchange and correlation potential were treated using local density approximation (LDA) with Perdew-Wang (PWC) functional which is commonly used to calculate the binding energy and geometries of hydrogen molecules adsorption [5]. DFT semi-core pseudo potentials (DSPP) treatment was adopted as the core treatment for relativistic effects. A double numerical plus polarization (DNP) with a polarization function was selected to be basis sets. K-point was set to 10 10 1 within the MonkhorstPack scheme. We used 3 3 1 supercell of graphene with a vacuum thick to avoid the interaction between the adjacent layers. ness of 20 A which was in consistent The calculated C C bond length was 1.42 A with the experimental datum. For B substitution doped graphene depicted in Fig. 3(a), each lattice contained two B atoms which brought the B doping concentration of 11.1 at.%. Similar congurations of B doping graphene can also be found in other previous works [15]. 3. Results and discussion We rstly study Y adsorption behavior on pristine graphene based on the assumption that Y atoms disperse uniformly on graphene sheet. Similar as other rare earth metal atoms attaching on carbon nano materials [20,21], the favorite adsorption site for an isolated Y atom on single side of graphene is above the center of a hexagonal ring. Meanwhile, the distance between Y and graphene The adsorption energy of Y on graphene Ead [Y] sheet lY G is 2.03 A. is 2.064 eV, which is determined by the following function, Ead [Y] = E Y E [Y] E [G], G (1)
Fig. 1. Optimized geometries of twelve hydrogen molecules adsorption on Y coated double-sided pristine graphene. Green and dark gray balls denote Y and carbon atoms. Light gray and yellow balls are hydrogen molecules attaching on up and opposite side of graphene. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)

where E [Y/G] denotes the total energy of Y/graphene after fully relaxation. E [Y] and E [G] are the total energies of an isolated metal atom and graphene sheet, respectively. Before attaching on graphene, the electronic conguration of Y is 4d1 5s2 . Mulliken population analysis shows that after the adsorption of Y, the electronic congurations of Y and C change to 4d1.416 5s0.850 5p0.112 and 2s1.292 2p2.744 , respectively. Compare to the contribution of other orbitals, the change of electrons of C 3d-orbital is negligible. It is obvious that 1.150 e electrons transfer from Y-5s orbital to C-2p orbital. As the Y atom approaching to graphene sheet, Y atom is positively charged with charge of 0.522 e, while the carbon atoms near Y are negatively charged. This electron potential difference arouses an electric eld between metal atom and graphene, which leads to back-donation of some electrons from the occupied orbitals of graphene to Y-4d and 5p orbitals and enhance the interaction between them. The donation/back-donation binding mechanism can also be found in the case of Ca decorating graphene and carbon nanotubes [22,23]. It has widely been proved that more metal atoms attachment can lead to an enhancement of hydrogen storage capacity [24,25]. When the 2nd Y atom approaches on the other side of graphene, the most favorable adsorption site is hollow site of the same hexagon. Meanwhile, Y carries more charges of 0.578 e, and the carbon atoms

nearby are more negatively charged. This results in a stronger electric eld and thus brings up to a smaller vertical distance lY G of between the adatom and graphene sheet. Calculation results 1.96 A show that the adsorption energy of the 2nd Y on the other side of graphene is 3.392 eV, indicating the enhancement of the binding energy between the 2nd attached Y and graphene. For Y decorated single-sided graphene, once a hydrogen molecule approaches to Y atom, the bond length of hydrogen lH H is elongated and each hydrogen atom carries positive charge of 0.008 e and 0.005 e due to the electron transfer from hydrogen to Y. The adsorption of hydrogen leads to a decrease of the vertical distance between Y and graphene, and an increase of charge transfer from metal atom to the ground sheet. When more molecules are attached, the charge of Y decreases due to the directly electron transfer from H2 to Y atom. Fig. 1 depicts the relaxed structure of twelve hydrogen molecules adsorbing on Y coated double-sided graphene with periodic boundary conditions. It is observed that each metal atom can catch 6 H2 without any dissociation of hydrogen molecules. The

206

W. Liu et al. / Applied Surface Science 296 (2014) 204208

Table 1 The average adsorption energy Ead [H2 ], charges of Y and the geometries of hydrogen molecules attachment on Y decorated single and double-side pristine graphene. Structures Y/G/H2 Y/G/2H2 Y/G/3H2 Y/G/4H2 Y/G/5H2 Y/G/6H2 2Y/G/2H2 2Y/G/4H2 2Y/G/6H2 2Y/G/8H2 2Y/G/10H2 2Y/G/12H2 Ead [H2 ] (eV) 0.671 0.688 0.693 0.721 0.663 0.633 0.398 0.466 0.471 0.527 0.506 0.495 Charge of Y (e) up/down 0.532 0.308 0.169 0.001 0.204 0.437 0.520/0.552 0.438/0.496 0.293/0.296 0.130/0.136 0.045/0.046 0.295/0.295 LYC () up/down 2.17 2.20 2.25 2.27 2.28 2.37 1.98/1.99 2.00/2.09 2.09/2.08 2.16/2.16 2.16/2.16 2.24/2.23

attachment of the 7th H2 leads to a weak binding between molecule and the metal atom. The average adsorption energies and optimized geometries of the adsorption of H2 on Y coating single and doubleside graphene are summarized in Table 1. The average adsorption energy of hydrogen on Y/G is dened by Ead [H2 ] = E [Y/G/nH2 ] E [Y/G] nE [H2 ] , n (2)

Fig. 2. (a) and (b) are optimized geometries of Y decorated single and double side of B-doped graphene, respectively. Green and dark gray balls denote Y and carbon atoms. B atoms are described by pink balls. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)

where E [Y/G] and E [H2 ] represent the total energy of Y decorated single-side graphene and the energy of free hydrogen molecule. E [Y/G/nH2 ] denotes the total energy of Y/G/nH2 system after fully relaxation, and n is the number of the adsorbed hydrogen molecules. Similarly, the average adsorption energy of hydrogen molecules on 2Y/G is calculated by Ead [H2 ] = E [2Y/G/nH2 ] E [2Y/G] nE [H2 ] , n (3)

where E [2Y/G/nH2 ] is the total energy of hydrogen molecules and Y decorated double-side graphene after relaxation. For the case of single side coating, it is observed that as more hydrogen molecules are attached, the charge of Y decreases. The vertical distance between Y and graphene increases, indicating a decline of the binding energy between them. When Y/G attracts four H2 , the binding energy between the 4th H2 and Y/G is the strongest. Meanwhile, Y atom carries 0.001 e positive charge. When the 5th and 6th molecules approach to Y atom, instead of sharing the same level with the four H2 molecules, they move to an upper layer, and Y atom is negatively charged. As the number of attached hydrogen molecules changes from one to six, the adsorption energy of hydrogen on Y decorated single side of graphene does not change signicantly. Similar phenomena are also observed in the case of hydrogen molecules adsorption on Y decorated doublesided graphene. In the congurations of 6H2 /Y/G and 12H2 /2Y/G, the bonds of H H are all elongated, indicating the weakening of 1s orbital of hydrogen. Hydrogen molecules are adsorbed positively charged and without any dissociation. For Y decorated double-side graphene, the hydrogen storage capacity is 5.78 wt.% with the average adsorption energy of 0.495 eV per H2 , indicating the potential of Y decorated double-sided graphene as a promising hydrogen storage candidate. The above predictions of hydrogen storage capacity are on the assumption that metal atoms are uniformly adsorbed on graphene sheet without any aggregation. However, the metal binding energy on pristine graphene is signicantly smaller than the cohesive energy of bulk Y material (4.33 eV [26]), indicating the trend of aggregation of the isolated Y atoms. This phenomenon can also be found when isolated Y atoms decorated on carbon nanotubes [27]. B-doping had been proved to be an effective way to change the electronic structure of graphene, and B doped graphene has been successfully synthesized through chemical vapor deposition [28,29]. When a B atom substitutionally incorporates into graphene

sheet, it does not evoke large lattice distortion because it is a neighbor to carbon in the element table and has a similar atomic diameter as carbon atom. We introduce B atoms to 3 3 1 graphene supercell with the doping concentration of 11.1 at.%. It has already been obtained that the B doping concentration can be up to 20 at.%. Thus, it is believable that our model with a lower B concentration is stable [30]. After two B atoms substitutionally doped with two C atoms in (experimenthe same hexagon, C C bond are shorten from 1.42 A The bond length of B C is tal datum of pure graphene) to 1.37 A. Different adsorption sites of Y atom on B-doped graphene 1.49 A. are considered. The adsorption energy of Y on B-doped single and double-sided graphene is calculated by formula (4), Ead [mY(B/G)] = E [mY/B/G] mE [Y] E [B/G] , m (4)

where E [mY/B/G] denotes the total energy of Y on B-doped single and double-sided graphene after fully relaxation. E [Y] and E [B/G] are the total energies of an isolated metal atom and B-doped graphene sheet, respectively. m equals to one or two indicates Y decorated single or double-sided B-doped graphene. Simulation result shows that hollow site is the favorite adsorption site with the adsorption energy of 4.856 eV. Thus, the binding energy between Y and the sheet is higher than the cohesive energy of bulk Y material (4.33 eV), which indicates that B doping can successfully avoid the aggregation of Y atoms on graphene. The relaxed structure of Y on B-doped single-sided graphene is shown in Fig. 2(a). Simulation results indicate that after adsorption of Y atom, B and C atoms do not share a same vector perpendicular to graphene layer. The bond length of C C and B C in the attaching hexagon changes to 1.40 A respectively. and 1.48 A, The charge populations are also shown in Fig. 2(a). Because the conguration of B is 2s2 2p1 , B doping forms electron deciency in the structure. This electron deciency acts as a strong charge acceptor in the graphene sheet, which leads to a more efcient charge transfer from Y to the B-doped graphene. Thus, Y atom is more positively charged with 0.613 e. The electric eld formed between Y and graphene is enhanced, and thus enhances the interaction between Y and graphene. Meanwhile, the electronic conguration of Y is 4d1.122 5s0.981 5p0.284 , a result from Mulliken population analysis. Similar to the case of Y adsorbing on pristine graphene, the binding of Y and B-doped graphene also has electron donation and back donation mechanism. The electrons transfer from sheet to Y

W. Liu et al. / Applied Surface Science 296 (2014) 204208

207

Fig. 4. PDOS plots of H, Y, B, and C atoms in Y decorated double-sided B/graphene. The PDOS of Y before the adsorption of hydrogen molecules is also drawn. Solid, dash, and dot lines denote s, p, and d orbitals. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)

Fig. 3. Optimized structures of twelve hydrogen molecules adsorption on Y coated double-sided graphene with boron doping. Green, pink, and dark gray balls denote Y, boron and carbon atoms. Light gray and yellow balls are hydrogen molecules attaching on up and opposite side of graphene, respectively. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)

4d and 5p orbital is caused by the electric eld formed between Y atom and B/graphene sheet. Fig. 2(b) depicts Y decorated double-sided B/graphene. After the decoration of the second Y on the other side of B/graphene, the curving of the sheet disappears. Each boron and carbon atoms are sharing the same coordinate vertical to the sheet. The bond lengths and 1.42 A, of B C and C C in the Y decorating hexagon are 1.49 A respectively. For Y decorated single-sided B/graphene, as the rst hydrogen molecule approaching to Y, H H bond is elongated and weakened. Each atom of hydrogen molecule carries 0.004 and 0.005 electron. The electrons transferring from hydrogen molecule to Y atom makes Y lose more electrons to the B/graphene sheet. Y and B atom carry 0.678 and 0.195 electron. On one side of graphene, the rst to forth hydrogen molecules are adsorbed around Y and parallel to B/graphene surface. Y atoms are positively charged. When the fth and sixth hydrogen are attached, they do not share the same level with the four hydrogen molecules attached before. They move to the upper layer and have some angle with the lower

layer of hydrogen. The same phenomenon can be observed for the case of hydrogen storage of Y decorated double-sided B/graphene, depicted in Fig. 3. L1 in Fig. 3 indicates hydrogen molecules in the layer that parallel to graphene sheet, and L2 denotes hydrogen molecules in the layer beyond L1. Each supercell can store twelve hydrogen molecules with adsorption energy of 0.568 eV per hydrogen. When we add more hydrogen molecules to the system, they do not make strong bond with Y. For 12H2 /2Y/B/graphene, all hydrogen molecules are positively charged, and Y carries negative charge of 0.475 e. Twelve molecules transfer 1.340 electrons to two Y atoms, meanwhile Y atoms also get parts of electrons from B/graphene sheet due to the back donation of electrons. More specic result can be obtained by Mulliken population calculations. Before and after 12 hydrogen adsorption on Y, the electronic congurations of Y are 5s0.904 4d1.33 5p0.201 and 5s0.476 4d2.356 5p0.642 , respectively. The electrons transfer from Y 5s orbital to B/graphene is caused by the electric eld between Y atom and the sheet. This electron transferring from hydrogen and B/graphene to Y plays an important role in the enhancement of hydrogen storage capacity of this system. The analysis of density of states gives insight information about the interaction among twelve hydrogen molecules and Y decorated double-sided B/graphene. From Fig. 4, it is obvious that 5s orbital of Y around Fermi level disappears after the attachment of hydrogen molecules. There are several overlaps of main peaks of 1s orbital of hydrogen in L1 and Y 5d orbital at 7.5, 0.5 and 3.7 eV, indicating strong binding and hybridizing between orbitals of hydrogen and Y. The PDOS overlaps between hydrogen in L1 and L2 at several energy levels indicates the strong interaction and hybridization between them. Thus, the enhanced adsorption of hydrogen in L2 is mainly attributed to the interaction with the hydrogen in L1. The polarization of H (L2) also makes some contribution to the enhancement of the binding energy of hydrogen. PDOS result also shows that there are no evident hybridization between hydrogen and B/graphene. 4. Conclusion In summary, we studied Y decorated pristine and boron doped graphene as a candidate for hydrogen storage using LDA-DFT calculations. Although Y decorated double-sided pristine graphene can meet the criterions which U.S. DOE proposed, the binding energy between Y and graphene was smaller than the cohesive energy of bulk Y material, indicating the trend of aggregation of Y on graphene which will cause a decrease of hydrogen storage capacity. Boron substitution successfully increased the binding energy between Y and B/graphene which was larger than cohesive energy

208

W. Liu et al. / Applied Surface Science 296 (2014) 204208 [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] Z.M. Ao, F.M. Peeters, Phys. Rev. B 81 (2010) 205406. F.D. Wang, F. Wang, N.N. Zhang, Chem. Phys. Lett. 555 (2013) 212216. Y. Li, G.F. Zhao, C.S. Liu, Int. J. Hydrogen Energy 37 (2012) 57545761. M. Pumera, Energy Environ. Sci. 4 (2011) 668674. M.I. Rojas, E.P.M. Leiva, Phys. Rev. B 76 (2007) 155415. S.B. Chu, L.B. Hu, X.R. Hu, Int. J. Hydrogen Energy 36 (2011) 12324. Y.L. Liu, L. Ren, Y. He, J. Phys. Condens. Mater. 22 (2010) 445301. R.F. Lu, D.W. Rao, Z.L. Lu, J. Phys. Chem. C (2012) 2129121296. Y. Gao, N.Q. Zhao, J.J. Li, Int. J. Hydrogen. Energy (2012) 1183511841. C. Li, J.B. Li, F.M. Wu, J. Phys. Chem. C (2011) 2322132252. E. Beheshti, A. Nojeh, P. Servati, Carbon 49 (2011) 15611567. A. Sigal, M.I. Rojas, E.P.M. Leiva, Int. J. Hydrogen Energy 36 (2011) 35373546. A. Sigal, M.I. Rojas, E.P.M. Leiva, Phys. Rev. Lett. 107 (2011) 158701. A. Remhof, A. Borgschulte, O. Friedrichs, Scr. Mater. 66 (2012) 280283. W. Liu, A. Savara, J. Phys. Chem. Lett. 3 (2012) 582586. Y. Ito, J.H. Warner, R. Brown, Phys. Chem. Chem. Phys. 12 (2010) 16181623. K.M. Fair, X.Y. Cui, L. Li, Phys. Rev. B 87 (2013) 014102. R.F. Lu, D.W. Rao, Z.L. Lu, J. Phys. Chem. C 116 (2012) 2129121296. M. Li, Y.F. Li, Z. Zhou, Nano Lett. 9 (2009) 19441948. L. Wang, K. Lee, Y.Y. Sun, ACS Nano 3 (2009) 29953000. Z.W. Zhang, W.T. Zheng, Q. Jiang, Int. J. Hydrogen. Energy 37 (2012) 50905099. X.B. Xiao, W.B. Zhang, W.Y. Yu, N. Wang, B.Y. Tang, Phys. B 404 (2009) 22342240. B. Chakrabory, P. Modak, S.J. Banerjee, Phys. Chem. C 116 (2012) 2250222508. J. Kang, Y.H. Kim, G.C. Glatzmaier, J. Chem. Phys. 139 (2013) 011709. H. Wang, Y. Zhou, D. Wu, Small 9 (2013) 13161320. T. Shirasaki, A. Derre, M. Menetrier, A. Tressaud, S. Flandrois, Carbon 38 (2000) 1461.

of Y. Thus, the uniform dispersion of Y on B/graphene was reliable. The optimized geometry of hydrogen molecules adsorption of Y decorated double-sided B/graphene has been obtained. Each Y atom can attach at most 6 hydrogen molecules with average adsorption energy of 0.568 eV, which brought out the hydrogen storage capacity of 5.78 wt.%. The enhancement of hydrogen binding energy is mainly caused by the hybridization of Y 5d and H 1s orbital. The interaction of hydrogen molecules in L2 and L1 played a major role for the adsorption of the hydrogen in L2. Acknowledgements The building of models and DFT calculations are supported by the High Performance Computing Center of Harbin Institute of Technology. References
[1] W. Liu, Y.H. Zhao, Y. Li, Q. Jiang, E.J. Lavernia, J. Phys. Chem. C 113 (2009) 20282033. [2] Z.M. Ao, A.D. Hernandez-Nieves, F.M. Peeters, Phys. Chem. Chem. Phys. 14 (2012) 14631467. [3] Z.W. Zhang, J.C. Li, Q. Jiang, J. Phys. Chem. C 114 (2010) 77337737. [4] K.S. Novoselov, A.K. Geim, S.V. Morozov, Science 306 (2004) 666669.