Ab Initio Molecular Dynamics Study of Dissociative Adsorption of H2 on Defective Graphene-supported Cu19 Cluster
-
Abstract: The dissociative adsorption of H2 on Cu19 and defective graphene-supported Cu19 clusters are investigated using ab initio molecular dynamics. The molecular-level trajectories show that, on Cu19, the preferred adsorption site is the bridge-hollow site, where the two H atoms are adsorbed at the bridge and hollow sites beside a Cu atom, with an adsorption energy of –0.74 eV. In contrast, on the defective graphene-supported Cu19 cluster, the favorite adsorption site is located where the two H atoms are adsorbed at hollow-hollow sites with an adsorption energy of –1.27 eV. In general, the average adsorption energy on the defective graphene-supported Cu19 cluster is –1.07 eV, which is about 84% larger than that of –0.58 eV on the Cu19 cluster. This indicates that the adsorption capacity is greatly enhanced for the dissociative adsorption of H2 on the defective graphene-supported Cu19 cluster. The d-band center shifts to the Fermi level, illustrating the enhanced adsorption capacity on the defective graphene-supported Cu19 cluster. The integrated crystal orbital Hamilton population analysis reveals that stronger bond interactions between hydrogen atoms with their bonded Cu atoms lead to much larger adsorption energies on the defective graphene-supported Cu19 cluster compared to the Cu19 cluster.
-
Figure 1. Structures of the reactants. (a) H2, (b) Cu19 cluster, and (c) defective graphene-supported Cu19 cluster. The indicated units of the bond lengths are in angstroms.
Figure 2. Potential energy versus time for the molecular-level dissociative adsorption of H2: (a) at a bridge-hollow site on the Cu19 cluster, (b) at a hollow-hollow site on the graphene-supported Cu19 cluster.
Figure 3. The structures of final adsorption states at bridge-hollow sites and bridge-bridge sites of the dissociative adsorption of H2 on the Cu19 cluster. The indicated units of the bond lengths are in angstroms.
Figure 4. Structures of final adsorption states at hollow–hollow sites and bridge–hollow sites of the dissociative adsorption of H2 on the graphene-supported Cu19 cluster. The indicated units of the bond lengths are in angstroms.
Figure 5. The pDOS of the d-orbitals for Cu19 and Cu19/G. The blue dashed line represents the location of d-band center, and the red solid line indicates the location of Fermi level Ef.
Figure 6. (a) The relationship between ICOHP value and adsorption energy for every adsorption state on both Cu19 and Cu19/G. (b) The relationship between the charge (Δe) transferred from Cu atoms to the two H atoms and adsorption energy for every adsorption state on Cu19 and Cu19/G.
Table I. The H2 dissociative adsorption energy
$E_{\mathrm{a}\mathrm{d}}$ of every adsorption state (Ad. state) on Cu19 and Cu19/G.Cu19 Cu19/G Ad. state Ead/eV Ad. state Ead/eV BH1 −0.74 BH1/G −1.00 BH2 −0.58 BH2/G −1.06 BH3 −0.63 HH1/G −0.92 BH4 −0.49 HH2/G −0.98 BH5 −0.48 HH3/G −1.20 BH6 −0.64 HH4/G −1.27 BB1 −0.48 BB2 −0.62 
下载: 导出CSV
-
[1] B. Sakintuna, F. Lamari-Darkrim, and M. Hirscher, Int. J. Hydrogen Energy 32, 1121 (2007). doi: 10.1016/j.ijhydene.2006.11.022 [2] R. S. Dhayal, W. E. van Zyl, and C. W. Liu, Dalton Trans. 48, 3531 (2019). doi: 10.1039/C8DT04639E [3] S. Sakong and A. Groß, Surf. Sci. 525, 107 (2003). doi: 10.1016/S0039-6028(02)02550-5 [4] S. Amaya-Roncancio, C. Toncón-Leal, I. Arellano-Ramírez, D. A. Torres-Cerón, E. Restrepo-Parra, and K. Sapag, Chem. Phys. 559, 111546 (2022). doi: 10.1016/j.chemphys.2022.111546 [5] L. Álvarez-Falcón, F. Viñes, A. Notario-Estévez, and F. Illas, Surf. Sci. 646, 221 (2016). doi: 10.1016/j.susc.2015.08.005 [6] E. W. Smeets, G. Füchsel, and G. J. Kroes, J. Phys. Chem. C 123, 23049 (2019). doi: 10.1021/acs.jpcc.9b06539 [7] G. H. Guvelioglue, P. Ma, X. He, R. C. Forrey, and H. Cheng, Phys. Rev. B 73, 155436 (2006). doi: 10.1103/PhysRevB.73.155436 [8] F. Göltl, C. Houriez, M. Guitou, G. Chambaud, and P. Sautet, J. Phys. Chem. C 118, 5374 (2014). doi: 10.1021/jp4118634 [9] E. C. Tyo and S. Vajda, Nat. Nanotech. 10, 577 (2015). doi: 10.1038/nnano.2015.140 [10] Z. Luo, A. W. Castleman Jr., and S. N. Khanna, Chem. Rev. 116, 14456 (2016). doi: 10.1021/acs.chemrev.6b00230 [11] M. Peng, C. Dong, R. Gao, D. Xiao, H. Liu, and D. Ma, ACS Cent. Sci. 7, 262 (2020). [12] L. Triguero, U. Wahlgren, P. Boussard, and P. Siegbahn, Chem. Phys. Lett. 237, 550 (1995). doi: 10.1016/0009-2614(95)00353-6 [13] X. J. Kuang, X. Q. Wang and G. B. Liu, Transit. Met. Chem. 35, 841 (2010). doi: 10.1007/s11243-010-9402-x [14] G. H. Guvelioglu, P. Ma, X. He, R. C. Forrey, and H. Cheng, Phys. Rev. Lett. 94, 026103 (2005). doi: 10.1103/PhysRevLett.94.026103 [15] L. Ma, M. Melander, T. Weckman, S. Lipasti, K. Laasonen, and J. Akola, J. Mol. Graphics Model. 65, 61 (2016). doi: 10.1016/j.jmgm.2016.02.007 [16] F. Montejo-Alvaro, J. Oliva, A. Zarate, M. Herrera-Trejo, H. Hdz-García, and A. Mtz-Enriquez, Phys. E 110, 52 (2019). doi: 10.1016/j.physe.2019.02.005 [17] Y. Yang, A. C. Reber, S. E. Gilliland III, C. E. Castano, B. F. Gupton, and S. N. Khanna, J. Phys. Chem. C 122, 25396 (2018). doi: 10.1021/acs.jpcc.8b07538 [18] F. Meng, M. Peng, Y. Chen, X. Cai, F. Huang, L. Yang, X. Liu, T. Li, X. Wen, N. Wang, D. Xiao, H. Jiang, L. Xia, H. Liu, and D. Ma, Appl. Catal. B: Environ. 301, 120826 (2022). doi: 10.1016/j.apcatb.2021.120826 [19] R. Shi, J. Zhao, S. Liu, W. Sun, H. Li, P. Hao, Z. Li, and J. Ren, Carbon 130, 185 (2018). doi: 10.1016/j.carbon.2018.01.011 [20] D. H. Lim, J. H. Jo, D. Y. Shin, J. Wilcox, H. C. Ham, and S. W. Nam, Nanoscale 6, 5087 (2014). doi: 10.1039/C3NR06539A [21] T. Abdollahi and D. Farmanzadeh, J. Alloys Compd. 735, 117 (2018). doi: 10.1016/j.jallcom.2017.11.051 [22] S. Darby, T. V. Mortimer-Jones, R. L. Johnston, and C. Roberts, J. Chem. Phys. 116, 1536 (2002). doi: 10.1063/1.1429658 [23] M. Yang, K. A. Jackson, C. Koehler, T. Frauenheim, and J. Jellinek, J. Chem. Phys. 124, 024308 (2006). doi: 10.1063/1.2150439 [24] M. Kabir, A. Mookerjee, and A. K. Bhattacharya, Phys. Rev. A 69, 043203 (2004). doi: 10.1103/PhysRevA.69.043203 [25] S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010). doi: 10.1063/1.3382344 [26] G. Kresse and J. Furthmüller, Phys. Rev. B 54, 11169 (1996). doi: 10.1103/PhysRevB.54.11169 [27] G. Kresse and J. Furthmüller, Comput. Mater. Sci. 6, 15 (1996). doi: 10.1016/0927-0256(96)00008-0 [28] P. E. Blöchl, Phys. Rev. B 50, 17953 (1994). doi: 10.1103/PhysRevB.50.17953 [29] J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996). doi: 10.1103/PhysRevLett.77.3865 [30] W. Tang, E. Sanville, and G. Henkelman, J. Phys.: Condens. Matter 21, 084204 (2009). doi: 10.1088/0953-8984/21/8/084204 [31] B. Hammer and J. K. Nørskov, Adv. Catal. 45, 71 (2000). doi: 10.1016/S0360-0564(02)45013-4 [32] R. Dronskowski and P. E. Blöchl, J. Phys. Chem. 97, 8617 (1993). doi: 10.1021/j100135a014 [33] R. Nelson, C. Ertural, J. George, V. L. Deringer, G. Hautier, and R. Dronskowski, J. Comupt. Chem. 41, 1931 (2020). doi: 10.1002/jcc.26353 [34] S. Maintz, V. L. Deringer, A. L. Tchougréeff, and R. Dronskowski, J. Comput. Chem. 37, 1030 (2016). doi: 10.1002/jcc.24300 -
点击查看大图
计量
- 文章访问数: 347
- HTML全文浏览量: 163
- PDF下载量: 14
- 被引次数: 0
