Theoretical Study of CH<sub>4</sub> Adsorption and C-H Bond Activation of CH<sub>4</sub> on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au)

Tetsuya Ohkawa; Kei Kuramoto

doi:doi:10.11648/j.ijctc.20160403.12

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Theoretical Study of CH₄ Adsorption and C-H Bond Activation of CH₄ on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au)

Tetsuya Ohkawa, Kei Kuramoto

Published in International Journal of Computational and Theoretical Chemistry (Volume 4, Issue 3)

Received: 29 November 2016 Accepted: 8 December 2016 Published: 10 January 2017

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Abstract

We have investigated the CH₄ adsorption and the C-H bond breaking activation on the metal ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au) and M@M (111)/H (covered by hydrogen atoms) 3 and 1-layer surfaces (4-type surfaces) using spin-polarized Density Functional Theory (DFT). We find that the adsorption energies of methane are related to the d-band center of metal ad-atoms. In particular, the distances between CH₄ and Ni, Pd, and Pt ad-atoms of 4-type surfaces are shortened and the adsorption energies of CH₄ on metal ad-atoms are stronger than the perfect surfaces because the d-band center of metal ad-atoms are close to the Fermi level. Furthermore, we have investigated the activation barrier energies of C-H bond breaking of CH₄ on Ni, Pt, and Ag ad-atoms of 4-type surfaces because Pt ad-atom exhibits stronger adsorption energy of CH₄, Ag ad-atom exhibits weaker ones, and Ni utilizes for the steam reforming reaction. We find that Ni and Pt ad-atoms show lower activation barrier energies, and they are related to the CH₄ adsorption energies as well as the d-band centers.

Published in	International Journal of Computational and Theoretical Chemistry (Volume 4, Issue 3)
DOI	10.11648/j.ijctc.20160403.12
Page(s)	21-30
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2017. Published by Science Publishing Group

Keywords

Methane Adsorption, C-H Bond Breaking, Ad-atom, Density Functional Theory

References

[1]	J. R. Rostrup-Nielsen, J. H. B. Hansen, J. Catal. 144, 38 (1993).
[2]	M. C. J. Brandford, M. A. Vannice, Appl. Catal. A Gen. 142, 97 (1996).
[3]	K. Tomoshige, Y. G. Chen, K. Fujimoto, J. Catal. 181, 91 (1999).
[4]	K. Otsuka, S. Kobayashi, S. Takenaka, Appl. Catal. A Gen. 190, 261 (2000).
[5]	A. Erdöhelyi, J. Cserényi, F. Solymosi, J. Catal. 141, 287 (1993)
[6]	R. Takahashi, S. Sato, T. Sodesawa, M. Kato, S. Takenaka, S. Yoshida, J. Catal. 204, 259 (2001).
[7]	O. Tokunaga, Y. Osada, S. Ogasawara, Fuel 68, 990 (1989).
[8]	S. Tang, L. Li, J. Lin, H. C. Zeng, K. L. Tan, K. Li, J. Catal. 194, 424 (2000).
[9]	A. Malaika, B. Krzyzynska, M. Kozlowski, Int. J. Hydrogen Energy 35, 7470 (2010).
[10]	J. M. Ginsburg, J. Pina, T. E. Solh, H. I. de Lasa, Ind. Eng. Chem. Res. 44, 4846 (2005).
[11]	J. R. Rostrup-Nielsen, Catal. Today 37, 225 (1997).
[12]	V. C. H. Kroll, H. M. Swaan, C. Mirodatos, J. Catal. 161, 409 (1996).
[13]	H. M. Swaan, V. C. H. Kroll, G. A. Martin, C. Mirodatos, Catal. Today 21, 571 (1994).
[14]	H. F. Abbas, W. M. A. W. Daud, Int. J. Hydrogen Energy 35, 141 (2010).
[15]	C. H. Bartholomew, Appl. Catal. A Gen. 212, 17 (2001).
[16]	H. S. Bengaard, J. K. Nørskov, J. Sehested, B. S. Clausen, L. P. Nielsen, A. M. Molenbroek, and J. R. Rostrup-Nielsen, J. Catal. 209, 365 (2002).
[17]	J. R. Rostrup-Nielsen, Springer, Berlin (1984) (editor: J. R. Anderson, M. Boudart).
[18]	C. T. Rettner, H. E. Pfnur, and D. J. Auerbach, Phys. Rev. Lett. 54, 2716 (1985).
[19]	C. T. Rettner, H. E. Pfnur, and D. J. Auerbach, J. Chem. Phys. 84, 4163 (1986).
[20]	P. M. Holmblad, J. Wambach and I. Chorkendorff, J. Chem. Phys. 102, 8255 (1995).
[21]	L. B. F. Juurlink, P. R. McCabe, R. R. Smith, C. L. DiCologero, and A. L. Utz, Phys. Rev. Lett. 83, 868 (1999).
[22]	M. B. Lee, Q. Y. Yang, and S. T. Ceyer, J. Chem. Phys. 87, 2724 (1987).
[23]	R. R. Smith, D. R. Killelea, D. F. DelSesto, and A. L. Utz, Science, 304, 992 (2004).
[24]	R. Bisson, M. Sacchi, T. T. Dang, B. Yoder, P. Maroni, and R. D. Beck, J. Phys. Chem. A, 111, 12679 (2007).
[25]	H. Yang and J. L. Whitten, J. Chem. Phys. 96, 5529 (1992).
[26]	P. Kratzer, B. Hammer, and J. K. Nørskov, J. Chem. Phys. 105, 5595 (1996).
[27]	S. Nave, A. K. Tiwari, and B. Jackson, J. Chem. Phys. 132, 054705 (2010).
[28]	T. P. Beebe Jr., D. W. Goodman, B. D. Kay, and J. T. Yates Jr., J. Chem. Phys. 87, 2305 (1987).
[29]	F. Abild-Pedersen, O. Lytken, J. Engbæk, G. Nielsen, I. Chorkendorff, and J. K. Nørskov, Surf. Sci. 590, 127 (2005).
[30]	A. Kokaji, N. Bonini, S. de Gironcoli, C. Sbraccia, G. Fratesi, and S. Baroni, J. Am. Chem. Soc. 128, 12448 (2006).
[31]	P. L. Rodríguez-Kessler and A. R. Rodríguez-Domínguez, J. Phys. Chem. C 119, 12378 (2015).
[32]	S. Yuan, L. Meng, and J. Wang, J. Phys. Chem. C 117, 14796 (2013).
[33]	P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G. L. Chiarotti, M. Cococcioni, I. Dabo, A. Dal Corso, S. Fabris, G. Fratesi, S. de Gironcoli, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A. P. Seitsonen, A. Smogunov, P. Umari, R. M. Wentzcovitch, J. Phys.: Condens. Matter, 21, 395502 (2009).
[34]	J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).
[35]	H. J. Monkhorst and J. D. Pack, Phys. Rev. B 13, 5188 (1976).
[36]	G. Henkelman, B. P. Uberuaga, and H. Jónsson, J. Chem. Phys. 113, 9901 (2000).
[37]	V. Shah, T. Li, K. L. Baumert, H. Cheng, and D. S. Sholl, Surf. Sci. 527, 217-227 (2003).
[38]	S. G. Wang, X. Y. Liao, J. Hu, D. B. Cao, Y. W. Li, J. Wang, and H. Jiao, Surf. Sci. 601, 1271 (2007).
[39]	H. Liu, R. Zhang, R. Yan, B. Wang, and K. Xie, Appl. Surf. Sci. 257, 8955 (2011).
[40]	R. Zhang, T. Duan, L. Ling, and B. Wang, Appl. Surf. Sci. 341, 100 (2015).
[41]	S. G. Wang, D. B. Cao, Y. W. Li, J. G. Wang, and H. J. Jiao, J. Phys. Chem. B 110, 9976 (2006).
[42]	G. Gajewski and C. W. Pao, J. Chem. Phys. 135, 064707 (2011).
[43]	K. Li, C. He, M. Jiao, Y. Wang, and Z. Wu, CARBON, 74, 255 (2014).
[44]	K. Li, M. Jiao, Y. Wang, and Z. Wu, Surf. Sci. 617, 149 (2013).
[45]	B. Hammer and J. K. Nørskov, Surf. Sci. 343, 211 (1995).
[46]	B. Hammer, Top. Catal. 37, 3 (2006).
[47]	V. Pallassana and M. Neurock, J. Catal. 191, 301 (2000).
[48]	J. Ding, Z. Qiao, W. Feng, Y. Yao, and Q. Niu, Phys. Rev. B 84, 195444 (2011).
[49]	R. M. Watwe, H. S. Bengaard, J. R. Rostrup-Nielsen, J. A. Dumesic, and J. K. Nørskov, J. Catal. 189, 16 (2000).

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APA Style

Tetsuya Ohkawa, Kei Kuramoto. (2017). Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au). International Journal of Computational and Theoretical Chemistry, 4(3), 21-30. https://doi.org/10.11648/j.ijctc.20160403.12

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ACS Style

Tetsuya Ohkawa; Kei Kuramoto. Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au). Int. J. Comput. Theor. Chem. 2017, 4(3), 21-30. doi: 10.11648/j.ijctc.20160403.12

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AMA Style

Tetsuya Ohkawa, Kei Kuramoto. Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au). Int J Comput Theor Chem. 2017;4(3):21-30. doi: 10.11648/j.ijctc.20160403.12

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@article{10.11648/j.ijctc.20160403.12,
  author = {Tetsuya Ohkawa and Kei Kuramoto},
  title = {Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au)},
  journal = {International Journal of Computational and Theoretical Chemistry},
  volume = {4},
  number = {3},
  pages = {21-30},
  doi = {10.11648/j.ijctc.20160403.12},
  url = {https://doi.org/10.11648/j.ijctc.20160403.12},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20160403.12},
  abstract = {We have investigated the CH4 adsorption and the C-H bond breaking activation on the metal ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au) and M@M (111)/H (covered by hydrogen atoms) 3 and 1-layer surfaces (4-type surfaces) using spin-polarized Density Functional Theory (DFT). We find that the adsorption energies of methane are related to the d-band center of metal ad-atoms. In particular, the distances between CH4 and Ni, Pd, and Pt ad-atoms of 4-type surfaces are shortened and the adsorption energies of CH4 on metal ad-atoms are stronger than the perfect surfaces because the d-band center of metal ad-atoms are close to the Fermi level. Furthermore, we have investigated the activation barrier energies of C-H bond breaking of CH4 on Ni, Pt, and Ag ad-atoms of 4-type surfaces because Pt ad-atom exhibits stronger adsorption energy of CH4, Ag ad-atom exhibits weaker ones, and Ni utilizes for the steam reforming reaction. We find that Ni and Pt ad-atoms show lower activation barrier energies, and they are related to the CH4 adsorption energies as well as the d-band centers.},
 year = {2017}
}

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TY  - JOUR
T1  - Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au)
AU  - Tetsuya Ohkawa
AU  - Kei Kuramoto
Y1  - 2017/01/10
PY  - 2017
N1  - https://doi.org/10.11648/j.ijctc.20160403.12
DO  - 10.11648/j.ijctc.20160403.12
T2  - International Journal of Computational and Theoretical Chemistry
JF  - International Journal of Computational and Theoretical Chemistry
JO  - International Journal of Computational and Theoretical Chemistry
SP  - 21
EP  - 30
PB  - Science Publishing Group
SN  - 2376-7308
UR  - https://doi.org/10.11648/j.ijctc.20160403.12
AB  - We have investigated the CH4 adsorption and the C-H bond breaking activation on the metal ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au) and M@M (111)/H (covered by hydrogen atoms) 3 and 1-layer surfaces (4-type surfaces) using spin-polarized Density Functional Theory (DFT). We find that the adsorption energies of methane are related to the d-band center of metal ad-atoms. In particular, the distances between CH4 and Ni, Pd, and Pt ad-atoms of 4-type surfaces are shortened and the adsorption energies of CH4 on metal ad-atoms are stronger than the perfect surfaces because the d-band center of metal ad-atoms are close to the Fermi level. Furthermore, we have investigated the activation barrier energies of C-H bond breaking of CH4 on Ni, Pt, and Ag ad-atoms of 4-type surfaces because Pt ad-atom exhibits stronger adsorption energy of CH4, Ag ad-atom exhibits weaker ones, and Ni utilizes for the steam reforming reaction. We find that Ni and Pt ad-atoms show lower activation barrier energies, and they are related to the CH4 adsorption energies as well as the d-band centers.
VL  - 4
IS  - 3
ER  -

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Author Information

Tetsuya Ohkawa

Department of Electrical Engineering and Computer Sciences, University of Hyogo, Himeji, Hyogo, Japan
Kei Kuramoto

Department of Electrical Engineering and Computer Sciences, University of Hyogo, Himeji, Hyogo, Japan

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APA Style

Tetsuya Ohkawa, Kei Kuramoto. (2017). Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au). International Journal of Computational and Theoretical Chemistry, 4(3), 21-30. https://doi.org/10.11648/j.ijctc.20160403.12

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ACS Style

Tetsuya Ohkawa; Kei Kuramoto. Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au). Int. J. Comput. Theor. Chem. 2017, 4(3), 21-30. doi: 10.11648/j.ijctc.20160403.12

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AMA Style

Tetsuya Ohkawa, Kei Kuramoto. Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au). Int J Comput Theor Chem. 2017;4(3):21-30. doi: 10.11648/j.ijctc.20160403.12

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@article{10.11648/j.ijctc.20160403.12,
  author = {Tetsuya Ohkawa and Kei Kuramoto},
  title = {Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au)},
  journal = {International Journal of Computational and Theoretical Chemistry},
  volume = {4},
  number = {3},
  pages = {21-30},
  doi = {10.11648/j.ijctc.20160403.12},
  url = {https://doi.org/10.11648/j.ijctc.20160403.12},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20160403.12},
  abstract = {We have investigated the CH4 adsorption and the C-H bond breaking activation on the metal ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au) and M@M (111)/H (covered by hydrogen atoms) 3 and 1-layer surfaces (4-type surfaces) using spin-polarized Density Functional Theory (DFT). We find that the adsorption energies of methane are related to the d-band center of metal ad-atoms. In particular, the distances between CH4 and Ni, Pd, and Pt ad-atoms of 4-type surfaces are shortened and the adsorption energies of CH4 on metal ad-atoms are stronger than the perfect surfaces because the d-band center of metal ad-atoms are close to the Fermi level. Furthermore, we have investigated the activation barrier energies of C-H bond breaking of CH4 on Ni, Pt, and Ag ad-atoms of 4-type surfaces because Pt ad-atom exhibits stronger adsorption energy of CH4, Ag ad-atom exhibits weaker ones, and Ni utilizes for the steam reforming reaction. We find that Ni and Pt ad-atoms show lower activation barrier energies, and they are related to the CH4 adsorption energies as well as the d-band centers.},
 year = {2017}
}

Copy | Download

TY  - JOUR
T1  - Theoretical Study of CH4 Adsorption and C-H Bond Activation of CH4 on Metal Ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au)
AU  - Tetsuya Ohkawa
AU  - Kei Kuramoto
Y1  - 2017/01/10
PY  - 2017
N1  - https://doi.org/10.11648/j.ijctc.20160403.12
DO  - 10.11648/j.ijctc.20160403.12
T2  - International Journal of Computational and Theoretical Chemistry
JF  - International Journal of Computational and Theoretical Chemistry
JO  - International Journal of Computational and Theoretical Chemistry
SP  - 21
EP  - 30
PB  - Science Publishing Group
SN  - 2376-7308
UR  - https://doi.org/10.11648/j.ijctc.20160403.12
AB  - We have investigated the CH4 adsorption and the C-H bond breaking activation on the metal ad-atom of M@M (111) (M=Ni, Pd, Pt, Cu, Ag, Au) and M@M (111)/H (covered by hydrogen atoms) 3 and 1-layer surfaces (4-type surfaces) using spin-polarized Density Functional Theory (DFT). We find that the adsorption energies of methane are related to the d-band center of metal ad-atoms. In particular, the distances between CH4 and Ni, Pd, and Pt ad-atoms of 4-type surfaces are shortened and the adsorption energies of CH4 on metal ad-atoms are stronger than the perfect surfaces because the d-band center of metal ad-atoms are close to the Fermi level. Furthermore, we have investigated the activation barrier energies of C-H bond breaking of CH4 on Ni, Pt, and Ag ad-atoms of 4-type surfaces because Pt ad-atom exhibits stronger adsorption energy of CH4, Ag ad-atom exhibits weaker ones, and Ni utilizes for the steam reforming reaction. We find that Ni and Pt ad-atoms show lower activation barrier energies, and they are related to the CH4 adsorption energies as well as the d-band centers.
VL  - 4
IS  - 3
ER  -

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