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Cu-CeO2 systems are widely used in solid oxide fuel cells and water gas shift reaction because of its special catalytic ability. The interfacial properties of the Cu/CeO2 (110) with the adsorption of Cu atom and Cu cluster are investigated in terms of first-principles based on density functional theory. It is found that: 1) the single Cu adatom prefers to be adsorbed on the oxygen bridge site; 2) the adsorbed tetrahedron structure of Cu4 cluster is the most stable cluster configuration on CeO2(110) surface; 3) the metal-introduced gap states in the gap area are mainly from the adsorbed Cu (cluster), its neighboring oxygcr and the reduced cerium ion(s), indicating that the activity of CeO2(110) surface is improved by copper adsorption; 4) the adsorbed Cu adatom and Cu4 cluster are oxidized to Cuδ+ and Cu4δ+ by their neighboring Ce ion(s) with the formation of Ce3+ ion(s), the reaction could be summarized as Cux/Ce4+→ Cuxδ+/Ce3+; 5) the adsorption of small clusters introduces more Ce3+ ions than a single Cu atom does, indicating that more Cuδ+-Ce3+ catalytic active centers are formed. The current study on Cu/CeO2(110) together with our previous results on Cu/CeO2(111) presents a good understanding of the synergies between Cu and ceria, and reveals the improvement of the activity of ceria by Cu adsorption.
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Keywords:
- Cu/CeO2 /
- DFT+U /
- adsorption /
- electronic structure
[1] Park J B, Graciani J, Evans J, Stacchiola D, Senanayake S D, Barrio L, Liu P, Sanz J F, Hrbek J, Rodriguez J A 2009 J. Am. Chem. Soc. 132 356
[2] Yang F, Graciani J s, Evans J, Liu P, Hrbek J, Sanz J F, Rodriguez J A 2011 J. Am. Chem. Soc. 133 3444
[3] Gamarra D, Munuera G, Hungría A, Fernández-García M, Conesa J, Midgley P, Wang X, Hanson J, Rodríguez J, Martínez-Arias A 2007 J. Phys. Chem. C 111 11026
[4] Kydd R, Teoh W Y, Wong K, Wang Y, Scott J, Zeng Q H, Yu A B, Zou J, Amal R 2008 Adv. Funct. Mater. 19 369
[5] Yen H, Seo Y, Kaliaguine S, Kleitz F 2012 Angew. Chem. Int. Edit. 51 12032
[6] Kim T, Liu G, Boaro M, Lee S I, Vohs J M, Gorte R J, Al-Madhi O, Dabbousi B 2006 J. Power Sources 155 231
[7] He H, Gorte R J, Vohs J M 2005 Electrochem. Solid-State Lett. 8 A279
[8] Yang Z X, Xie L G, Ma D W, Wang G T 2011 J. Phys. Chem. C 115 6730
[9] Yang Z X, Wang Q T, Wei S Y 2011 Phys. Chem. Chem. Phys. 13 9363
[10] Lu Z S, Yang Z X, Hermansson K 2011 Advanced Materials Research 213 166
[11] Yang Z X, He B L, Lu Z S, Hermansson K 2010 J. Phys. Chem. C 114 4486
[12] Branda M M, Hernández N C, Sanz J F, Illas F 2010 J. Phys. Chem. C 114 1934
[13] Lu Z S, Yang Z X, He B L, Castleton C, Hermansson K 2011 Chem. Phys. Lett. 510 60
[14] Tang Y H, Zhang H, Cui L X, Ouyang C, Shi S Q, Tang W H, Li H, Chen L Q 2012 J. Power Sources 197 10
[15] Lu Z S, L G X, Yang Z X 2007 Acta Phys. Sin. 56 5382 (in Chinese) [路战胜, 罗改霞, 杨宗献 2007 物理学报 56 5382]
[16] Szabová L, Camellone M F, Huang M, Matolín V, Fabris S 2010 J. Chem. Phys. 133 234705
[17] Nolan M, Parker S C, Watson G W 2005 Surf. Sci. 595 223
[18] Nolan M, Grigoleit S, Sayle D C, Parker S C, Watson G W 2005 Surf. Sci. 576 217
[19] Cui L X, Tang Y H, Zhang H, Hector L G, Ouyang C, Shi S Q, Li H, Chen L Q 2012 Phys. Chem. Chem. Phys. 14 1923
[20] Matolin V, Sedlacek L, Matolinova I, Šutara F, Skála T, Šmíd B, Libra J, Nehasil V, Prince K C 2008 J. Phys. Chem. C 112 3751
[21] Hornés A, Hungría A B, Bera P, Cámara A L, Fernández-García M, Martínez-Arias A, Barrio L, Estrella M, Zhou G, Fonseca J J, Hanson J C, Rodriguez J A 2009 J. Am. Chem. Soc. 132 34
[22] Kresse G, Hafner J 1993 Phys. Rev. B 47 558
[23] Kresse G, Furthmuller J 1996 Comput. Mater. Sci. 6 15
[24] Blöchl P E 1994 Phys. Rev. B 50 17953
[25] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[26] Fabris S, de Gironcoli S, Baroni S, Vicario G, Balducci G 2005 Phys. Rev. B 71 041102(R)
[27] Yang Z X, Woo T K, Hermansson K 2006 J. Chem. Phys. 124 224704
[28] Castleton C W M, Kullgren J, Hermansson K 2007 J. Chem. Phys. 127 244704
[29] Kmmerle E A, Heger G 1999 J. Solid State Chem. 147 485
[30] Lu Z S, Kullgren J, Yang Z X, Hermansson K 2012 J. Phys. Chem. C 116 8417
[31] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[32] Lippmann T, Schneider J R 2000 J. Appl. Crystallogr. 33 156
[33] Henkelman G, Arnaldsson A, Jonsson H 2006 Comput. Mater. Sci. 36 354
[34] Ganduglia-Pirovano M V, Da Silva J L F, Sauer J 2009 Phys. Rev. Lett. 102 26101
[35] Kim H Y, Lee H M, Henkelman G 2012 J. Am. Chem. Soc. 134 1560
[36] Lu Z S, Yang Z X, 2010 J. Phys.: Condens. Matter 22 475003
-
[1] Park J B, Graciani J, Evans J, Stacchiola D, Senanayake S D, Barrio L, Liu P, Sanz J F, Hrbek J, Rodriguez J A 2009 J. Am. Chem. Soc. 132 356
[2] Yang F, Graciani J s, Evans J, Liu P, Hrbek J, Sanz J F, Rodriguez J A 2011 J. Am. Chem. Soc. 133 3444
[3] Gamarra D, Munuera G, Hungría A, Fernández-García M, Conesa J, Midgley P, Wang X, Hanson J, Rodríguez J, Martínez-Arias A 2007 J. Phys. Chem. C 111 11026
[4] Kydd R, Teoh W Y, Wong K, Wang Y, Scott J, Zeng Q H, Yu A B, Zou J, Amal R 2008 Adv. Funct. Mater. 19 369
[5] Yen H, Seo Y, Kaliaguine S, Kleitz F 2012 Angew. Chem. Int. Edit. 51 12032
[6] Kim T, Liu G, Boaro M, Lee S I, Vohs J M, Gorte R J, Al-Madhi O, Dabbousi B 2006 J. Power Sources 155 231
[7] He H, Gorte R J, Vohs J M 2005 Electrochem. Solid-State Lett. 8 A279
[8] Yang Z X, Xie L G, Ma D W, Wang G T 2011 J. Phys. Chem. C 115 6730
[9] Yang Z X, Wang Q T, Wei S Y 2011 Phys. Chem. Chem. Phys. 13 9363
[10] Lu Z S, Yang Z X, Hermansson K 2011 Advanced Materials Research 213 166
[11] Yang Z X, He B L, Lu Z S, Hermansson K 2010 J. Phys. Chem. C 114 4486
[12] Branda M M, Hernández N C, Sanz J F, Illas F 2010 J. Phys. Chem. C 114 1934
[13] Lu Z S, Yang Z X, He B L, Castleton C, Hermansson K 2011 Chem. Phys. Lett. 510 60
[14] Tang Y H, Zhang H, Cui L X, Ouyang C, Shi S Q, Tang W H, Li H, Chen L Q 2012 J. Power Sources 197 10
[15] Lu Z S, L G X, Yang Z X 2007 Acta Phys. Sin. 56 5382 (in Chinese) [路战胜, 罗改霞, 杨宗献 2007 物理学报 56 5382]
[16] Szabová L, Camellone M F, Huang M, Matolín V, Fabris S 2010 J. Chem. Phys. 133 234705
[17] Nolan M, Parker S C, Watson G W 2005 Surf. Sci. 595 223
[18] Nolan M, Grigoleit S, Sayle D C, Parker S C, Watson G W 2005 Surf. Sci. 576 217
[19] Cui L X, Tang Y H, Zhang H, Hector L G, Ouyang C, Shi S Q, Li H, Chen L Q 2012 Phys. Chem. Chem. Phys. 14 1923
[20] Matolin V, Sedlacek L, Matolinova I, Šutara F, Skála T, Šmíd B, Libra J, Nehasil V, Prince K C 2008 J. Phys. Chem. C 112 3751
[21] Hornés A, Hungría A B, Bera P, Cámara A L, Fernández-García M, Martínez-Arias A, Barrio L, Estrella M, Zhou G, Fonseca J J, Hanson J C, Rodriguez J A 2009 J. Am. Chem. Soc. 132 34
[22] Kresse G, Hafner J 1993 Phys. Rev. B 47 558
[23] Kresse G, Furthmuller J 1996 Comput. Mater. Sci. 6 15
[24] Blöchl P E 1994 Phys. Rev. B 50 17953
[25] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[26] Fabris S, de Gironcoli S, Baroni S, Vicario G, Balducci G 2005 Phys. Rev. B 71 041102(R)
[27] Yang Z X, Woo T K, Hermansson K 2006 J. Chem. Phys. 124 224704
[28] Castleton C W M, Kullgren J, Hermansson K 2007 J. Chem. Phys. 127 244704
[29] Kmmerle E A, Heger G 1999 J. Solid State Chem. 147 485
[30] Lu Z S, Kullgren J, Yang Z X, Hermansson K 2012 J. Phys. Chem. C 116 8417
[31] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[32] Lippmann T, Schneider J R 2000 J. Appl. Crystallogr. 33 156
[33] Henkelman G, Arnaldsson A, Jonsson H 2006 Comput. Mater. Sci. 36 354
[34] Ganduglia-Pirovano M V, Da Silva J L F, Sauer J 2009 Phys. Rev. Lett. 102 26101
[35] Kim H Y, Lee H M, Henkelman G 2012 J. Am. Chem. Soc. 134 1560
[36] Lu Z S, Yang Z X, 2010 J. Phys.: Condens. Matter 22 475003
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