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First principles calculations are performed to study the geometric structures and the nitrogen adsorption properties of BaO adlayer on Ru(0001) surface. It is suggested that BaO adlayer is more stable on Ru(0001) surface at low coverage. A configuration is observed in surface phase at low coverage. In this structure oxygen is adsorbed on the hcp site of one p(1 1) cell, and barium is adsorbed close to the top site of the same p(1 1) cell. Bond length of oxygen and ruthenium is calculated to be 0.209 nm, longer than the EXAFS experimental value about 0.018 nm. Nitrogen prefers to be adsorbed on the sites close to barium. Nitrogen adsorption energies at those sites are calculated to be in a range from 0.70 to 0.87 eV, which are bigger than those at the sites close to oxygen. Adsorption sites near barium atoms have more activities to weaken nitrogen. The lowest N-N stretching vibrational frequency on the sites is about 1946 cm-1, less than the highest frequency on sites around oxygen (about 130 cm- 1). Bond strengths of nitrogen on Ru(0001) /BaO surface are between those on clean Ru(0001) and Ru(0001) /Ba surface. The adsorption properties of sites around BaO layer are determined by chemical characteristic of barium and oxygen. Electron transfer from barium to ruthenium enhances the hybridization between ruthenium and nitrogen by reducing and increasing the occupation of * and * orbitals respectively.
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Keywords:
- ammonia synthesis catalyst /
- Ru(0001)/BaO /
- surface formation energy /
- molecular vibration
[1] Kowalczyk Z, Krukowski M, Rarog-Pilecka W, Szmigiel D, Zielinski J 2003 Appl. Catal. a-Gen. 248 67
[2] Rossetti I, Pernicone N, Forni L 2001 Appl. Catal. a-Gen. 208 271
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[28] Zhao X X, Tao X M, Mi Y M, Wu J B, Wang L L, Tan M Q 2011 Acta Chim. Sin. 69 2201 (in Chinese) [赵新新, 陶向明, 宓一鸣, 吴建宝, 汪丽莉, 谭明秋 2011 化学学报 69 2201]
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[34] [35] Kresse G, Furthmuller J 1996 Comp. Mater. Sci. 6 15
[36] Kresse G, Furthmuller J 1996 Phys. Rev. B 54 11169
[37] [38] Blhl P E 1994 Phys. Rev. B 50 17953
[39] [40] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[41] [42] [43] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[44] Kittel C 1976 Introduction to Solid State Physics (7th Ed.) (New York: John Wiley and Sons) pp23-57
[45] [46] [47] Methfessel M, Hennig D, Scheffler M 1992 Phys. Rev. B 46 4816
[48] Feibelman P J, Houston J E, Davis H L, Oneill D G 1994 Surf. Sci. 302 81
[49] [50] Mannstadt W 2003 Surf. Sci. 525 119
[51] [52] [53] Kim Y D, Seitsonen A P, Over H 2000 Surf. Sci. 465 1
[54] Honkala K, Hellman A, Remediakis I N, Logadottir A, Carlsson A, Dahl S, Christensen C H, Norskov J K 2005 Science 307 555
[55] [56] Hellman A, Honkala K, Remediakis I N, Logadottir A, Carlsson A, Dahl S, Christensen C H, Norskov J K 2009 Surf. Sci. 603 1731
[57] [58] Cheng L, Ge Q F 2007 Surf. Sci. 601 L65
[59] [60] [61] Bader R F W 1990 Atoms in Molecules-A Quantum Theory (Oxford: Oxford University Press) p116
[62] Mortensen J J, Hammer B, Noskov J K 1998 Surf. Sci. 414 315
[63] -
[1] Kowalczyk Z, Krukowski M, Rarog-Pilecka W, Szmigiel D, Zielinski J 2003 Appl. Catal. a-Gen. 248 67
[2] Rossetti I, Pernicone N, Forni L 2001 Appl. Catal. a-Gen. 208 271
[3] [4] [5] Rarog-Pilecka W, Miskiewicz E, Szmigiel D, Kowalczyk Z 2005 J. Catal. 231 11
[6] [7] Zhong Z, HAika K 1998 Inorg. Chim. Acta 280 183
[8] Zeng H S, Inazu K, Aika K 2002 J. Catal. 211 33
[9] [10] [11] Truszkiewicz E, Rarog-Pilecka W, Schmidt-Szatowski K, Jodzis S, Wilczkowska E, Lomot D, Kaszkur Z, Karpinski Z, Kowalczyk Z 2009 J. Catal. 265 181
[12] [13] Hansen T W, Wagner J B, Hansen P L, Dahl S, Topsoe H, Jacobsen C J H 2001 Science 294 1508
[14] [15] Hansen T W, Hansen P L, Dahl S, Jacobsen C J H 2002 Catal. Lett. 84 7
[16] Bielawa H, Hinrichsen O, Birkner A, Muhler M 2001 Ang. Chem. Inter. Ed. 40 1061
[17] [18] [19] Guraya M, Sprenger S, Rarog-Pilecka W, Szmigiel D, Kowalczyk Z, Muhler M 2004 Appl. Surf. Sci. 238 77
[20] McClaine B C, Siporin S E, Davis R J 2001 J. Phys. Chem. B 105 7525
[21] [22] [23] Dahl S, Logadottir A, Egeberg R C, Larsen J H, Chorkendorff I, Tornqvist E, Norskov J K 1999 Phys. Rev. Lett. 83 1814
[24] [25] Zhao X X, Tao X M, Chen W B, Cai J Q, Tan M Q 2005 Acta Phys. Sin. 54 5849 (in Chinese) [赵新新, 陶向明, 陈文斌, 蔡建秋, 谭明秋 2005 物理学报 54 5849]
[26] [27] Zhao X X, Tao X M, Mi Y M, Chen S, Tan M Q 2009 Acta Phys. Chim. Sin. 25 2305 (in Chinese) [赵新新, 陶向明, 宓一鸣, 陈戍, 谭明秋 2009 物理化学学报 25 2305]
[28] Zhao X X, Tao X M, Mi Y M, Wu J B, Wang L L, Tan M Q 2011 Acta Chim. Sin. 69 2201 (in Chinese) [赵新新, 陶向明, 宓一鸣, 吴建宝, 汪丽莉, 谭明秋 2011 化学学报 69 2201]
[29] [30] [31] Kim Y K, Morgan G A, Yates J T 2005 Surf. Sci. 598 14
[32] [33] Zambelli T, Trost J, Wintterlin J, Ertl G 1996 Phys. Rev. Lett. 76 795
[34] [35] Kresse G, Furthmuller J 1996 Comp. Mater. Sci. 6 15
[36] Kresse G, Furthmuller J 1996 Phys. Rev. B 54 11169
[37] [38] Blhl P E 1994 Phys. Rev. B 50 17953
[39] [40] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[41] [42] [43] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[44] Kittel C 1976 Introduction to Solid State Physics (7th Ed.) (New York: John Wiley and Sons) pp23-57
[45] [46] [47] Methfessel M, Hennig D, Scheffler M 1992 Phys. Rev. B 46 4816
[48] Feibelman P J, Houston J E, Davis H L, Oneill D G 1994 Surf. Sci. 302 81
[49] [50] Mannstadt W 2003 Surf. Sci. 525 119
[51] [52] [53] Kim Y D, Seitsonen A P, Over H 2000 Surf. Sci. 465 1
[54] Honkala K, Hellman A, Remediakis I N, Logadottir A, Carlsson A, Dahl S, Christensen C H, Norskov J K 2005 Science 307 555
[55] [56] Hellman A, Honkala K, Remediakis I N, Logadottir A, Carlsson A, Dahl S, Christensen C H, Norskov J K 2009 Surf. Sci. 603 1731
[57] [58] Cheng L, Ge Q F 2007 Surf. Sci. 601 L65
[59] [60] [61] Bader R F W 1990 Atoms in Molecules-A Quantum Theory (Oxford: Oxford University Press) p116
[62] Mortensen J J, Hammer B, Noskov J K 1998 Surf. Sci. 414 315
[63]
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