Understanding of the activity difference between nanogold and bulk gold by relativistic effects

能源化学(英文) ›› 2015, Vol. 21 ›› Issue (4): 485-489.

Understanding of the activity difference between nanogold and bulk gold by relativistic effects

Keju Sun^a,b, Masanori Kohyama^b, Shingo Tanaka^b, Seiji Takeda^a

a The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan;
b Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda, Osaka 563-8577, Japan

收稿日期:2015-03-03 修回日期:2015-03-09 发布日期:2015-08-21
通讯作者: Keju Sun
基金资助:
This study was supported by Grant-in-Aid for Specially Promoted Research Grant no. 19001005 from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT). A part of this study was supported by the Management Expenses Grants for National Universities Corporations fromMEXT, and by Japan Science and Technology Agency (JST), Core Research for Evolutional Science and Technology (CREST).

Understanding of the activity difference between nanogold and bulk gold by relativistic effects

Keju Sun^a,b, Masanori Kohyama^b, Shingo Tanaka^b, Seiji Takeda^a

a The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan;
b Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda, Osaka 563-8577, Japan

Received:2015-03-03 Revised:2015-03-09 Published:2015-08-21
Contact: Keju Sun
Supported by:
This study was supported by Grant-in-Aid for Specially Promoted Research Grant no. 19001005 from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT). A part of this study was supported by the Management Expenses Grants for National Universities Corporations fromMEXT, and by Japan Science and Technology Agency (JST), Core Research for Evolutional Science and Technology (CREST).

摘要/Abstract

摘要： It is a challenge to thoroughly understand the astonishing difference in catalytic activity between nanogold and bulk gold for some oxidation reactions. In this work, the Au-O interactions in various surroundings were investigated by DFT calculations and compared with the Ag-O interactions. We have found the three points. First, only Au-O bond can be significantly strengthened by the linear O-Au-O structure. Second, the Au-O bond is always stronger than the Ag-O bond when the bonds are embedded in common surroundings. Third, the Au-O bond becomes weaker than the Ag-O bond when the number of neighboring Au atoms becomes large, because the Au-O interactions are suppressed by the presence of neighboring gold atoms. The origin of these three points can be attributed to wider spatial extension of d orbitals of gold, induced by strong relativistic effects. The strong relativistic effects make nanogold with smaller coordinate numbers highly active due to the ease in forming strong Au-O bonds, especially for the O-Au-O bond, whereas gold atoms in bulk with larger coordination numbers chemically inert due to the strong suppression by neighboring gold atoms destabilizing the O-Au-O bond.

关键词: Nanogold, Au-O interactions, Relativistic effects, DFT calculations

Abstract: It is a challenge to thoroughly understand the astonishing difference in catalytic activity between nanogold and bulk gold for some oxidation reactions. In this work, the Au-O interactions in various surroundings were investigated by DFT calculations and compared with the Ag-O interactions. We have found the three points. First, only Au-O bond can be significantly strengthened by the linear O-Au-O structure. Second, the Au-O bond is always stronger than the Ag-O bond when the bonds are embedded in common surroundings. Third, the Au-O bond becomes weaker than the Ag-O bond when the number of neighboring Au atoms becomes large, because the Au-O interactions are suppressed by the presence of neighboring gold atoms. The origin of these three points can be attributed to wider spatial extension of d orbitals of gold, induced by strong relativistic effects. The strong relativistic effects make nanogold with smaller coordinate numbers highly active due to the ease in forming strong Au-O bonds, especially for the O-Au-O bond, whereas gold atoms in bulk with larger coordination numbers chemically inert due to the strong suppression by neighboring gold atoms destabilizing the O-Au-O bond.

Key words: Nanogold, Au-O interactions, Relativistic effects, DFT calculations

Keju Sun, Masanori Kohyama, Shingo Tanaka, Seiji Takeda. Understanding of the activity difference between nanogold and bulk gold by relativistic effects[J]. 能源化学(英文), 2015, 21(4): 485-489.

Keju Sun, Masanori Kohyama, Shingo Tanaka, Seiji Takeda. Understanding of the activity difference between nanogold and bulk gold by relativistic effects[J]. Journal of Energy Chemistry, 2015, 21(4): 485-489.

参考文献

[1] B. Hammer, J.K. Norskov, Nature 376 (6537) (1995) 238.

[2] M. Haruta, T. Kobayashi, H. Sano, N. Yamada, Chem. Lett. 16 (2) (1987) 405.

[3] H. Sakurai, A. Ueda, T. Kobayashi, M. Haruta, Chem. Commun. (3) (1997) 271.

[4] B.S. Uphade, S. Tsubota, T. Hayashi, M. Haruta, Chem. Lett. 27 (12) (1998) 1277.

[5] J.L. Gong, C.B. Mullins, J. Am. Chem. Soc. 130 (49) (2008) 16458.

[6] T.M. Salama, R. Ohnishi, T. Shido, M. Ichikawa, J. Catal. 162 (2) (1996) 169.

[7] M. Valden, X. Lai, D.W. Goodman, Science 281 (5383) (1998) 1647.

[8] N. Lopez, J.K. Norskov, J. Am. Chem. Soc. 124 (38) (2002) 11262.

[9] N.A. Hodge, C.J. Kiely, R.Whyman, M.R.H. Siddiqui, G.J. Hutchings, Q.A. Pankhurst, F.E.Wagner, R.R. Rajaram, S.E. Golunski, Catal. Today 72 (1-2) (2002) 133.

[10] Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Science 301 (5635) (2003) 935.

[11] A. Sanchez, S. Abbet, U. Heiz, W.D. Schneider, H. Hakkinen, R.N. Barnett, U. Landman, J. Phys. Chem. A 103 (48) (1999) 9573.

[12] T. Fujitani, I. Nakamura, T. Akita, M. Okumura, M. Haruta, Angew. Chem. Int. Ed. 48 (50) (2009) 9515.

[13] M. Haruta, Cattech 6 (3) (2002) 102.

[14] P. Pyykko, Chem. Rev. 88 (3) (1988) 563.

[15] T.E. Jones, S. Piccinin, C. Stampfl, Mater. Chem. Phys. 141 (1) (2013) 14.

[16] K.J. Sun, M. Kohyama, S. Tanaka, S. Takeda, J. Phys. Chem. A 116 (38) (2012) 9568.

[17] K.J. Sun, M. Kohyama, S. Tanaka, S. Takeda, ChemCatChem 5 (8) (2013) 2217.

[18] A. Citra, L. Andrews, J. Mol. Struct.: Theochem 489 (2-3) (1999) 95.

[19] G. Kresse, J. Hafner, Phys. Rev. B 48 (17) (1993) 13115.

[20] J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (18) (1996) 3865.

[21] P.E. Blochl, Phys. Rev. B 50 (24) (1994) 17953.

[22] G. Kresse, D. Joubert, Phys. Rev. B 59 (3) (1999) 1758.

[23] B.D. Todd, R.M. Lyndenbell, Surf. Sci. 281 (1-2) (1993) 191.

[24] K.J. Sun, Y.H. Zhao, H.Y. Su,W.X. Li, Theor. Chem. Acc. 131 (2) (2012) 1118.

[25] K.P. Huber, G. Herzberg, Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules, Van Nostrand Reinhold Company, New York, 1979.

[26] A. Hecq, M. Vandy, M. Hecq, J. Chem. Phys. 72 (4) (1980) 2876.

[27] K.J. Sun, M. Kohyama, S. Tanaka, S. Takeda, J. Comput. Chem. 32 (15) (2011) 3276.

[28] E.J. Baerends, W.H.E. Schwarz, P. Schwerdtfeger, J.G. Snijders, J. Phys. B: At. Mol. Opt. Phys. 23 (19) (1990) 3225.

[29] J. Autschbach, S. Siekierski, M. Seth, P. Schwerdtfeger,W.H.E. Schwarz, J. Comput. Chem. 23 (8) (2002) 804.

[30] N. Bartlett, Gold Bull 31 (1) (1998) 22.

[31] J.B. Mann, Atomic Structure Calculations II. Hartree-Fock Wavefunctions and Radial Expectation Values: Hydrogen to Lawrencium, Los Alamos Scientific Laboratory, Los Alamos, NM, 1968.

[32] R.D. Shannon, Acta Crystallogr. Sect. A 32 (Sep1) (1976) 751.

[33] R. Arratia-Perez, A.F. Ramos, G.L. Malli, Phys. Rev. B 39 (5) (1989) 3005.

[34] P. Pyykko, M. Patzschke, J. Suurpere, Chem. Phys. Lett. 381 (1-2) (2003) 45.

[35] K.J. Sun, M. Kohyama, S. Tanaka, S. Takeda, Surf. Sci. 628 (2014) 41.

[36] M. Mavrikakis, P. Stoltze, J.K. Norskov, Catal. Lett. 64 (2-4) (2000) 101.

[37] J.Wang, B.E. Koel, J. Phys. Chem. A 102 (44) (1998) 8573.

[38] J.H. Liu, A.Q.Wang, Y.S. Chi, H.P. Lin, C.Y. Mou, J. Phys. Chem. B 109 (1) (2005) 40.

[39] C.W. Yen, M.L. Lin, A.Q. Wang, S.A. Chen, J.M. Chen, C.Y. Mou, J. Phys. Chem. C 113 (41) (2009) 17831.

[40] M.S. Chen, Y. Cal, Z. Yan, K.K. Gath, S. Axnanda, D.W. Goodman, Surf. Sci. 601 (23) (2007) 5326.

[41] H.H. Yao, X.H. Zi, H.X. Dai, H. He, Ind. Catal. 19 (8) (2011) 16.

[42] F. Gao, Y.L.Wang, D.W. Goodman, J. Phys. Chem. C 113 (33) (2009) 14993.

[43] H.J. Zhang, N. Toshima, Appl. Catal. A 447 (2012) 81.

[44] H. Altass, A.F. Carley, P.R. Davies, R.J. Davies, Chem. Commun. 49 (74) (2013) 8223.

[45] S. Sarina, H.Y. Zhu, E. Jaatinen, Q. Xiao, H.W. Liu, J.F. Jia, C. Chen, J. Zhao, J. Am. Chem. Soc. 135 (15) (2013) 5793.

[46] B.E. Solsona, T. Garcia, C. Jones, S.H. Taylor, A.F. Carley, G.J. Hutchings, Appl. Catal. A 312 (2006) 67.

[47] D. Tongsakul, S. Nishimura, K. Ebitani, ACS Catal. 3 (10) (2013) 2199.

Understanding of the activity difference between nanogold and bulk gold by relativistic effects

Understanding of the activity difference between nanogold and bulk gold by relativistic effects

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