铂钌团簇活化甲醇C―H和O―H键的理论研究

doi:10.3866/PKU.WHXB201504014

Abstract

Abstract:

Density functional theory calculations were performed to study the mechanism and reactivity of methanol oxidation mediated by Pt_nRu_m (n+m=3, n≠0) clusters. The potential energy surfaces and pathways of the initial O―H and C―H bond activations were predicted. The results show that the activation of methanol proceeds preferentially along the C―H bond activation pathway. The calculated reactivity order was Pt₂Ru>Pt₃> PtRu₂. Frontier molecular orbital analysis showed that the initial C/O―H bond activation is a proton transfer process. The solvent effect was also investigated. This study will enable a deeper understanding of C/O―H bond activation and provide new ideas for catalyst selection and optimizing conditions for methanol activation.

Key words: Density functional theory, Cluster, Methanol, Reactivity, Proton transfer

MSC2000:

O641

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ZHAO Jun-Feng, SUN Xiao-Li, LI Ji-Lai, HUANG Xu-Ri. Theoretical Study of Methanol C―H and O―H Bond Activation by PtRu Clusters[J].Acta Phys. -Chim. Sin., 2015, 31(6): 1077-1085.

References

(1) de Visser, S. P.; Shaik, S. J. Am. Chem. Soc. 2003, 125, 7413. doi: 10.1021/ja034142f
(2) Schwarz, H.; Schröder, D. Pure Appl. Chem. 2000, 72, 2319.
(3) Schwarz, H. Angew. Chem. Int. Edit. 2011, 50, 10096. doi: 10.1002/anie.201006424
(4) Sun, X. L.; Li, J. L.; Huang, X. R.; Sun, C. C. Curr. Inorg. Chem. 2012, 2, 64. doi: 10.2174/1877944111202010064
(5) Li, J. L.; Zhang, X.; Huang, X. R. Phys. Chem. Chem. Phys. 2012, 14, 246. doi: 10.1039/C1CP22187F
(6) Li, J. L.; Geng, C. Y.; Huang, X. R.; Zhang, X.; Sun, C. C. Organometallics 2007, 26, 2203. doi: 10.1021/om070039d
(7) Li, J. L.; Wu, X. N.; Schlangen, M.; Zhou, S. D.; González- Navarrete, P.; Tang, S. Y.; Schwarz, H. Angew. Chem. Int. Edit. 2015, doi: 10.1002/anie.201412441.
(8) Shaik, S.; de Visser, S. P.; Ogliaro, F.; Schwarz, H.; Schröder, D. Curr. Opin. Chem. Biol. 2002, 6, 556. doi: 10.1016/S1367-5931(02)00363-0
(9) Ye, S.; Neese, F. Curr. Opin. Chem. Biol. 2009, 13, 89. doi: 10.1016/j.cbpa.2009.02.007
(10) Ye, S.; Neese, F. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 1228. doi: 10.1073/pnas.1008411108
(11) Neese, F. J. Inorg. Biochem. 2006, 100, 716. doi: 10.1016/j.jinorgbio.2006.01.020
(12) Geng, C. Y.; Ye, S.; Neese, F. Angew. Chem. Int. Edit. 2010, 49, 5717. doi: 10.1002/anie.v49:33
(13) Geng, C. Y.; Li, J. L.; Huang, X. R.; Liu, H. L.; Li, Z.; Sun, C. C. J. Comput. Chem. 2008, 29, 686.
(14) Decker, A.; Rohde, J. U.; Klinker, E. J.; Wong, S. D.; Que, L.; Solomon, E. I. J. Am. Chem. Soc. 2007, 129, 15983. doi: 10.1021/ja074900s
(15) Shaik, S.; Kumar, D.; de Visser, S. P.; Altun, A.; Thiel, W. Chem. Rev. 2005, 105, 2279. doi: 10.1021/cr030722j
(16) Shaik, S.; Cohen, S.; Wang, Y.; Chen, H.; Kumar, D.; Thiel, W. Chem. Rev. 2009, 110, 949.
(17) Schöneboom, J. C.; Cohen, S.; Lin, H.; Shaik, S.; Thiel, W. J. Am. Chem. Soc. 2004, 126, 4017. doi: 10.1021/ja039847w
(18) Kwon, Y. H.; Kim, S. C.; Lee, S. Y. Macromolecules 2009, 42, 5244. doi: 10.1021/ma900781c
(19) Martínez-Huerta, M. V.; Rodríguez, J. L.; Tsiouvaras, N.; Peña, M. A.; Fierro, J. L. G.; Pastor, E. Chem. Mater. 2008, 20, 4249. doi: 10.1021/cm703047p
(20) Michel, C.; Goltl, F.; Sautet, P. Phys. Chem. Chem. Phys. 2012, 14, 15286. doi: 10.1039/c2cp43014b
(21) Ranea, V. A.; Michaelides, A.; Ramírez, R.; de Andres, P. L.; Vergés, J. A.; King, D. A. Phys. Rev. Lett. 2004, 92, 136104. doi: 10.1103/PhysRevLett.92.136104
(22) Usami, Y.; Kagawa, K.; Kawazoe, M.; Yasuyuki, M.; Sakurai, H.; Haruta, M. Appl. Catal. A-Gen. 1998, 171, 123. doi: 10.1016/S0926-860X(98)00082-9
(23) Hamnett, A. Catal. Today 1997, 38, 445. doi: 10.1016/S0920-5861(97)00054-0
(24) Childers, C. L.; Huang, H. L.; Korzeniewski, C. Langmuir 1999, 15, 786. doi: 10.1021/la980798o
(25) Xu, C.; Wang, R.; Chen, M.; Zhang, Y.; Ding, Y. Phys. Chem. Chem. Phys. 2010, 12, 239. doi: 10.1039/B917788D
(26) Hernández-Fernández, P.; Montiel, M.; Ocón, P.; Fierro, J. L. G.; Wang, H.; Abruña, H. D.; Rojas, S. J. Power Sources 2010, 195, 7959. doi: 10.1016/j.jpowsour.2010.06.009
(27) Wen, Z.; Liu, J.; Li, J. Adv. Mater. 2008, 20, 743.
(28) Li, Y.; Tang, L.; Li, J. Electrochem. Commun. 2009, 11, 846. doi: 10.1016/j.elecom.2009.02.009
(29) Zhao, Y.; Zhan, L.; Tian, J.; Nie, S.; Ning, Z. Electrochim. Acta 2011, 56, 1967. doi: 10.1016/j.electacta.2010.12.005
(30) Santhosh, P.; Gopalan, A.; Lee, K. P. J. Catal. 2006, 238, 177. doi: 10.1016/j.jcat.2005.12.014
(31) McIntyre, D. R.; Burstein, G. T.; Vossen, A. J. Power Sources 2002, 107, 67. doi: 10.1016/S0378-7753(01)00987-9
(32) Raghuveer, V.; Viswanathan, B. J. Power Sources 2005, 144, 1. doi: 10.1016/j.jpowsour.2004.11.033
(33) Hays, C. C.; Manoharan, R.; Goodenough, J. B. J. Power Sources 1993, 45, 291. doi: 10.1016/0378-7753(93)80018-K
(34) Dang, D.; Gao, H. L.; Peng, L. J.; Su, Y. L.; Liao, S. J.; Wang, Y. Acta Phys. -Chim. Sin. 2011, 27, 2379. [党岱, 高海丽, 彭良进, 苏允兰, 廖世军, 王晔. 物理化学学报, 2011, 27, 2379.] doi: 10.3866/PKU.WHXB20110922
(35) Ali, L. I.; Ali, A. G. A.; Aboul-Fotouh, S. M.; Aboul-Gheit, A. K. Appl. Catal. A-Gen. 1999, 177, 99. doi: 10.1016/S0926-860X (98)00248-8
(36) Lafuente, E.; Muñoz, E.; Benito, A. M.; Maser, W. K.; Martínez, M. T.; Alcaide, F.; Ganborena, L.; Cendoya, I.; Miguel, O.; Rodríguez, J.; Urriolabeitia, E. P.; Navarro, R. J. Mater. Res. 2006, 21, 2841. doi: 10.1557/jmr.2006.0355
(37) Reddington, E.; Sapienza, A.; Gurau, B.; Viswanathan, R.; Sarangapani, S.; Smotkin, E. S.; Mallouk, T. E. Science 1998, 280, 1735. doi: 10.1126/science.280.5370.1735
(38) Oleg, A. P. J. Solid State Electr. 2008, 12, 609. doi: 10.1007/s10008-007-0500-4
(39) Sun, Y. P.; Xing, L.; Scott, K. J. Power Sources 2010, 195, 1. doi: 10.1016/j.jpowsour.2009.07.028
(40) Luo, J.; Njoki, P. N.; Lin, Y.; Mott, D.; Wang, L.; Zhong, C. J. Langmuir 2006, 22, 2892. doi: 10.1021/la0529557
(41) Luo, J.; Maye, M. M.; Kariuki, N. N.; Wang, L.; Njoki, P.; Lin, Y.; Schadt, M.; Naslund, H. R.; Zhong, C. J. Catal. Today 2005, 99, 291. doi: 10.1016/j.cattod.2004.10.013
(42) Morante-Catacora, T. Y.; Ishikawa, Y.; Cabrera, C. R. J. Electroanal. Chem. 2008, 621, 103. doi: 10.1016/j.jelechem.2008.04.029
(43) Neto, A. O.; Dias, R. R.; Tusi, M. M.; Linardi, M.; Spinacé, E. V. J. Power Sources 2007, 166, 87. doi: 10.1016/j.jpowsour.2006.12.088
(44) Yi, Q.; Zhang, J.; Chen, A.; Liu, X.; Xu, G.; Zhou, Z. J. Appl. Electrochem. 2008, 38, 695. doi: 10.1007/s10800-008-9490-x
(45) Liu, Y. C.; Qiu, X. P.; Huang, Y. Q.; Zhu, W. T. J. Power Sources 2002, 111, 160. doi: 10.1016/S0378-7753(02)00298-7
(46) Thomas, J. M. Angew. Chem. Int. Edit. 1994, 33, 913.
(47) Eller, K.; Schwarz, H. Chem. Rev. 1991, 91, 1121. doi: 10.1021/cr00006a002
(48) Kulesza, P. J.; Matczak, M.; Wolkiewicz, A.; Grzybowska, B.; Galkowski, M.; Malik, M. A.; Wieckowski, A. Electrochim. Acta 1999, 44, 2131. doi: 10.1016/S0013-4686(98)00321-1
(49) Gasteiger, H. A.; Markovic, N.; Ross, P. N.; Cairns, E. J. J. Phys. Chem. 1993, 97, 12020. doi: 10.1021/j100148a030
(50) Lu, Q.; Li, J. P. Guangdong Chemical Industry 2006, 33, 8. [陆勤, 李俊鹏. 广东化工, 2006, 33, 8.],
(51) Zhong, W.; Liu, Y.; Zhang, D. J. Mol. Model. 2012, 18, 3051. doi: 10.1007/s00894-011-1318-7
(52) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.02; Gaussian Inc.:Wallingford, CT, 2009.
(53) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/ 1.464913
(54) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299. doi: 10.1063/1.448975
(55) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270. doi: 10.1063/1.448799
(56) Fukui, K. J. Phys. Chem. 1970, 74, 4161. doi: 10.1021/j100717a029
(57) Neese, F. WIREs Comput. Mol. Sci. 2012, 2, 73. doi: 10.1002/wcms.81
(58) Neese, F. J. Am. Chem. Soc 2006, 128, 10213. doi: 10.1021/ja061798a
(59) Sun, X. L.; Huang, X. R.; Li, J. L.; Huo, R. P.; Sun, C. C. J. Phys. Chem. A 2012, 116, 1475. doi: 10.1021/jp2120302
(60) Sun, X. L.; Geng, C. Y.; Huo, R. P.; Ryde, U.; Bu, Y. X.; Li, J. L. J. Phys. Chem. B 2014, 118, 1493.
(61) Sun, X. H.; Sun, X. L.; Geng, C. Y.; Zhao, H. T.; Li, J. L. J. Phys. Chem. A 2014, 118, 7146. doi: 10.1021/jp505662x
(62) Huo, R. P.; Zhang, X.; Huang, X. R.; Li, J. L.; Sun, C. C. J. Mol. Model. 2013, 19, 1009. doi: 10.1007/s00894-012-1616-8
(63) Sun, X. L.; Li, J. L.; Huang, X. R.; Sun, C. C. Acta Chim. Sin. 2012, 70, 1245. [孙小丽, 李吉来, 黄旭日, 孙家钟. 化学学报, 2012, 70, 1245.] doi: 10.6023/A1201134
(64) Huo, R. P.; Zhang, X.; Huang, X. R.; Li, J. L.; Sun, C. C. J. Phys. Chem. A 2011, 115, 3576. doi: 10.1021/jp200231n
(65) Pettersen, E. F.; Goddard, T. D.; Huang, C. C.; Couch, G. S.; Greenblatt, D. M.; Meng, E. C.; Ferrin, T. E. J. Comput. Chem. 2004, 25, 1605.
(66) Zhang, X.; Schwarz, H. Theor. Chem. Acc. 2011, 129, 389. doi: 10.1007/s00214-010-0861-0
(67) Li, J. L.; Mata, R. A.; Ryde, U. J. Chem. Theory Comput. 2013, 9, 1799. doi: 10.1021/ct301094r
(68) Zhang, X.; Schwarz, H. Chem. -Eur. J. 2010, 16, 5882. doi: 10.1002/chem.201000567
(69) Li, J. L.; Ryde, U. Inorg. Chem. 2014, 53, 11913. doi: 10.1021/ic5010837
(70) Li, J. L.; González-Navarrete, P.; Schlangen, M.; Schwarz, H. Chem. -Eur. J. 2015, 21, 7780. doi: 10.1002/chem.201500715
(71) Greeley, J.; Mavrikakis, M. J. Am. Chem. Soc. 2002, 124, 7193. doi: 10.1021/ja017818k
(72) Greeley, J.; Mavrikakis, M. J. Am. Chem. Soc. 2004, 126, 3910. doi: 10.1021/ja037700z

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Theoretical Study of Methanol C―H and O―H Bond Activation by PtRu Clusters

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