铂钌团簇活化甲醇C―H和O―H键的理论研究

doi:10.3866/PKU.WHXB201504014

摘要/Abstract

摘要：

采用密度泛函理论研究了Pt_nRu_m (n+m=3, n≠0)团簇活化甲醇C―H和O―H键的反应活性和机理. 分别给出以O―H和C―H键活化为初始步骤的势能曲线. 计算结果表明反应是以C―H键的活化为初始步骤; 三种团簇与甲醇反应的活性顺序为Pt₂Ru>Pt₃>PtRu₂. 前线轨道分析表明Pt_nRu_m团簇活化初始的C―H和O―H键的活化过程是质子转移(PT). 此外还讨论了溶剂化对反应的影响. 本研究可为C―H键和O―H键的活化提供更深入的理解, 为甲醇活化反应催化剂选择以及其使用条件的优化提供新思路.

关键词: 密度泛函理论, 团簇, 甲醇, 活性, 质子转移

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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赵俊凤, 孙小丽, 李吉来, 黄旭日. 铂钌团簇活化甲醇C―H和O―H键的理论研究[J]. 物理化学学报, 2015, 31(6): 1077-1085.

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.

参考文献

(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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