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

点击下载补充材料PDF格式文件

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

[1]	王丹,丁迅雷,廖珩璐,戴佳钰. 单个金或银原子掺杂的氧化钒团簇上的甲烷活化反应[J]. 物理化学学报, 2019, 35(9): 1005 -1013 .
[2]	张舒怡,鲍静娴,吴博,钟良枢,孙予罕. 甲烷/甲醇光催化转化研究进展[J]. 物理化学学报, 2019, 35(9): 923 -939 .
[3]	陈强,姜利学,李海方,陈娇娇,赵艳霞,何圣贵. 钒硼双原子阳离子活化甲烷研究[J]. 物理化学学报, 2019, 35(9): 1014 -1020 .
[4]	韩萌茹,周亚男,周旋,储伟. 通过g-C₃N₄担载MNi₁₂ (Fe, Co, Cu, Zn)纳米团簇调节甲烷化[J]. 物理化学学报, 2019, 35(8): 850 -857 .
[5]	龚铃堰, 廖广志, 陈权生, 栾和鑫, 冯玉军. 表面活性剂溶胀胶束：性能及应用[J]. 物理化学学报, 2019, 35(8): 816 -828 .
[6]	罗思琪,王美娜,赵微微,王毅琳. 表面活性剂与叶酸的相互作用及其对光氧化降解的影响[J]. 物理化学学报, 2019, 35(7): 766 -774 .
[7]	郭锦成,林燕芬,田娜,孙世刚. Ru修饰Pd二十四面体纳米晶的合成及其甲醇电催化氧化性能[J]. 物理化学学报, 2019, 35(7): 749 -754 .
[8]	赵越,崔佳桐,胡继闯,马嘉璧. VO_1-4⁺阳离子与n-C_mH_2m+2 (m = 3, 5, 7)烷烃的反应性研究：氧含量和碳链长度的影响[J]. 物理化学学报, 2019, 35(5): 531 -538 .
[9]	杨晓冬,陈驰,周志有,孙世刚. 碳基非贵金属氧还原电催化剂的活性位结构研究进展[J]. 物理化学学报, 2019, 35(5): 472 -485 .
[10]	林舟,申琳璠,瞿希铭,张俊明,姜艳霞,孙世刚. 盐封后碳化钼电催化剂的制备及其氢析出性能[J]. 物理化学学报, 2019, 35(5): 523 -530 .
[11]	刘恒昌,冯玉军. CO₂诱导的五嵌段非离子共聚物与阴离子氟碳表面活性剂的相互作用[J]. 物理化学学报, 2019, 35(4): 408 -414 .
[12]	尹雅芝,胡兵,刘国亮,周晓海,洪昕林. 利用ZnO@ZIF-8核壳结构构建高选择性、高稳定性的Pd/ZnO催化剂用于CO₂加氢制甲醇[J]. 物理化学学报, 2019, 35(3): 327 -336 .
[13]	徐向宇,廖艳清,孙建川,王旭辉,陈帅奇,吕志,宋家庆. 活性氧化铝及其再生氧化铝对水中氟离子的吸附[J]. 物理化学学报, 2019, 35(3): 317 -326 .
[14]	刘艳芳,胡兵,尹雅芝,刘国亮,洪昕林. 无表面活性剂条件下一锅法制备金属/氧化锌复合材料用于催化二氧化碳加氢制甲醇反应[J]. 物理化学学报, 2019, 35(2): 223 -229 .
[15]	翟岩亮, 张少龙, 张络明, 尚蕴山, 王文轩, 宋宇, 姜彩彤, 巩雁军. 不同B，Al分布对ZSM-5分子筛的甲醇制丙烯反应性能的影响[J]. 物理化学学报, 2019, 35(11): 1248 -1258 .