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

Click here to download Supporting Info material in PDF type

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. doi: 10.3866/PKU.WHXB201504014

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

[1]	Hanyu Xu, Xuedan Song, Qing Zhang, Chang Yu, Jieshan Qiu. Mechanistic Insights into Water-Mediated CO₂ Electrochemical Reduction Reactions on Cu@C₂N Catalysts: A Theoretical Study [J]. Acta Phys. -Chim. Sin., 2024, 40(1): 2303040-.
[2]	Heran Wang, Kai Chen, Shuo Fu, Haoxuan Wang, Jiaxuan Yuan, Xingyi Hu, Wenjuan Xu, Baoxiu Mi. Isomeric Bisbenzophenothiazines: Synthesis, Theoretical Calculations, and Photophysical Properties [J]. Acta Phys. -Chim. Sin., 2024, 40(1): 2303047-.
[3]	Meng Li, Fulin Yang, Jinfa Chang, Alex Schechter, Ligang Feng. MoP-NC Nanosphere Supported Pt Nanoparticles for Efficient Methanol Electrolysis [J]. Acta Phys. -Chim. Sin., 2023, 39(9): 2301005-0.
[4]	Yanhui Yu, Peng Rao, Suyang Feng, Min Chen, Peilin Deng, Jing Li, Zhengpei Miao, Zhenye Kang, Yijun Shen, Xinlong Tian. Atomic Co Clusters for Efficient Oxygen Reduction Reaction [J]. Acta Phys. -Chim. Sin., 2023, 39(8): 2210039-0.
[5]	Cheng Luo, Qing Long, Bei Cheng, Bicheng Zhu, Linxi Wang. A DFT Study on S-Scheme Heterojunction Consisting of Pt Single Atom Loaded G-C₃N₄ and BiOCl for Photocatalytic CO₂ Reduction [J]. Acta Phys. -Chim. Sin., 2023, 39(6): 2212026-.
[6]	Zhen Liu, Xiangfu Meng, Wanmiao Gu, Jun Zha, Nan Yan, Qing You, Nan Xia, Hui Wang, Zhikun Wu. Introducing Novel, Multiple Cd Coordination Modes into Gold Nanoclusters by Combined Doping for Enhancing Electrocatalytic Performance [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2212064-.
[7]	Jie Wang, Guigao Liu, Qinbai Yun, Xichen Zhou, Xiaozhi Liu, Ye Chen, Hongfei Cheng, Yiyao Ge, Jingtao Huang, Zhaoning Hu, Bo Chen, Zhanxi Fan, Lin Gu, Hua Zhang. Epitaxial Growth of Unconventional 4H-Pd Based Alloy Nanostructures on 4H-Au Nanoribbons towards Highly Efficient Electrocatalytic Methanol Oxidation [J]. Acta Phys. -Chim. Sin., 2023, 39(10): 2305034-.
[8]	Ruoning Li, Xue Zhang, Na Xue, Jie Li, Tianhao Wu, Zhen Xu, Yifan Wang, Na Li, Hao Tang, Shimin Hou, Yongfeng Wang. Hierarchical Self-Assembly of Ag-Coordinated Motifs on Ag(111) [J]. Acta Phys. -Chim. Sin., 2022, 38(8): 2011060-.
[9]	Haoran Lu, Yaqing Wei, Run Long. Charge Localization Induced by Nanopore Defects in Monolayer Black Phosphorus for Suppressing Nonradiative Electron-Hole Recombination through Time-Domain Simulation [J]. Acta Phys. -Chim. Sin., 2022, 38(5): 2006064-.
[10]	Yishun Yang, Min Zhou, Yanxia Xing. Symmetry-Dependent Transport Properties of γ-Graphyne-based Molecular Magnetic Tunnel Junctions [J]. Acta Phys. -Chim. Sin., 2022, 38(4): 2003004-.
[11]	Ying Liu, Xiaofang Liu, Lin Xia, Chaojie Huang, Zhaoxuan Wu, Hui Wang, Yuhan Sun. Methanol Synthesis by CO_x Hydrogenation over Cu/ZnO/Al₂O₃ Catalyst via Hydrotalcite-Like Precursors: the Role of CO in the Reactant Mixture [J]. Acta Phys. -Chim. Sin., 2022, 38(3): 2002017-.
[12]	Mengting Li, Xingqun Zheng, Li Li, Zidong Wei. Research Progress of Hydrogen Oxidation and Hydrogen Evolution Reaction Mechanism in Alkaline Media [J]. Acta Phys. -Chim. Sin., 2021, 37(9): 2007054-.
[13]	Lin Lv, Liyang Zhang, Xuebing He, Hong Yuan, Shuxin Ouyang, Tierui Zhang. Energy-Efficient Hydrogen Production via Electrochemical Methanol Oxidation Using a Bifunctional Nickel Nanoparticle-Embedded Carbon Prism-Like Microrod Electrode [J]. Acta Phys. -Chim. Sin., 2021, 37(7): 2007079-.
[14]	Xingang Fei, Haiyan Tan, Bei Cheng, Bicheng Zhu, Liuyang Zhang. 2D/2D Black Phosphorus/g-C₃N₄ S-Scheme Heterojunction Photocatalysts for CO₂ Reduction Investigated using DFT Calculations [J]. Acta Phys. -Chim. Sin., 2021, 37(6): 2010027-.
[15]	Congming Li, Kuo Chen, Xiaoyue Wang, Nan Xue, Hengquan Yang. Understanding the Role of Cu/ZnO Interaction in CO₂ Hydrogenation to Methanol [J]. Acta Phys. -Chim. Sin., 2021, 37(5): 2009101-.

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

PDF

Like

Knowledge

Abstract

Supporting Info

Cite this article

share this article

References

Related Articles 15

Metrics

Recommended 0