Citation: WANG Yong-Cheng, JIA Yi-Ming, WANG Wen-Xue, MA Pan-Pan. Theoretical Investigation for Two-state Reactivity of CO₂ Hydrogenation Catalyzed by Ru in Gas Phase[J]. Chinese Journal of Structural Chemistry, ;2016, 35(12): 1819-1828. doi: 10.14102/j.cnki.0254-5861.2011-1119 shu

Theoretical Investigation for Two-state Reactivity of CO₂ Hydrogenation Catalyzed by Ru in Gas Phase

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

Corresponding author: WANG Yong-Cheng, ycwang@163.com
Received Date: 8 January 2016
Accepted Date: 27 September 2016

Fund Project: National Natural Science Foundation of China 21263023

Figures(5)

Gas-phase CO₂ catalyzed activation hydrogenation by Ru atoms was studied with density functional theory. Based on the structure optimization of different potential energy surfaces, there are two crossing points between singlet and triplet potential energy surfaces and there is a crossing point between quintet and triplet potential energy surfaces in the whole catalytic cycle. Spin transition probabilities in the vicinity of the intersections have been calculated by the Landau-Zener model theory. There are three minimum energy crossing points (MECPs) with strong spin-orbital coupling effect and higher spin transition probability, and all spin inversion occurred in s orbital and different d orbitals of ruthenium, indicating this is a typical two-state reactivity (TSR) reaction. Finally, the lowest energy reaction path is ensured.
- two-state reactivity(TSR),
- carbon dioxide hydrogenation,
- minimum energy crossing point (MECP),
- transition metal catalyzed,
- intersystem crossing (ISC)
1. [1]
  Shi H, Chen G, Zhang C, Zou Z. Polymeric g-C3N4 coupled with NaNbO3 nanowires toward enhanced photocatalytic reduction of CO₂ into renewable fuel[J]. Acs Catalysis, 2014,4:3637-3643. doi: 10.1021/cs500848f
2. [2]
  Raksakoon C, Maihom T, Probst M, Limtrakul J. Hydration of carbon dioxide in copper-alkoxide functionalized metal-organic frameworks: a DFT study[J]. J. Phys. Chem. C, 2015,119:3564-3571. doi: 10.1021/jp511185p
3. [3]
  Daza Y. A, Kent R. A, Yung M. M, Kuhn J. N. Carbon dioxide conversion by reverse water-gas shift chemical looping on perovskite-type oxides[J]. Ind. Eng. Chem. Res, 2014,53:5828-5837. doi: 10.1021/ie5002185
4. [4]
  Zall C. M, Linehan J. C, Appel A. M. A molecular copper catalyst for hydrogenation of CO₂ to formate[J]. ACS Catalysis, 2015,5:5301-5305. doi: 10.1021/acscatal.5b01646
5. [5]
  Yang X, Kattel S, Senanayake S. D, Boscoboinik J. A, Nie X, Graciani J. Low pressure CO₂ hydrogenation to methanol over gold nanoparticles activated on a CeOXTiO2 interface[J]. J. Am. Chem. Soc, 2015,137:10104-10107. doi: 10.1021/jacs.5b06150
6. [6]
  Kobayashi K, Tanaka K. Reactivity of CO₂ activated on transition metals and sulfur ligands[J]. Inorg. Chem, 2015,54:5085-5095. doi: 10.1021/ic502745u
7. [7]
  Miller A. J. M, Labinger J. A, Bercaw J. E. Trialkylborane-assisted CO₂ reduction by late transition metal hydrides[J]. Organomet. Chem, 2011,30:4308-4314. doi: 10.1021/om200364w
8. [8]
  Mondal B, Neese F, Ye S. Control in the rate-determining step provides a promising strategy to develop new catalysts for CO₂ hydrogenation: a local pair natural orbital coupled cluster theory study[J]. Inorg. Chem, 2015,54:7192-7198. doi: 10.1021/acs.inorgchem.5b00469
9. [9]
  Jessop P. G, Ikariya T, Noyori R. Homogeneous hydrogenation of carbon dioxide[J]. Chem. Rev, 1995,95:259-272. doi: 10.1021/cr00034a001
10. [10]
  Solymosi F, Erdöhelyi A. Hydrogenation of CO₂ to CH4 over alumina-supported noble metals[J]. J. Mol Catal Rev, 1980:8471-8474.
11. [11]
  Weatherbee G. D, Bartholomew C. H. Hydrogenation of CO₂ on group VIII metals: IV[J]. Specific activities and selectivities of silica-supported Co, Fe, and Ru. J. Catal, 1984,87:352-362.
12. [12]
  Chen X. Y, Zhao Y. X, Wang S. G. Relativistic DFT study on the reaction mechanism of second-row transition metal Ru with CO₂[J]. J. Phys. Chem. A, 2006,110:3552-3558. doi: 10.1021/jp053296+
13. [13]
  Wang W. H, Himeda Y, Muckerman J. T, Manbeck G. F, Fujita. E. CO₂ Hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO₂ reduction[J]. Chem. Rev, 2015,115:12936-12973. doi: 10.1021/acs.chemrev.5b00197
14. [14]
  Declercq R, Bouhadir G, Bourissou D, Légaré M. A, Courtemanche M. A, Nahi K. S. Hydroboration of carbon dioxide using ambiphilic phosphine-borane catalysts: on the role of the formaldehyde adduct[J]. ACS Catalysis, 2015,5:2513-2520. doi: 10.1021/acscatal.5b00189
15. [15]
  Karamad M, Hansen H. A, Rossmeisl J, Norskov J. K. Mechanistic pathway in the electrochemical reduction of CO₂ on RuO2[J]. ACS Catalysis, 2015,5:4075-4081. doi: 10.1021/cs501542n
16. [16]
  Tominaga K. I, Sasaki Y, Kawai M, Watanabe T, Saito M. Ruthenium complex catalysed hydrogenation of carbon dioxide to carbon monoxide, methanol and methane[J]. J. Chem. Soc. Chem. Commun, 1993,7:629-631.
17. [17]
  Tsuchiya K, Huang J. D, Tominaga K. Reverse water-gas shift reaction catalyzed by mononuclear Ru complexes[J]. ACS Catalysis, 2013,3:2865-2868. doi: 10.1021/cs400809k
18. [18]
  Harvey J. N, Poli R, Smith K. M. Understanding the reactivity of transition metal complexes involving multiple spin states[J]. Coord. Chem. Rev, 2003,238:347-361.
19. [19]
  Shaik S. Spin-orbital coupling in the oxidative activation of H-H by FeO+. Selection rules and reactivity effects[J]. J.Am. Chem. Soc, 1997,119:1773-1786. doi: 10.1021/ja963033g
20. [20]
  Nian J, Wang Y, Ma W, Ji D, Wang C, La M. Theoretical investigation for the cycle reaction of N₂O (x¹Σ⁺) with CO (¹Σ⁺) catalyzed by IrO n⁺(n = 1 2) and utilizing the energy span model to study its kinetic information[J]. J.Phys. Chem. A, 2011,115:11023-11032.
21. [21]
  Ma W. P, Wang Y. C, Lv L. L, Jin Y. Z, Nian J. Y, Ji D. F, Wang Q. A theoretician’s view of the Ce+ mediated activation of the N-H bond in ammonia[J]. Comput. Theor. Chem, 2011,977:69-77. doi: 10.1016/j.comptc.2011.09.016
22. [22]
  Schröder D, Shaik S, Schwarz H. Two-state reactivity as a new concept in organometallic chemistry[J]. Acc. Chem. Res, 2000,33:139-145. doi: 10.1021/ar990028j
23. [23]
  Frisch, M. J[J]. , .
24. [24]
  Becke A. D. Density-functional thermochemistry[J]. III. The role of exact exchange. J. Chem. Phys, 1993,98:5648-5652.
25. [25]
  Lee C, Yang W, Parr R. G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J]. Phys. Rev. B, 1988,37:785-789. doi: 10.1103/PhysRevB.37.785
26. [26]
  Frisch M. J, Pople J. A, Binkley J. S. Self-consistent molecular orbital methods 25[J]. Supplementary functions for Gaussian basis sets. J. Chem. Phys, 1984,80:3265-3269.
27. [27]
  Yoshizawa K, Shiota Y, Yamabe T. Intrinsic reaction coordinate analysis of the conversion of methane to methanol by an iron-oxo species: a study of crossing seams of potential energy surfaces[J]. J. Chem. Phys, 1999,111:538-545. doi: 10.1063/1.479333
28. [28]
  Harvey J. N, Aschi M, Schwarz H. The singlet and triplet states of phenyl cation[J]. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces. Theor. Chem. Acc, 1998,99:95-99.
29. [29]
  Coveney P. V, Child M. S, Barany A. The two-state S matrix for the Landau-Zener potential curve crossing model: predissociation and resonant scattering[J]. J. Phys. B: At. Mol. Phys, 1985,18:4557-4580. doi: 10.1088/0022-3700/18/23/009
30. [30]
  Zhu C. Y, Nakamura H. Theory of nonadiabatic transition for general two-state curve crossing problems[J]. II. Landau-Zener case. J. Chem. Phys, 1995,102:7448-7461.
31. [31]
  Wittig C. The Landau-Zener Formu[J]. J.Phys. Chem. B, 2005,109:8428-8430. doi: 10.1021/jp040627u
32. [32]
  Goodrow A, Bell A. T, Head-Gordon M. Are spin-forbidden crossings a Bottleneck in methanol oxidation[J]. J.Phys. Chem. C, 2009,113:19361-19364. doi: 10.1021/jp906603r
33. [33]
  Jin Y. Z, Wang Y. C, Geng Z. Y, Wang H. J, Gan Y. Z. Competitive activation of C-H and C-F bonds in gas phase reaction of Ir+ with CH3F: a DFT study[J]. J. Organomet. Chem, 2012,717:195-201. doi: 10.1016/j.jorganchem.2012.07.017
34. [34]
  Steinfeld J I, Francisco J. S, Hase W. L. Chemical kinetics and dynamics[J]. Prentice Hall, 1999.
35. [35]
  Shavitt . On the problem of calculating the rate constants of elementary reactions[J]. Chem. Phys, 1959,31:1359-1367.
36. [36]
  Lu T, Chen F. Multiwfn: a multifunctional wavefunction analyzer[J]. J. Comp. Chem, 2012,33:580-592. doi: 10.1002/jcc.v33.5
37. [37]
  Fedorov D. G, Koseki S, Schmidt M. W, Gordon M. S. Spin-orbital coupling in molecules: chemistry beyond the adiabatic approximation[J]. Int. Rev. Phys. Chem, 2003,22:551-592. doi: 10.1080/0144235032000101743
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19. [19]
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Theoretical Investigation for Two-state Reactivity of CO2 Hydrogenation Catalyzed by Ru in Gas Phase

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通讯作者: 陈斌, bchen63@163.com

Theoretical Investigation for Two-state Reactivity of CO₂ Hydrogenation Catalyzed by Ru in Gas Phase