Citation: Ci Chenggang, Dong Long, Zang Jiechao, Luo Guoxiang. Mechanistic Insight into the Photo-splitting of Water to Dihydrogen Catalyzed by Si-Substituted Keggin-type Polyoxometalate[J]. Chemistry, ;2020, 83(9): 837-843. shu

Mechanistic Insight into the Photo-splitting of Water to Dihydrogen Catalyzed by Si-Substituted Keggin-type Polyoxometalate

1.
Key Laboratory of Computational Catalytic Chemistry of Guizhou Province, Department of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun, 558000
2.
School of Chemistry and Chemical Engineering, Daqing Normal University, Daqing, 163712

Corresponding author: Ci Chenggang, chenggci@sgmtu.edu.cn
Received Date: 24 March 2020
Accepted Date: 4 April 2020

Figures(5)

The photo-splitting mechanism of water to obtain H₂ by Keggin-type polyoxometalate (POM) [SiW₁₂O₄₀]^4- has been investigated using DFT and TD-DFT calculations. The catalytic cycle can be divided into four steps, i.e. (1) photoexcitation, (2) electron transfer and formation of one-electron-reduced (OER) intermediate, (3) formation of two-electron-reduced (TER) intermediate, and (4) H₂ release and regeneration of the catalyst. Once an electron is transferred from CH₃OH to POM, the following steps are thermodynamically favorable and induce the second electron transfer from ·CH₂OH, H[SiW₁₂O₄₀]^4-, or [SiW₁₂O₄₀]^5- to OER intermediate H[SiW₁₂O₄₀]^4- or [SiW₁₂O₄₀]^5- to form TER intermediate [SiW₁₂O₄₀]^6-, H[SiW₁₂O₄₀]^5-, or H₂[SiW₁₂O₄₀]^4-, and accompanied by the generation of H₂. Coupled proton and electron transfer pathway is energetic favorable. The participation of CH₃OH and H₂O is favorable to form H₂. The POM acts as photosensitizer, catalyst, electron reservoir and donner in the entire catalytic cycle.
- Polyoxometalates,
- Photo-splitting of water,
- H₂-generation,
- Mechanism,
- DFT
1. [1]
  Tachibana Y, Vayssieres L, Durrant J. Nat. Photon., 2012, 6: 511~518.
2. [2]
  Dalle K E, Warnan J, Leung J J, et al. Chem. Rev., 2019, 119(4): 2752~2875.
3. [3]
4. [4]
5. [5]
6. [6]
7. [7]
  Hou Y, Pang H, Zhang L, et al. J. Power Sources, 2020, 446: 227319.
8. [8]
  Wang S S, Yang G Y. Chem. Rev., 2015, 115: 4893~4962.
9. [9]
  Ding Y S, Wang H Y, Ding Y. Dalton Transac., 2020, 49: 3457~3462.
10. [10]
  Paille G, Boulmier A, Bensaid A, et al. Chem. Commun., 2019, 55: 4166~4169.
11. [11]
  Zhang Z Y, Lin Q P, Zheng S T, et al. Chem. Commun., 2011, 47: 3918~3920.
12. [12]
  Akid R, Darwent J R. J. Chem. Soc., Dalton Transac., 1985, 395~399.
13. [13]
  Keïta B, Nadjo L. J. Electroanal. Chem., 1985, 191: 441~448.
14. [14]
  Dang L Q, You W S, Zhang X, et al. Chin. Chem. Lett., 2006, 17(7): 973~976.
15. [15]
  Nie Y H, Chen W L, Liu Z J, et al. Inorg. Chem. Commun., 2015, 61: 184~186.
16. [16]
  Huang B S, Hart J N. Phys. Chem. Chem. Phys., 2020, 22: 1727~1737.
17. [17]
  Kataoka Y, Yano N, Handa M, et al. Dalton Transac., 2019, 48: 7302~7312.
18. [18]
  Kayanuma M, Stoll T, Daniel C, et al. Phys. Chem. Chem. Phys., 2015, 17: 10497~10509.
19. [19]
  Ravelli D, Dondi D, Fagnoni M, et al. J. Comput. Chem., 2011, 32: 2983~2987.
20. [20]
  Ravelli D, Dondi D, Fagnoni M, et al. Phys. Chem. Chem. Phys., 2013, 15: 2890~2986.
21. [21]
  Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 16; Gaussian, Inc., Wallingford, CT, 2016.
22. [22]
  Lee C, Yang C, Parr R G. Phys. Rev. B, 1988, 37: 785~789.
23. [23]
  Becke A D. J. Chem. Phys., 1993, 98: 5648~5652.
24. [24]
  Stephens P J, Devlin F J, Chabalowski C F, et al. J. Phys. Chem., 1994, 98: 11623~11627.
25. [25]
  Hay P J, Wadt W R. J. Chem. Phys., 1985, 82: 270~283.
26. [26]
  Francl M M, Pietro W J, Hehre W J, et al. J. Chem. Phys., 1982, 77: 3654~3661.
27. [27]
  Hehre W J, Ditchfield R, Pople J A. J. Chem. Phys., 1972, 56: 2257.
28. [28]
  Hariharan P C, Pople J A. Theor. Chim. Acta, 1973, 28: 213~222.
29. [29]
  Casida M E, Jamorski C, Casida K C, et al. J. Chem. Phys., 1998, 108: 4439~4449.
30. [30]
  Stratmann R E, Scuseria G E, Frisch M J. J. Chem. Phys., 1998, 109: 8218~8224.
31. [31]
  Zhao Y, Truhlar D G. Theor. Chem. Acc., 2008, 120: 215~241.
32. [32]
  Zhao Y, Truhlar D G. J. Chem. Theory Comput., 2008, 4: 1849~1868.
33. [33]
  Xu X, Goddard Ⅲ W A. PNAS, 2004, 101: 2673~2677.
34. [34]
  Yanai T, Tew D P, Handy N C. Chem. Phys. Lett., 2004, 393: 51~57.
35. [35]
  Becke A D. Phys. Rev. A, 1988, 38: 3098~3100.
36. [36]
  Perdew J P. Phys. Rev. B, 1986, 33: 8822~8824.
37. [37]
  Chai J D, Head-Gordon M. J. Chem. Phys., 2008, 128: 084106.
38. [38]
  O'Boyle N M, Tenderholt A L, Langner K M. J. Comput. Chem., 2008, 29: 839~845.
39. [39]
  Cancès E, Mennucci B, Tomasi J. J. Chem. Phys., 1997, 107: 3032~3041.
40. [40]
  Niu J Y, You X Z, Duan C Y, et al. Inorg. Chem., 1996, 35: 4211~4217.
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沈阳化工大学材料科学与工程学院沈阳 110142