Citation: Zhuoyan Lv, Yangming Ding, Leilei Kang, Lin Li, Xiao Yan Liu, Aiqin Wang, Tao Zhang. Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst[J]. Acta Physico-Chimica Sinica, ;2025, 41(4): 100038. doi: 10.3866/PKU.WHXB202408015 shu

Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst

Zhuoyan Lv ^1,2 ,
Yangming Ding ¹ ,
Leilei Kang ^1,, ,
Lin Li ¹ ,
Xiao Yan Liu ^1,, ,
Aiqin Wang ¹ ,
Tao Zhang ¹

1.
CAS Key Laboratory of Science and Technology on Applied Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Leilei Kang, Xiao Yan Liu,
Received Date: 27 August 2024
Revised Date: 25 September 2024
Accepted Date: 2 October 2024

Fund Project: This work was financially supported by the NSFC Center for Single-Atom Catalysis (22388102), the Fundamental Research Funds for the Central Universities (20720220009), the DNL Cooperation Fund, CAS (DNL202002), LiaoNing Revitalization Talents Program (XLYC2007070), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0540000).

Direct epoxidation of propylene (DEP) by molecular oxygen is an ideal way to synthesize propylene oxide (PO), yet it remains quite challenging. We demonstrated here that the PO formation rate and selectivity could be enhanced simultaneously through photo-thermo-catalysis over the Cu/TiO₂ catalyst. At 180 ℃, by introducing light, the PO formation rate increased more than 20-fold (from 8.2 to 180.6 μmol∙g⁻¹∙h⁻¹) and the corresponding selectivity improved more than 3-fold (from 8% to 27%), breaking the traditional perception that the semiconductors exhibit very low reactivity for this reaction. Kinetic study results showed that the apparent activation energy for PO formation could sharply decrease under light irradiation (from 95 to 40 kJ∙mol⁻¹). In situ electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were applied to characterize the dynamics of the valence state of the copper oxide species and the activation intermediates of molecular oxygen. Evidence for the activation of oxygen, which could direct to the PO formation pathway, was captured. The light-driven electrons could promote the formation of active Cu⁺, which could form the side-on μ-peroxo Cu(II)₂ structure, weaken the O―O bond, and improve the PO formation rate and selectivity. This work paves a new way for designing semiconductor-supported photocatalysts for DEP reactions with molecular oxygen.
- Photo-thermo-catalysis,
- Cu/TiO₂,
- Selective oxidation,
- Direct propylene epoxidation,
- Oxygen activation
1. [1]
  (1) Khatib, S. J.; Oyama, S. T. Catal. Rev. Sci. Eng. 2015, 57, 306. doi: 10.1080/01614940.2015.1041849
2. [2]
  (2) Teržan, J.; Huš, M.; Likozar, B.; Djinović, P. ACS Catal. 2020, 10, 13415. doi: 10.1021/acscatal.0c03340
3. [3]
  (3) Pu, T.; Setiawan, A.; Mosevitzky Lis, B.; Zhu, M.; Ford, M. E.; Rangarajan, S.; Wachs, I. E. ACS Catal. 2022,12, 4375. doi: 10.1021/acscatal.1c05939
4. [4]
  (4) Guo, M.; Dongfang, N.; Iannuzzi, M.; van Bokhoven, J. A.; Artiglia, L. ACS Catal. 2024, 14, 10234. doi: 10.1021/acscatal.4c01566
5. [5]
  (5) Thommes, T.; Reitzmann, A.; Kraushaar-Czarnetzki, B. Appl Catal A: Gen 2007, 318, 160. doi: 10.1016/j.apcata.2006.10.051
6. [6]
  (6) Gambo, Y.; Adamu, S.; Abdulrasheed, A. A.; Lucky, R. A.; Ba-Shammakh, M. S.; Hossain, M. M. Appl Catal A: Gen 2021, 609, 117914. doi: 016/j.apcata.2020.117914
7. [7]
  (7) Haruta M.; Huang J. Res. Chem. Intermediat. 2012, 38, 1. doi: 10.1007/s11164-011-0424-6
8. [8]
  (8) Zohour, B.; Noon, D.; Seubsai, A.; Senkan, S. Ind. Eng. Chem. Res. 2014, 53, 6243. doi: 10.1021/ie402416s
9. [9]
  (9) Su, W. G.; Wang, S. G.; Ying, P. L.; Feng, Z. C.; Li, C. J. Catal. 2009, 268, 165. doi: 10.1016/j.jcat.2009.09.017
10. [10]
  (10) Zhu, W. M.; Zhang, Q. H.; Wang, Y. J. Phys. Chem. C 2008, 112, 7731. doi: 10.1021/jp800927y
11. [11]
  (11) Zhan, C.; Wang, Q. X.; Zhou, L. Y.; Han, X.; Wanyan, Y. Y.; Chen, J. Y.; Zheng, Y. P.; Wang, Y.; Fu, G.; Xie, Z. X.; et al. J. Am. Chem. Soc. 2020, 142, 14134. doi: 10.1021/jacs.0c03882
12. [12]
  (12) Qadir, M. I.; Dupont, J. Angew. Chem. Int. Ed. 2023, 62. doi: 10.1002/anie.202301497
13. [13]
  (13) Wang, Z. J.; Song, H.; Liu, H.; Ye, J. Angew. Chem. Int. Ed. 2020, 59, 8016. doi: 10.1002/anie.201907443
14. [14]
  (14) Fang, S.; Hu, Y. H. Chem. Soc. Rev. 2022, 51, 3609. doi: 10.1039/d1cs00782c
15. [15]
  (15) Pichat, P.; Herrmann, J.; Disdier, J.; Mozzanega, M. J. Phys. Chem. 1979, 83, 3122. doi: 10.1021/J100487A012
16. [16]
  (16) Tanaka, T.; Yoshida, H.; Nakagawa, H.; Funabiki, T.; Yoshida, S. Catal. Today 1993, 16, 297. doi: 10.1016/0920-5861(93)80069-D
17. [17]
  (17) Tachikawa, T.; Tojo, S.; Fujitsuka, M.; Majima, T. Langmuir 2004, 20, 4236. doi:10.1021/la0496439
18. [18]
  (18) Murata, C.; Yoshida, H.; Kumagai, J.; Hattori, T. J. Phys. Chem. B 2003, 107, 4364. doi:10.1021/jp0277006
19. [19]
  (19) Yoshida, H.; Shimizu, T.; Murata, C.; Hattori, T. J. Catal. 2003, 220, 226. doi: 10.1016/s0021-9517(03)00292-6
20. [20]
  (20) Yoshida, H.; Tanaka, T.; Yamamoto, M.; Yoshida, T.; Funabiki, T.; Yoshida, S. J. Catal.1997, 171, 351. doi:10.1006/jcat.1997.1813
21. [21]
  (21) Marimuthu, A.; Zhang, J.; Linic, S. Science 2013, 339, 1590. doi: 10.1126/science.1231631
22. [22]
  (22) Lv, Z.; Kang, L.; Pan, X.; Su, Y.; Wang, H.; Li, L.; Liu, X. Y.; Wang, A.; Zhang, T. ACS Catal. 2024, 14, 10172. doi: 10.1021/acscatal.4c01749
23. [23]
  (23) Kang, L.; Liu, X. Y.; Wang, A.; Li, L.; Ren, Y.; Li, X.; Pan, X.; Li, Y.; Zong, X.; Liu, H.; et al. Angew. Chem. Int. Ed. 2020, 59, 12909. doi: 10.1002/anie.202001701
24. [24]
  (24) Zhu, R.; Kang, L.; Li, L.; Pan, X.; Wang, H.; Su, Y.; Li, G.; Cheng, H.; Li, R.; Liu, X.; et al. Acta Phys. -Chim. Sin. 2023, 40, 2303003. doi: 10.3866/PKU.WHXB202303003
25. [25]
  (25) Yang, J.; Liu, W.; Xu, M.; Liu, X.; Qi, H.; Zhang, L.; Yang, X.; Niu, S.; Zhou, D.; Liu, Y.; et al. J. Am. Chem. Soc. 2021,143, 14530. doi: 10.1021/jacs.1c03788
26. [26]
  (26) Liu, X.; Wang, A.; Li, L.; Zhang, T.; Mou, C.-Y.; Lee, J.-F. J.Catal. 2011, 278, 288. doi: 10.1016/j.jcat.2010.12.016
27. [27]
  (27) Torres, D.; Lopez, N.; Illas, F.; Lambert, R. M. Angew. Chem. Int. Ed. 2007, 46, 2055. doi: 10.1002/anie.200603803
28. [28]
  (28) Huang, Y.; Liu, Z.; Gao, G.; Xiao, G.; Du, A.; Bottle, S.; Sarina, S.; Zhu, H. ACS Catal. 2017, 7, 4975. doi: 10.1021/acscatal.7b01180
29. [29]
  (29) Li, D.; Zhao, Y.; Miao, Y.; Zhou, C.; Zhang, L.-P.; Wu, L.-Z.; Zhang, T. Adv. Mater.2022, 34, 2207793. doi: 10.1002/adma.202207793
30. [30]
  (30) Hikov, T.; Schroeter, M. K.; Khodeir, L.; Chemseddine, A.; Muhler, M.; Fischer, R. A. Phys. Chem. Chem. Phys. 2006, 8, 1550. doi: 10.1039/b512113b
31. [31]
  (31) Liu, Y.; Zhang, B.; Luo, L.; Chen, X.; Wang, Z.; Wu, E.; Su, D.; Huang, W. Angew. Chem. Int. Ed. 2015, 54, 15260. doi: 10.1002/anie.201509115
32. [32]
  (32) Luo, L.; Gong, Z.; Xu, Y.; Ma, J.; Liu, H.; Xing, J.; Tang, J. J. Am. Chem. Soc. 2021, 144, 740. doi: 10.1021/jacs.1c09141
33. [33]
  (33) Zhang, Y.; Zhao, J.; Wang, H.; Xiao, B.; Zhang, W.; Zhao, X.; Lv, T.; Thangamuthu, M.; Zhang, J.; Guo, Y.; et al. Nat. Commun. 2022,13, doi: 10.1038/s41467-021-27698-3
34. [34]
  (34) Bello, I.; Chang, W. H.; Lau, W. M. J. Appl. Phys. 1994, 75, 3092. doi: 10.1063/1.356160
35. [35]
  (35) Li, W.; Wu, G.; Hu, W.; Dang, J.; Wang, C.; Weng, X.; da Silva, I.; Manuel, P.; Yang, S.; Guan, N.; et al. J. Am. Chem. Soc. 2022,144, 4260. doi: 10.1021/jacs.2c00792
36. [36]
  (36) He, J. L.; Zhai, Q. G.; Zhang, Q. H.; Deng, W. P.; Wang, Y. J. Catal. 2013, 299, 53. doi: 10.1016/j.jcat.2012.11.032
37. [37]
  (37) Wang, Y. N.; Ma, W. H.; Wang, D. Y.; Zhong, Q. Chem. Eng. J. 2017, 307, 1047. doi: 10.1016/j.cej.2016.09.035
38. [38]
  (38) Xiong, W.; Gu, X.-K.; Zhang, Z.; Chai, P.; Zang, Y.; Yu, Z.; Li, D.; Zhang, H.; Liu, Z.; Huang, W. Nat. Commun. 2021, 12, 5921. doi: 10.1038/s41467-021-26257-0
39. [39]
  (39) Wang, A.; Zhang, L.; Yu, Z.; Zhang, S.; Li, L.; Ren, Y.; Yang, J.; Liu, X.; Liu, W.; Yang, X.; et al. J. Am. Chem. Soc. 2023, 146, 695. doi: 10.1021/jacs.3c10551
40. [40]
  (40) Huang, M.; Zhang, S.; Wu, B.; Wei, Y.; Yu, X.; Gan, Y.; Lin, T.; Yu, F.; Sun, F.; Jiang, Z.; et al. ACS Catal. 2022, 12, 9515. doi: 10.1021/acscatal.2c02424
41. [41]
  (41) Rana, S.; Pandey, B.; Dey, A.; Haque, R.; Rajaraman, G.; Maiti, D. ChemCatChem 2016,8, 3367. doi: 10.1002/cctc.201600843
42. [42]
  (42) Ren, L.; Dai, W.; Yang, X.; Cao, Y.; Xie, Z.; Fan, K. Chin. J. Catal. 2006,27, 115. doi: 10.1016/s1872-2067(06)60009-0
43. [43]
  (43) Solomon, E.; Ginsbach, J.; Heppner, D.; Kieber, M.; Kjaergaard, C.; Smeets, P.; Tian, L.; Woertink, J. Faraday Discuss. 2011, 148, 11. doi: 10.1039/c005500j
44. [44]
  (44) Chen, P.; Root, D.; Cecelia, C.; Kiyoshi, F.; Solomon, E. J. Am. Chem. Soc. 2002,125, 466. doi: 10.1021/ja020969i
45. [45]
  (45) Woertinka, J.; Smeetsa, P.; Groothaertb, M.; Vancea, M.; Selsb, B.; Schoonheydtb, R.; Solomona, E. Proc. Natl. Acad. Sci. U. S. A. 2009,106, 18908. doi: 10.1073/pnas.0910461106
46. [46]
  (46) Li, X.; Qiao, Y.; Guo, S.; Xu, Z.; Zhu, H.; Zhang, X.; Yuan, Y.; He, P.; Ishida, M.; Zhou, H. Adv. Mater. 2018, 30, 1705197. doi: 10.1002/adma.201705197
47. [47]
  (47) Dong, J.-C.; Zhang, X.-G.; Briega-Martos, V.; Jin, X.; Yang, J.; Chen, S.; Yang, Z.-L.; Wu, D.-Y.; Feliu, J. M.; Williams, C. T.; et al. Nat. Energy 2018, 4, 60. doi: 10.1038/s41560-018-0292-z
48. [48]
  (48) Denisov, I., Makris, T.; Sligar, S.; Kincaid, J. J. Phys. Chem. A 2008, 112, 13172. doi: 10.1021/jp8017875
49. [49]
  (49) Bordiga, S.; Damin, A.; Bonino, F.; Ricchiardi, G.; Lamberti, C.; Zecchina, A. Angew. Chem. Int. Ed. 2002, 114, 4928. doi: 10.1002/ange.200290031
50. [50]
  (50) Gordon, C. P.; Engler, H.; Tragl, A. S.; Plodinec, M.; Lunkenbein, T.; Berkessel, A.; Teles, J. H.; Parvulescu, A.-N.; Coperet, C. Nature 2020, 586, 708. doi: 10.1038/s41586-020-2826-3
51. [51]
  (51) Song, Y. Y.; Wang, G. C. J. Phys. Chem. C 2018, 122, 21500. doi: 10.1021/acs.jpcc.8b07044
52. [52]
  (52) Fernandez, E.; Boronat, M.; Corma, A. J. Phys. Chem. C 2020, 124, 21549. doi: 10.1021/acs.jpcc.0c0629
53. [53]
  (53) Sun, B.; Wang, G.-C. J. Phys. Chem. C 2024, 128, 13829. doi: 10.1021/acs.jpcc.4c03206
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Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuOx/TiO2 Catalyst

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Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst