Citation: Jiajie Li, Xiaocong Ma, Jufang Zheng, Qiang Wan, Xiaoshun Zhou, Yahao Wang. Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms[J]. University Chemistry, ;2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117 shu

Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua 321004, Zhejiang Province, China

Received Date: 27 June 2024
Revised Date: 29 August 2024

In recent years, electrocatalytic organic synthesis has attracted increasing attention. Its advantages such as low pollution and high atomic efficiency give it a huge advantage over traditional organic synthesis methods and meet the social requirements of green chemistry. Therefore, detecting the reaction process and key intermediates at the electrode interface from the molecular level has important guiding significance for understanding the reaction mechanism and designing more efficient catalysts. Raman spectroscopy is a type of vibrational spectroscopy that is non-destructive and uninterrupted by water. In particular, surface-enhanced Raman spectroscopy has ultra-high surface sensitivity. It can provide key information on the catalyst surface structure, adsorbed substances and intermediates during the reaction, and provide a reliable platform for exploring the reaction mechanism. This article reviews the recent advances in electrocatalytic organic reaction mechanisms probed by in-situ Raman spectroscopy. Specifically, Raman spectroscopy reveals important intermediates, active substances and reaction pathways in electrocatalytic hydrogenation, activations of C―O, C―X (X = F, Cl, Br, I) and C―H bonds. By analyzing specific cases, it aims to help students understand the research frontiers of organic electrosynthesis and stimulate interest in exploring synthetic electrochemistry, one of IUPAC’s “Top Ten Emerging Technologies in Chemistry” in 2023.
- Raman spectroscopy,
- Organic electrochemical synthesis,
- Electrocatalysis,
- Reaction mechanism
1. [1]
  Novaes, L. F. T.; Liu, J.; Shen, Y.; Lu, L.; Meinhardt, J. M.; Lin, S. Chem. Soc. Rev. 2021, 50 (14), 7941.
2. [2]
  Francke, R. Curr. Opin. Electrochem. 2022, 36, 101111.
3. [3]
  Heo, J.; Ahn, H.; Won, J.; Son, J. G.; Shon, H. K.; Lee, T. G.; Han, S. W.; Baik, M.-H. Science 2020, 370 (6513), 214.
4. [4]
  Ma, C.; Fang, P.; Liu, Z.-R.; Xu, S.-S.; Xu, K.; Cheng, X.; Lei, A.; Xu, H.-C.; Zeng, C.; Mei, T.-S. Sci. Bull. 2021, 66 (23), 2412.
5. [5]
  Wu, X.; Wang, Y.; Wu, Z.-S. Chem 2022, 8 (10), 2594.
6. [6]
  Downes, C. A.; Marinescu, S. C. ChemSusChem 2017, 10 (22), 4374.
7. [7]
  Chong, X.; Liu, C.; Huang, Y.; Huang, C.; Zhang, B. Natl. Sci. Rev. 2020, 7 (2), 285.
8. [8]
  Li, N.; Pan, C.; Lu, G.; Pan, H.; Han, Y.; Wang, K.; Jin, P.; Liu, Q.; Jiang, J. Adv. Mater. 2023, 36 (5), 2311023.
9. [9]
  Shi, Z.; Chen, J.; Li, K.; Liu, Y.; Tang, Y.; Zhang, L. Chem. Eng. J. 2023, 461, 141933.
10. [10]
  Drasbæk, D. B.; Welander, M. M.; Traulsen, M. L.; Sudireddy, B. R.; Holtappels, P.; Walker, R. A. J. Mater. Chem. A 2022, 10 (10), 5550.
11. [11]
  Xue, H.; Yang, T.; Zhang, Z.; Zhang, Y.; Geng, Z.; He, Y. Appl. Catal. B, 2023, 330, 122641.
12. [12]
  Pople, J. M. M.; Nicholls, T. P.; Pham, L. N.; Bloch, W. M.; Lisboa, L. S.; Perkins, M. V.; Gibson, C. T.; Coote, M. L.; Jia, Z.; Chalker, J. M. J. Am. Chem. Soc. 2023, 145 (21), 11798.
13. [13]
  Zhang, B.; He, J.; Gao, Y.; Levy, L.; Oderinde, M. S.; Palkowitz, M. D.; Dhar, T. G. M.; Mandler, M. D.; Collins, M. R.; Schmitt, D. C.; et al. Nature 2023, 623 (7988), 745.
14. [14]
  Wang, Y.; Zhao, R.; Ackermann, L. Adv. Mater. 2023, 35 (49), 2300760.
15. [15]
  Gu, Z.; Zhang, Z.; Ni, N.; Hu, C.; Qu, J. Environ. Sci. Technol. 2022, 56 (7), 4356.
16. [16]
  Yuan, S.; Xue, Y.; Ma, R.; Ma, Q.; Chen, Y.; Fan, J. Sci. Total Environ. 2023, 866, 161444.
17. [17]
  Yang, Y.; Wang, H.; Li, J.; He, B.; Wang, T.; Liao, S. Environ. Sci. Technol. 2012, 46 (12), 6815.
18. [18]
  Li, C.-Y.; Tian, Z.-Q. Chem. Soc. Rev. 2024, 53 (7), 3579.
19. [19]
  Hess, C. Chem. Soc. Rev. 2021, 50 (5), 3519.
20. [20]
  Wang, Y.-H.; Zheng, S.; Yang, W.-M.; Zhou, R.-Y.; He, Q.-F.; Radjenovic, P.; Dong, J.-C.; Li, S.; Zheng, J.; Yang, Z.-L.; et al. Nature 2021, 600 (7887), 81.
21. [21]
  Wang, Y.-H.; Wei, J.; Radjenovic, P.; Tian, Z.-Q.; Li, J.-F. Anal. Chem. 2019, 91 (3), 1675.
22. [22]
  Elliott, A. B. S.; Horvath, R.; Gordon, K. C. Chem. Soc. Rev. 2012, 41 (5), 1929.
23. [23]
  Wang, Y. H.; Wang, X. T.; Ze, H.; Zhang, X. G.; Radjenovic, P. M.; Zhang, Y. J.; Dong, J. C.; Tian, Z. Q.; Li, J. F. Angew. Chem. Int. Ed. 2021, 60 (11), 5708.
24. [24]
  Lin, X.-M.; Wang, X.-T.; Deng, Y.-L.; Chen, X.; Chen, H.-N.; Radjenovic, P. M.; Zhang, X.-G.; Wang, Y.-H.; Dong, J.-C.; Tian, Z.-Q.; et al. Nano Lett. 2022, 22 (13), 5544.
25. [25]
26. [26]
  Keeler, A. J.; Salazar-Banda, G. R.; Russell, A. E. Curr. Opin. Electrochem. 2019, 17, 90.
27. [27]
  Wang, Y. H.; Liang, M. M.; Zhang, Y. J.; Chen, S.; Radjenovic, P.; Zhang, H.; Yang, Z. L.; Zhou, X. S.; Tian, Z. Q.; Li, J. F. Angew. Chem. Int. Ed. 2018, 57 (35), 11257.
28. [28]
  Xu, J.; Wang, Z. ChemElectroChem 2023, 10 (19), e202300370.
29. [29]
  Li, X.-C.; Wang, B.; Yu, Z.; Wan, Q.; Zheng, J.-F.; Maisonhaute, E.; Zhou, X.-S.; Wang, Y.-H. Sci. China: Chem. 2024, 2224.
30. [30]
  Hie, L.; Fine Nathel, N. F.; Hong, X.; Yang, Y. F.; Houk, K. N.; Garg, N. K. Angew. Chem. Int. Ed. 2016, 55 (8), 2810.
31. [31]
  Liu, C.; Tao, H.; Li, J.; Huang, J.; Zhang, Z.; Niu, Y.; Liu, Y.; Lian, C.; Liu, H. Chem. Eng. J. 2024, 287, 119804.
32. [32]
  Chong, Y.; Chen, T.; Li, Y.; Lin, J.; Huang, W.-H.; Chen, C.-L.; Jin, X.; Fu, M.; Zhao, Y.; Chen, G. ; et al. Environ. Sci. Technol. 2023, 57 (14), 5831.
33. [33]
  Qi, Y.; Zhang, Y.; Yang, L.; Zhao, Y.; Zhu, Y.; Jiang, H.; Li, C. Nat. Commun. 2022, 13 (1), 4602.
34. [34]
  Jahromi, A. F.; Ruiz-López, E.; Dorado, F.; Baranova, E. A.; de Lucas-Consuegra, A. Renew. Energ. 2022, 183, 515.
35. [35]
  Huang, H.; Yu, C.; Han, X.; Huang, H.; Wei, Q.; Guo, W.; Wang, Z.; Qiu, J. Energy Environ. Sci. 2020, 13 (12), 4990.
36. [36]
  Hu, X.; Lu, J.; Liu, Y.; Chen, L.; Zhang, X.; Wang, H. Environ. Chem. Lett. 2023, 21 (5), 2825.
37. [37]
  Vo, T.-G.; Ho, P.-Y.; Chiang, C.-Y. Appl. Catal. B 2022, 300, 120723.
38. [38]
  Cheng, Z.; Hu, J.; Zhou, W.; Deng, W.; Ma, M.; Tan, Y. J. Mater. Chem. A 2024, 12 (22), 13400.
39. [39]
  Wu, J.; Xie, W.; Zhang, Y.; Ke, X.; Li, T.; Fang, H.; Sun, Y.; Zeng, X.; Lin, L.; Tang, X. J. Energy Chem. 2024, 95, 670.
40. [40]
  Zhou, Y.; Shen, Y.; Li, H. Appl. Catal. B 2022, 317, 121776.
41. [41]
  Zhou, B.; Dong, C.-L.; Huang, Y.-C.; Zhang, N.; Wu, Y.; Lu, Y.; Yue, X.; Xiao, Z.; Zou, Y.; Wang, S. J. Energy Chem. 2021, 61, 179.
42. [42]
  Li, Z.; Huai, L.; Hao, P.; Zhao, X.; Wang, Y.; Zhang, B.; Chen, C.; Zhang, J. Chin. J. Catal. 2022, 43 (3), 793.
43. [43]
  Liu, P.; Huai, L.; Zhu, B.; Zhong, Y.; Zhang, J.; Chen, C. Green Chem. 2024, 26 (9), 5377.
44. [44]
  Cui, Z.; Dong, X. A.; Cho, S. G.; Tegomoh, M. N.; Dai, W.; Dong, F.; Co, A. C. Nat. Commun. 2022, 13 (1), 5840.
45. [45]
  Linnemann, J.; Kanokkanchana, K.; Tschulik, K. ACS Catal. 2021, 11 (9), 5318.
46. [46]
  Fang, Z.; Jackson, J. E.; Hegg, E. L. ACS Sustain. Chem. Eng. 2022, 10 (23), 7545.
47. [47]
  Peng, T.; Zhuang, T.; Yan, Y.; Qian, J.; Dick, G. R.; Behaghel de Bueren, J.; Hung, S.-F.; Zhang, Y.; Wang, Z.; Wicks, J.; et al. J. Am. Chem. Soc. 2021, 143 (41), 17226.
48. [48]
  Zhang, P.; Sheng, X.; Chen, X.; Fang, Z.; Jiang, J.; Wang, M.; Li, F.; Fan, L.; Ren, Y.; Zhang, B.; et al. Angew. Chem. Int. Ed. 2019, 58 (27), 9155.
49. [49]
  Kong, A.; Liu, M.; Zhang, H.; Cao, Z.; Zhang, J.; Li, W.; Han, Y.; Fu, Y. Chem. Eng. J. 2022, 445, 136719.
50. [50]
  Ma, J.; Wang, Z.; Majima, T.; Zhao, G. ACS Catal. 2022, 12 (22), 14062.
51. [51]
  Min, Y.; Mei, S.-C.; Pan, X.-Q.; Chen, J.-J.; Yu, H.-Q.; Xiong, Y. Nat. Commun. 2023, 14 (1), 5134.
52. [52]
  Liu, J.; Cai, Z.-Y.; Sun, W.-X.; Wang, J.-Z.; Shen, X.-R.; Zhan, C.; Devasenathipathy, R.; Zhou, J.-Z.; Wu, D.-Y.; Mao, B.-W.; et al. J. Am. Chem. Soc. 2020, 142 (41), 17489.
53. [53]
  Zhuo, Q.; Lu, J.; Niu, J.; Crittenden, J. C.; Yu, G.; Wang, S.; Yang, B.; Chen, Z. ACS EST Eng. 2022, 2 (10), 1756.
54. [54]
  Wang, A.; Huang, Y.-F.; Sur, U. K.; Wu, D.-Y.; Ren, B.; Rondinini, S.; Amatore, C.; Tian, Z.-Q. J. Am. Chem. Soc. 2010, 132 (28), 9534.
55. [55]
  Jiang, C.-C.; Li, X.-C.; Fan, J.-A.; Fu, J.-Y.; Huang-Fu, X.-N.; Li, J.-J.; Zheng, J.-F.; Zhou, X.-S.; Wang, Y.-H. Analyst 2022, 147 (7), 1341.
56. [56]
57. [57]
  Massignan, L.; Zhu, C.; Hou, X.; Oliveira, J. C. A.; Salamé, A.; Ackermann, L. ACS Catal. 2021, 11 (18), 11639.
58. [58]
  Sauermann, N.; Meyer, T. H.; Qiu, Y.; Ackermann, L. ACS Catal. 2018, 8 (8), 7086.
59. [59]
  Stevens, M. A.; Colebatch, A. L. Chem. Soc. Rev. 2022, 51 (6), 1881.
60. [60]
  Liu, X.; He, X.; Fang, Z.; Gong, S.; Xiong, D.; Chen, W.; Wang, J.; Chen, Z. Chem. Mater. 2024, 36 (2), 968.
61. [61]
  Tian, H.; Zhang, Y.; Yu, D.; Yang, X.; Wang, H.; Matindi, C.; Yin, Z.; Hui, H.; Mamba, B. B.; Li, J. Electrochim. Acta 2022, 426, 140796.
62. [62]
  Wang, K.; Guo, Z.; Zhou, M.; Yang, Y.; Li, L.; Li, H.; Luque, R.; Saravanamurugan, S. J. Energy Chem. 2024, 91, 542.
63. [63]
  Dang, K.; Dong, H.; Wang, L.; Jiang, M.; Jiang, S.; Sun, W.; Wang, D.; Tian, Y. Adv. Mater. 2022, 34 (27), 2200302.
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