Citation: Zhenchun Yang, Bixiao Guo, Zhenyu Hu, Kun Wang, Jiahao Cui, Lina Li, Chun Hu, Yubao Zhao. Molecular engineering towards dual surface local polarization sites on poly(heptazine imide) framework for boosting H₂O₂ photo-production[J]. Chinese Chemical Letters, ;2024, 35(8): 109251. doi: 10.1016/j.cclet.2023.109251 shu

Molecular engineering towards dual surface local polarization sites on poly(heptazine imide) framework for boosting H₂O₂ photo-production

Zhenchun Yang ^a ,
Bixiao Guo ^b ,
Zhenyu Hu ^a ,
Kun Wang ^a ,
Jiahao Cui ^a ,
Lina Li ^a ,
Chun Hu ^a ,
Yubao Zhao ^{a, *,}

a.
Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Institute of Environmental Research at Greater Bay, Guangzhou University, Guangzhou 510006, China
b.
Department of Environmental Science and Engineering, Guangzhou University, Guangzhou 510006, China

ybzhao@gzhu.edu.cn

Received Date: 7 July 2023
Revised Date: 7 October 2023
Accepted Date: 26 October 2023
Available Online: 2 November 2023

Figures(4)

The selective 2e⁻ ORR reaction on polymeric carbon nitride framework is one of the most promising approaches for solar-driven hydrogen peroxide production. Poly(heptazine imide) (PHI) as a class of K⁺-incorporated crystalline carbon nitride framework, is highly active for photocatalytic H₂O₂ production. An upgrade on the H₂O₂ photoproduction performance of PHI is realized and the mechanistic insights are revealed in this work. By photochemical reaction, the electron withdrawing groups of hydroxyl group and cyano group are grafted on the surface of PHI frameworks. The dual polarization sites on the surface contribute significantly to the enhancement of the exciton dissociation. The optimized PHI with dual polarization sites exhibits a remarkable photocatalytic H₂O₂ production performance, which is 2 times of the active pristine PHI. Most importantly, the photochemical reaction method is generally applicable to improve the exciton dissociation of a wide range of polymeric carbon nitride frameworks with various structure and compositions; and the thiourea-derived polymeric carbon nitride framework with dual surface polarization sites exhibits a remarkable photocatalytic performance with a high H₂O₂ production rate of 40.5 mmol h⁻¹ g⁻¹.
- Photocatalysis,
- Hydrogen peroxide production,
- Carbon nitride framework,
- Surface functionalization,
- ORR
1. [1]
  C. Cao, X. Wang, N. Yang, et al., Chem. Sci. 13 (2022) 863–889. doi: 10.1039/D1SC05482A
2. [2]
  Y. Wen, F. Huo, C. Yin, Chin. Chem. Lett. 30 (2019) 1834–1842. doi: 10.1016/j.cclet.2019.07.006
3. [3]
  Y. Xue, Y. Wang, Z. Pan, et al., Angew. Chem. Int. Ed. 60 (2021) 10469–10480. doi: 10.1002/anie.202011215
4. [4]
  J.M. Campos-Martin, G. Blanco-Brieva, J.L. Fierro, Angew. Chem. Int. Ed. 45 (2006) 6962–6984. doi: 10.1002/anie.200503779
5. [5]
  C. Xia, Y. Xia, P. Zhu, et al., Science 366 (2019) 226–231. doi: 10.1126/science.aay1844
6. [6]
  X. Hu, X. Zeng, Y. Liu, et al., Nanoscale 12 (2020) 16008–16027. doi: 10.1039/D0NR03178J
7. [7]
  C. Huang, E. Fan, H. Xu, et al., Solid State Sci. 113 (2021) 106533. doi: 10.1016/j.solidstatesciences.2021.106533
8. [8]
  Y. Huang, Y. Jian, L. Li, et al., Angew. Chem. Int. Ed. 60 (2021) 5245–5249. doi: 10.1002/anie.202014317
9. [9]
  H. Wang, Y. Xu, D. Xu, et al., ACS EST Eng. 2 (2022) 140–157. doi: 10.1021/acsestengg.1c00337
10. [10]
  C. Zhao, Z. Chen, R. Shi, et al., Adv. Mater. 32 (2020) 1907296. doi: 10.1002/adma.201907296
11. [11]
  S. Zhang, Y. Yang, Y. Zhai, et al., Chin. Chem. Lett. 34 (2023) 107652. doi: 10.1016/j.cclet.2022.06.075
12. [12]
  X. Chen, W. Zhang, L. Zhang, et al., ACS Appl. Mater. Interfaces 13 (2021) 25868–25878. doi: 10.1021/acsami.1c02953
13. [13]
  H. Cheng, H. Lv, J. Cheng, et al., Adv. Mater. 34 (2022) 2107480. doi: 10.1002/adma.202107480
14. [14]
  K. Sahel, L. Elsellami, I. Mirali, et al., Appl. Catal. B 188 (2016) 106–112. doi: 10.1016/j.apcatb.2015.12.044
15. [15]
  J. Luo, C. Fan, L. Tang, et al., Appl. Catal. B 301 (2022) 120757. doi: 10.1016/j.apcatb.2021.120757
16. [16]
  V. Briega-Martos, A. Ferre-Vilaplana, A. de la Peña, et al., ACS Catal. 7 (2017) 1015–1024. doi: 10.1021/acscatal.6b03043
17. [17]
  H. Zhang, L.H. Guo, L. Zhao, et al., J. Phys. Chem. Lett. 6 (2015) 958–963. doi: 10.1021/acs.jpclett.5b00149
18. [18]
  Y. Kofuji, S. Ohkita, Y. Shiraishi, et al., ACS Sustain. Chem. Eng. 5 (2017) 6478–6485. doi: 10.1021/acssuschemeng.7b00575
19. [19]
  L. Li, L. Xu, Z. Hu, et al., Adv. Funct. Mater. 31 (2021) 2106120. doi: 10.1002/adfm.202106120
20. [20]
  F. Liu, R. Shi, Z. Wang, et al., Angew. Chem. Int. Ed. 58 (2019) 11791–11795. doi: 10.1002/anie.201906416
21. [21]
  Y. Shiraishi, T. Takii, T. Hagi, et al., Nat. Mater. 18 (2019) 985–993. doi: 10.1038/s41563-019-0398-0
22. [22]
  Q. Tian, L. Jing, S. Ye, et al., Small 17 (2021) e2103224. doi: 10.1002/smll.202103224
23. [23]
  L. Xu, Y. Liu, L. Li, et al., ACS Catal. 11 (2021) 14480–14488. doi: 10.1021/acscatal.1c03690
24. [24]
  C. Liu, T. Bao, L. Yuan, et al., Adv. Funct. Mater. 32 (2021) 2111404.
25. [25]
  L. Li, D. Cruz, A. Savateev, et al., Appl. Catal. B 229 (2018) 249–253. doi: 10.1016/j.apcatb.2018.01.065
26. [26]
  M. Li, Q. Zheng, D.P. Durkin, et al., J. Hazard. Mater. 436 (2022) 129251. doi: 10.1016/j.jhazmat.2022.129251
27. [27]
  X. Li, J. Zhang, Y. Huo, et al., Appl. Catal. B 280 (2021) 119452. doi: 10.1016/j.apcatb.2020.119452
28. [28]
  Y. Fu, C.A. Liu, M. Zhang, et al., Adv. Energy Mater. 8 (2018) 1802525. doi: 10.1002/aenm.201802525
29. [29]
  D. Li, C. Wen, J. Huang, et al., Appl. Catal. B 307 (2022) 121099. doi: 10.1016/j.apcatb.2022.121099
30. [30]
  K. Li, L. Bao, S. Cao, et al., ACS Appl. Energy Mater. 4 (2021) 12965–12973. doi: 10.1021/acsaem.1c02602
31. [31]
  L. Dai, A. Dong, X. Meng, et al., Angew. Chem. Int. Ed. 62 (2023) e202300224. doi: 10.1002/anie.202300224
32. [32]
  J. Yang, A. Acharjya, M.Y. Ye, et al., Angew. Chem. Int. Ed. 60 (2021) 19797–19803. doi: 10.1002/anie.202104870
33. [33]
  Q. Zhi, W. Liu, R. Jiang, et al., J. Am. Chem. Soc. 144 (2022) 21328–21336. doi: 10.1021/jacs.2c09482
34. [34]
  Y. Zhao, P. Zhang, Z. Yang, et al., Nat. Commun. 12 (2021) 3701. doi: 10.1038/s41467-021-24048-1
35. [35]
  Q. Wu, J. Cao, X. Wang, et al., Nat. Commun. 12 (2021) 483. doi: 10.1038/s41467-020-20823-8
36. [36]
  Z. Teng, Q. Zhang, H. Yang, et al., Nat. Catal. 4 (2021) 374–384. doi: 10.1038/s41929-021-00605-1
37. [37]
  F. Yu, L. Wang, Q. Xing, et al., Chin. Chem. Lett. 31 (2020) 1648–1653. doi: 10.1016/j.cclet.2019.08.020
38. [38]
  G. Zhang, G. Li, T. Heil, et al., Angew. Chem. Int. Ed. 131 (2019) 3471–3475. doi: 10.1002/ange.201811938
39. [39]
  A. Savateev, S. Pronkin, J.D. Epping, et al., ChemCatChem 9 (2017) 167–174. doi: 10.1002/cctc.201601165
40. [40]
  A. Savateev, S. Pronkin, M.G. Willinger, et al., Chem. Asian J. 12 (2017) 1517–1522. doi: 10.1002/asia.201700209
41. [41]
  Z. Yang, L. Li, J. Cui, et al., Chem. Eur. J. 28 (2022) e202202122. doi: 10.1002/chem.202202122
42. [42]
  Z. Yang, L. Li, J. Gao, et al., ACS EST Eng. 2 (2022) 2142–2149. doi: 10.1021/acsestengg.2c00178
43. [43]
  Z. Yang, L. Li, S. Zeng, et al., ACS Appl. Mater. Interfaces 15 (2023) 8232–8240. doi: 10.1021/acsami.2c22366
44. [44]
  C. Merschjann, S. Tschierlei, T. Tyborski, et al., Adv. Mater. 27 (2015) 7993–7999. doi: 10.1002/adma.201503448
45. [45]
  R. Chen, Z. Ren, Y. Liang, et al., Nature 610 (2022) 296–301. doi: 10.1038/s41586-022-05183-1
46. [46]
  S. Wu, H. Yu, S. Chen, et al., ACS Catal. 10 (2020) 14380–14389. doi: 10.1021/acscatal.0c03359
47. [47]
  J. Cheng, Y. Hou, K. Lian, et al., ACS Catal. 12 (2022) 1797–1808. doi: 10.1021/acscatal.1c05013
48. [48]
  K.C. Bedin, A.C. Martins, A.L. Cazetta, et al., Chem. Eng. J. 286 (2016) 476–484. doi: 10.1016/j.cej.2015.10.099
49. [49]
  L. Kong, J. Wang, Y. Jia, et al., J. Raman Spectrosc. 41 (2010) 989–995. doi: 10.1002/jrs.2536
50. [50]
  Z. Zhai, H. Zhang, F. Niu, et al., ACS Nano 16 (2022) 21002–21012. doi: 10.1021/acsnano.2c08643
51. [51]
  L. Du, Q. Tian, X. Zheng, et al., Energy Environ. Mater. 5 (2021) 912–917.
52. [52]
  G. Zhang, Y. Xu, M. Rauf, et al., Adv. Sci. 9 (2022) e2201677. doi: 10.1002/advs.202201677
53. [53]
  S. Gao, X. Wang, C. Song, et al., Appl. Catal. B 295 (2021) 120272. doi: 10.1016/j.apcatb.2021.120272
54. [54]
  Z. Fang, Y. Bai, L. Li, et al., Nano Energy 75 (2020) 104865. doi: 10.1016/j.nanoen.2020.104865
55. [55]
  W. Ren, J. Cheng, H. Ou, et al., J. Catal. 389 (2020) 636–645. doi: 10.1016/j.jcat.2020.07.005
56. [56]
  L.L. Liu, F. Chen, J.H. Wu, et al., P. Natl. Acad. Sci. U. S. A. 120 (2023) e2215305120. doi: 10.1073/pnas.2215305120
57. [57]
  X. He, H. Shang, C. Wang, et al., Chin. Chem. Lett. 32 (2021) 3377–3381. doi: 10.1016/j.cclet.2021.04.028
58. [58]
  R.R. Pawar, Lalhmunsiama, M. Kim, et al., Appl. Clay Sci. 162 (2018) 339–350. doi: 10.1016/j.clay.2018.06.014
59. [59]
  S. Yu, J. Li, Y. Zhang, et al., Nano Energy 50 (2018) 383–392. doi: 10.1016/j.nanoen.2018.05.053
60. [60]
  J. Moan, E. Wold, Nature 279 (1979) 450–451. doi: 10.1038/279450a0
61. [61]
  S. Trasatti, Pure Appl. Chem. 58 (1986) 955–966. doi: 10.1351/pac198658070955
62. [62]
  H. Yu, R. Shi, Y. Zhao, et al., Adv. Mater. 29 (2017) 1605148. doi: 10.1002/adma.201605148
63. [63]
  M.O. Eze, L.C. Nnamani, R.I. Ojiako, et al., Free Rad. Res. Cornms. 4 (1987) 105–108.
64. [64]
  R. Palominos, J. Freer, M.A. Mondaca, et al., J. Photoch. Photobio. A 193 (2008) 139–145. doi: 10.1016/j.jphotochem.2007.06.017
65. [65]
  J. Luo, Y. Liu, C. Fan, et al., ACS Catal. 11 (2021) 11440–11450. doi: 10.1021/acscatal.1c03103
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2. [2]
  Liyong Ding , Zhenhua Pan , Qian Wang . 2D photocatalysts for hydrogen peroxide synthesis. Chinese Chemical Letters, 2024, 35(12): 110125-. doi: 10.1016/j.cclet.2024.110125
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5. [5]
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Molecular engineering towards dual surface local polarization sites on poly(heptazine imide) framework for boosting H2O2 photo-production

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Molecular engineering towards dual surface local polarization sites on poly(heptazine imide) framework for boosting H₂O₂ photo-production