Citation: Xiao Liu, Hangqi Liu, Qian Wang, Dandan Zheng, Sibo Wang, Masakazu Anpo, Guigang Zhang. Rational synthesis of poly(heptazine imides) nanorod in ternary LiCl/NaCl/KCl for visible light hydrogen production[J]. Chinese Chemical Letters, ;2025, 36(12): 111621. doi: 10.1016/j.cclet.2025.111621 shu

Rational synthesis of poly(heptazine imides) nanorod in ternary LiCl/NaCl/KCl for visible light hydrogen production

Xiao Liu ^a ,
Hangqi Liu ^a ,
Qian Wang ^a ,
Dandan Zheng ^{b, *,} ,
Sibo Wang ^a ,
Masakazu Anpo ^a ,
Guigang Zhang ^{a, *,}

a.
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, China
b.
College of Environment and Safety Engineering, Fuzhou University, Fuzhou 350108, China

ddzheng@fzu.edu.cn

guigang.zhang@fzu.edu.cn

Received Date: 20 January 2025
Revised Date: 17 July 2025
Accepted Date: 22 July 2025
Available Online: 23 July 2025

Figures(7)

Poly(heptazine imide) (PHI), a new allotrope of heptazine-based carbon nitride, is usually synthesized in the presence of binary molten salts (e.g., LiCl/NaCl, LiCl/KCl, NaCl/KCl) with diverse melting points and solvation abilities. However, the quantum efficiency of PHI for photocatalytic hydrogen production is still extremely restrained. Herein, a series of ternary molten salt mixtures (LiCl/NaCl/KCl) with varying compositions and properties, were employed for the rational control of the polymerization process of PHI and thus optimization in the optical properties, charge separation behaviors, and also photocatalytic performance. The results indicate that the ternary molten salts provide suitable environment for the development of a nanorod morphology, which significantly improves separation of photo-induced charge carriers. Hence, the optimized PHI presents a high apparent quantum yield (AQY = 52.9%) for visible-light driven hydrogen production.
- Poly(heptazine imide),
- Photocatalysis,
- Nanorod,
- Hydrogen production,
- Charge separation
1. [1]
  Q. Wang, K. Domen, Chem. Rev. 120 (2019) 919–985. doi: 10.3390/ijms20040919
2. [2]
  Q. Wang, X.C. Wang, F.X. Zhang, Next Energy 1 (2023) 100016. doi: 10.1016/j.nxener.2023.100016
3. [3]
  Y.O. Wang, H. Suzuki, J.J. Xie, et al., Chem. Rev. 118 (2018) 5201–5241. doi: 10.1021/acs.chemrev.7b00286
4. [4]
  F. Dawood, M. Anda, G.M. Shafiullah, Int. J. Hydrogen Energy 45 (2020) 3847–3869. doi: 10.1016/j.ijhydene.2019.12.059
5. [5]
  B. Zhang, W.J. Luo, L.Y. Pan, et al., Inorg. Chem. Front. 12 (2025) 161–170. doi: 10.1039/d4qi02452d
6. [6]
  A. Odenweller, F. Ueckerdt, G.F. Nemet, M. Jensterle, G. Luderer, Nat. Energy 7 (2022) 854–865. doi: 10.1038/s41560-022-01097-4
7. [7]
  Y.H. Zhang, Z.C. Yang, D.D. Zheng, et al., Int. J. Hydrogen Energy 69 (2024) 372–380. doi: 10.1016/j.ijhydene.2024.05.056
8. [8]
  H. Nishiyama, T. Yamada, M. Nakabayashi, et al., Nature 598 (2021) 304–307. doi: 10.1038/s41586-021-03907-3
9. [9]
  X.P. Tao, Y. Zhao, S.Y. Wang, C. Li, R.G. Li, Chem. Soc. Rev. 51 (2022) 3561–3608. doi: 10.1039/d1cs01182k
10. [10]
  J.F. Du, Y.L. Shen, F. Yang, et al., Inorg. Chem. Front. 10 (2023) 832–840. doi: 10.1039/d2qi01665f
11. [11]
  G.R. Zou, Q. Wang, G. Ye, et al., Adv. Funct. Mater. (2024), https://doi.org/10.1002/adfm.202420899. doi: 10.1002/adfm.202420899
12. [12]
  A. Fujishima, K. Honda, Nature 238 (1972) 37–38. doi: 10.1038/238037a0
13. [13]
  E.N. Musa, A.K. Yadav, K.T. Smith, et al., Angew. Chem. Int. Ed. 63 (2024) e202405681.
14. [14]
  F. Guo, M. Yang, R.X. Li, et al., ACS Catal. 12 (2022) 9486–9493. doi: 10.1021/acscatal.2c02789
15. [15]
  K. Sun, Y. Huang, F.S. Sun, et al., Nat. Chem. 16 (2024) 1638–1646. doi: 10.1038/s41557-024-01599-6
16. [16]
  W.B. Yu, H.R. Zhang, H.W. Zhang, et al., Adv. Funct. Mater. 34 (2024) 2410816. doi: 10.1002/adfm.202410816
17. [17]
  Y. Miseki, H. Kusama, H. Sugihara, K. Sayama, J. Phys. Chem. Lett. 1 (2010) 1196–1200. doi: 10.1021/jz100233w
18. [18]
  R.T. Chen, Z.F. Ren, Y. Liang, et al., Nature 610 (2022) 296–301. doi: 10.1038/s41586-022-05183-1
19. [19]
  W. Li, X.S. Chu, F. Wang, et al., Appl. Catal. B 304 (2022) 121000. doi: 10.1016/j.apcatb.2021.121000
20. [20]
  X. Wang, B.Y. Liu, S.Q. Ma, et al., Nat. Commun. 15 (2024) 2600. doi: 10.1038/s41467-024-47022-z
21. [21]
  H. Wang, H. Wang, Z.W. Wang, et al., Chem. Soc. Rev. 49 (2020) 4135–4165. doi: 10.1039/d0cs00278j
22. [22]
  Z.A. Lan, M. Wu, Z.P. Fang, et al., Angew. Chem. Int. Ed. 61 (2022) e202201482. doi: 10.1002/anie.202201482
23. [23]
  F.K. Kessler, Y. Zheng, D. Schwarz, et al., Nat. Rev. Mater. 2 (2017) 17030. doi: 10.1038/natrevmats.2017.30
24. [24]
  X.C. Wang, K. Maeda, A. Thomas, et al., Nat. Mater. 8 (2009) 76–80. doi: 10.1038/nmat2317
25. [25]
  M.L. Chang, Z.M. Pan, D.D. Zheng, et al., ChemSusChem 16 (2023) e202202255. doi: 10.1002/cssc.202202255
26. [26]
  D.D. Zheng, Q. Wang, Z.M. Pan, et al., Sci. China Mater. 67 (2024) 1900–1906. doi: 10.1007/s40843-023-2752-9
27. [27]
  H.J. Song, L.Y. Luo, S.Y. Wang, G. Zhang, B.J. Jiang, Chin. Chem. Lett. 35 (2024) 109347. doi: 10.1016/j.cclet.2023.109347
28. [28]
  X.J. Chen, R. Shi, Q. Chen, et al., Nano Energy 59 (2019) 644–650. doi: 10.1016/j.nanoen.2019.03.010
29. [29]
  J. Zhang, X.C. Liang, C. Zhang, et al., Angew. Chem. Int. Ed. 61 (2022) e202210849. doi: 10.1002/anie.202210849
30. [30]
  J. Zhang, G. Ye, C. Zhang, et al., ChemSusChem 15 (2022) e202201616. doi: 10.1002/cssc.202201616
31. [31]
  H.T. Wang, L.L. Yu, J.Z. Jiang, Arramel, J. Zou, Acta Phys. Chim. Sin. 40 (2024) 2305047. doi: 10.3866/PKU.WHXB202305047
32. [32]
  W.G. Zeng, Y.C. Dong, X.Y. Ye, et al., Chin. Chem. Lett. 35 (2024) 109252. doi: 10.1016/j.cclet.2023.109252
33. [33]
  D.D. Wu, S.N. Hu, H.Y. Xue, et al., J. Mater. Chem. A 7 (2019) 20223–20228. doi: 10.1039/c9ta05135j
34. [34]
  N.P. Dharmarajan, D. Vidyasagar, J.H. Yang, et al., Adv. Mater. 36 (2023) 2306895.
35. [35]
  Q. Wang, S.Y. Li, D.D. Zheng, et al., ACS Appl. Energy Mater. 7 (2024) 6090–6095. doi: 10.1021/acsaem.4c01512
36. [36]
  B.Y. Zhai, H.G. Li, G.Y. Gao, et al., Adv. Funct. Mater. 32 (2022) 2207375. doi: 10.1002/adfm.202207375
37. [37]
  G.G. Zhang, L.H. Lin, G.S. Li, et al., Angew. Chem. Int. Ed. 57 (2018) 9372–9376. doi: 10.1002/anie.201804702
38. [38]
  Y.X. Jin, D.D. Zheng, Z.P. Fang, et al., Interdiscip. Mater. 3 (2024) 389–399. doi: 10.1002/idm2.12159
39. [39]
  Y.M. Zou, S.Y. Li, D.D. Zheng, et al., Sci. China Chem. 67 (2024) 2215–2223. doi: 10.1007/s11426-024-2076-3
40. [40]
  Z.P. Chen, A. Savateev, S. Pronkin, et al., Adv. Mater. 29 (2017) 1700555. doi: 10.1002/adma.201700555
41. [41]
  M.J. Bojdys, J.O. Müller, M. Antonietti, A. Thomas, Chem. Eur. J. 14 (2008) 8177–8182. doi: 10.1002/chem.200800190
42. [42]
  M. Zhou, L.B. Zeng, R. Li, et al., Appl. Catal. B 317 (2022) 121719. doi: 10.1016/j.apcatb.2022.121719
43. [43]
  C.M. Pelicano, J.X. Li, M. Cabrero-Antonino, et al., J. Mater. Chem. A 12 (2024) 475–482. doi: 10.1039/d3ta05701a
44. [44]
  Y.X. Jin, C. Zhang, G.G. Zhang, Chin. J. Struct. Chem. 43 (2024) 100414.
45. [45]
  W. Zhong, D. Zheng, Y.X. Ou, A.Y. Meng, Y.R. Su, Acta Phys. Chim. Sin. 40 (2024) 2406005. doi: 10.3866/pku.whxb202406005
46. [46]
  Y. Pan, W.P. Si, Y.H. Li, et al., Chin. Chem. Lett. 35 (2024) 109877. doi: 10.1016/j.cclet.2024.109877
47. [47]
  S.P. Liu, V. Diez-Cabanes, D. Fan, et al., ACS Catal. 14 (2024) 2562–2571. doi: 10.1021/acscatal.3c05961
48. [48]
  H.L. Gao, S.C. Yan, J.J. Wang, et al., Phys. Chem. Chem. Phys. 15 (2013) 18077. doi: 10.1039/c3cp53774a
49. [49]
  Q.H. Deng, H.P. Li, W.X. Hu, W.G. Hou, Angew. Chem. Int. Ed. 62 (2023) e202314213. doi: 10.1002/anie.202314213
50. [50]
  J. Kröger, F. Podjaski, G. Savasci, et al., Adv. Mater. 34 (2022) 2107061. doi: 10.1002/adma.202107061
51. [51]
  Q. Wang, G.G. Zhang, W.D. Xing, et al., Angew. Chem. Int. Ed. 62 (2023) e202307930. doi: 10.1002/anie.202307930
52. [52]
  H. Schlomberg, J. Kröger, G. Savasci, et al., Chem. Mater. 31 (2019) 7478–7486. doi: 10.1021/acs.chemmater.9b02199
53. [53]
  A. Thomas, A. Fischer, F. Goettmann, et al., J. Mater. Chem. 18 (2008) 4893. doi: 10.1039/b800274f
54. [54]
  Z.L. Zhao, Z. Shu, J. Zhou, et al., J. Mater. Chem. A 10 (2022) 17668–17679. doi: 10.1039/d2ta04213d
55. [55]
  X.C. Li, X.X. Chen, Y.X. Fang, et al., Chem. Sci. 13 (2022) 7541–7551. doi: 10.1039/d2sc02043b
56. [56]
  K. Schwinghammer, M.B. Mesch, V. Duppel, et al., J. Am. Chem. Soc. 136 (2014) 1730–1733. doi: 10.1021/ja411321s
57. [57]
  D. Dontsova, S. Pronkin, M. Wehle, et al., Chem. Mater. 27 (2015) 5170–5179. doi: 10.1021/acs.chemmater.5b00812
58. [58]
  J.M. Wu, K.Y. Li, B. Zhou, et al., Angew. Chem. Int. Ed. (2024), https://doi.org/10.1002/anie.202421263. doi: 10.1002/anie.202421263
59. [59]
  T. Xiong, W.L. Cen, Y.X. Zhang, F. Dong, ACS Catal. 6 (2016) 2462–2472. doi: 10.1021/acscatal.5b02922
60. [60]
  G.G. Zhang, A. Savateev, Y.B. Zhao, L.N. Li, M. Antonietti, J. Mater. Chem. A 5 (2017) 12723–12728. doi: 10.1039/C7TA03777E
61. [61]
  T. T. Zhao, Q. Zhou, Y.Q. Lv, et al., Angew. Chem. Int. Ed. 59 (2020) 1139–1143. doi: 10.1002/anie.201911822
62. [62]
  P.L. Wang, S.Y. Fan, X.Y. Li, et al., Nano Energy 95 (2022) 107045. doi: 10.1016/j.nanoen.2022.107045
63. [63]
  A. Talebian-Kiakalaieh, M.J. Guo, E.M. Hashem, et al., Adv. Energy Mater. 13 (2023) 2301594. doi: 10.1002/aenm.202301594
64. [64]
  S.W. Cao, F. Tao, Y. Tang, Y.T. Li, J.G. Yu, Chem. Soc. Rev. 45 (2016) 4747–4765. doi: 10.1039/C6CS00094K
65. [65]
  T. Shmila, S. Mondal, S. Barzilai, et al., Small 19 (2023) 2303602. doi: 10.1002/smll.202303602
66. [66]
  G.G. Zhang, G.S. Li, Z.A. Lan, et al., Angew. Chem. Int. Ed. 56 (2017) 13445–13449. doi: 10.1002/anie.201706870
1. [1]
  Zhen Shi , Wei Jin , Yuhang Sun , Xu Li , Liang Mao , Xiaoyan Cai , Zaizhu Lou . Interface charge separation in Cu2CoSnS4/ZnIn2S4 heterojunction for boosting photocatalytic hydrogen production. Chinese Journal of Structural Chemistry, 2023, 42(12): 100201-100201. doi: 10.1016/j.cjsc.2023.100201
2. [2]
  Tianhao Li , Wenguang Tu , Zhigang Zou . In situ photocatalytically enhanced thermogalvanic cells for electricity and hydrogen production. Chinese Journal of Structural Chemistry, 2024, 43(1): 100195-100195. doi: 10.1016/j.cjsc.2023.100195
3. [3]
  Wengao Zeng , Yuchen Dong , Xiaoyuan Ye , Ziying Zhang , Tuo Zhang , Xiangjiu Guan , Liejin Guo . Crystalline carbon nitride with in-plane built-in electric field accelerates carrier separation for excellent photocatalytic hydrogen evolution. Chinese Chemical Letters, 2024, 35(4): 109252-. doi: 10.1016/j.cclet.2023.109252
4. [4]
  Guixu Pan , Zhiling Xia , Ning Wang , Hejia Sun , Zhaoqi Guo , Yunfeng Li , Xin Li . Preparation of high-efficient donor-π-acceptor system with crystalline g-C3N4 as charge transfer module for enhanced photocatalytic hydrogen evolution. Chinese Journal of Structural Chemistry, 2024, 43(12): 100463-100463. doi: 10.1016/j.cjsc.2024.100463
5. [5]
  Haojie Song , Laiyu Luo , Siyu Wang , Guo Zhang , Baojiang Jiang . Advances in poly(heptazine imide)/poly(triazine imide) photocatalyst. Chinese Chemical Letters, 2024, 35(10): 109347-. doi: 10.1016/j.cclet.2023.109347
6. [6]
  Xinlong Zheng , Zhongyun Shao , Jiaxin Lin , Qizhi Gao , Zongxian Ma , Yiming Song , Zhen Chen , Xiaodong Shi , Jing Li , Weifeng Liu , Xinlong Tian , Yuhao Liu . Recent advances of CuSbS₂ and CuPbSbS₃ as photocatalyst in the application of photocatalytic hydrogen evolution and degradation. Chinese Chemical Letters, 2025, 36(3): 110533-. doi: 10.1016/j.cclet.2024.110533
7. [7]
  Kai Han , Guohui Dong , Ishaaq Saeed , Tingting Dong , Chenyang Xiao . Boosting bulk charge transport of CuWO4 photoanodes via Cs doping for solar water oxidation. Chinese Journal of Structural Chemistry, 2024, 43(2): 100207-100207. doi: 10.1016/j.cjsc.2023.100207
8. [8]
  Qiang Zhang , Weiran Gong , Huinan Che , Bin Liu , Yanhui Ao . S doping induces to promoted spatial separation of charge carriers on carbon nitride for efficiently photocatalytic degradation of atrazine. Chinese Journal of Structural Chemistry, 2023, 42(12): 100205-100205. doi: 10.1016/j.cjsc.2023.100205
9. [9]
  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. Chinese Chemical Letters, 2024, 35(8): 109251-. doi: 10.1016/j.cclet.2023.109251
10. [10]
  Yueting Ma , Zhiyan Feng , Yuxin Dong , Zhiyong Yan , Hou Wang , Yan Wu . Harnessing the interfacial sulfur-edge and metal-edge sites in ZnIn₂S₄/MnS heterojunctions boosts charge transfer for photocatalytic hydrogen production. Chinese Chemical Letters, 2025, 36(6): 110922-. doi: 10.1016/j.cclet.2025.110922
11. [11]
  Miaosen Yang , Junyang Ding , Zhiwei Wang , Jingwen Zhang , Zimo Peng , Xijun Liu . NiMo-based alloy and its sulfides for energy-saving hydrogen production via sulfion oxidation assisted alkaline seawater splitting. Chinese Chemical Letters, 2025, 36(9): 110861-. doi: 10.1016/j.cclet.2025.110861
12. [12]
  Xiaxi Yao , Xiuli Hu , Fangcheng Huang , Xuhong Wang , Xuekun Hong , Dawei Wang . Improved hydrogen and oxygen evolution rates in Pt@TiO₂@RuO₂ hollow nanoshells through dielectric Mie resonance and spatial cocatalyst separation. Chinese Chemical Letters, 2025, 36(5): 110192-. doi: 10.1016/j.cclet.2024.110192
13. [13]
  Bowen Li , Ting Wang , Ming Xu , Yuqi Wang , Zhaoxing Li , Mei Liu , Wenjing Zhang , Ming Feng . Structuring MoO₃-polyoxometalate hybrid superstructures to boost electrocatalytic hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(2): 110467-. doi: 10.1016/j.cclet.2024.110467
14. [14]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245
15. [15]
  Weixu Li , Yuexin Wang , Lin Li , Xinyi Huang , Mengdi Liu , Bo Gui , Xianjun Lang , Cheng Wang . Promoting energy transfer pathway in porphyrin-based sp2 carbon-conjugated covalent organic frameworks for selective photocatalytic oxidation of sulfide. Chinese Journal of Structural Chemistry, 2024, 43(7): 100299-100299. doi: 10.1016/j.cjsc.2024.100299
16. [16]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
17. [17]
  Jiangqi Ning , Junhan Huang , Yuhang Liu , Yanlei Chen , Qing Niu , Qingqing Lin , Yajun He , Zheyuan Liu , Yan Yu , Liuyi Li . Alkyl-linked TiO2@COF heterostructure facilitating photocatalytic CO2 reduction by targeted electron transport. Chinese Journal of Structural Chemistry, 2024, 43(12): 100453-100453. doi: 10.1016/j.cjsc.2024.100453
18. [18]
  Jiaqi Ma , Lan Li , Yiming Zhang , Jinjie Qian , Xusheng Wang . Covalent organic frameworks: Synthesis, structures, characterizations and progress of photocatalytic reduction of CO2. Chinese Journal of Structural Chemistry, 2024, 43(12): 100466-100466. doi: 10.1016/j.cjsc.2024.100466
19. [19]
  Yanghanbin Zhang , Dongxiao Wen , Wei Sun , Jiahe Peng , Dezhong Yu , Xin Li , Yang Qu , Jizhou Jiang . State-of-the-art evolution of g-C3N4-based photocatalytic applications: A critical review. Chinese Journal of Structural Chemistry, 2024, 43(12): 100469-100469. doi: 10.1016/j.cjsc.2024.100469
20. [20]
  Yuehai Zhi , Chen Gu , Huachao Ji , Kang Chen , Wenqi Gao , Jianmei Chen , Dafeng Yan . The advanced development of innovative photocatalytic coupling strategies for hydrogen production. Chinese Chemical Letters, 2025, 36(1): 110234-. doi: 10.1016/j.cclet.2024.110234

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(16)
HTML views(5)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142