Citation: Sheng Qian, Jingying Wei, Junhua Wang, Yi Zhang, Huaiguo Xue, Tengfei Jiang, Jingqi Tian. Conjugated N-heterocycles in heterostructured support manipulate d-band center for hydrogen electrocatalysis[J]. Chinese Chemical Letters, ;2026, 37(8): 112106. doi: 10.1016/j.cclet.2025.112106 shu

Conjugated N-heterocycles in heterostructured support manipulate d-band center for hydrogen electrocatalysis

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China

tianjq@yzu.edu.cn

Received Date: 14 August 2025
Revised Date: 29 October 2025
Accepted Date: 11 November 2025
Available Online: 12 November 2025

Figures(5)

The interfacial electronic interaction between the support and catalyst has been demonstrated to play a significant role in regulating the d-band structure of metal centers. Still, it requires dedicated control over the interaction in a reasonable manner. Herein, we developed a heterostructured support by covalently linking carbon nitride quantum dots (CNQDs) on TiO₂, to anchor electroactive CoP clusters (TiO₂–CNQD/CoP) for hydrogen evolution reaction (HER). The interfacial electronic interaction between the heterostructured support (TiO₂–CNQD) and CoP can be controlled by varying the size of CNQDs, owing to the number of conjugated N-heterocycles in CNQDs induces tunable π-electron delocalization. As a result, a volcano-shaped correlation between the shift of the Co d-band center (Δd) and the HER performance was established, suggesting that TiO₂–CNQD/CoP-C2 with a moderate size of CNQD is the optimal HER catalyst. This study highlights the critical role of interfacial interaction in supported catalysts, providing a predictive descriptor focusing on the support design of advanced HER catalysts.
- Heterostructured support,
- d-Band center,
- Descriptor,
- Interfacial electron transfer,
- Electrocatalysis
1. [1]
  Y. Jiang, Z. Liang, H. Fu, et al., J. Am. Chem. Soc. 146 (2024) 9012–9025. doi: 10.1021/jacs.3c13367
2. [2]
  Y. Zhang, M. Zhao, J. Wu, et al., ACS Catal. 14 (2024) 7867–7876. doi: 10.1021/acscatal.4c01133
3. [3]
  J. Liu, J. Ren, Y. Du, et al., Adv. Funct. Mater. 34 (2024) 2315773. doi: 10.1002/adfm.202315773
4. [4]
  Y. Lu, C. Pei, W. Li, et al., Chin. Chem. Lett. 36 (2025) 111646. doi: 10.1016/j.cclet.2025.111646
5. [5]
  M. Li, H. Wang, Z. Yang, et al., Chin. Chem. Lett. 36 (2025) 110199. doi: 10.1016/j.cclet.2024.110199
6. [6]
  X. Liu, H. Pang, X. Kou, et al., Chin. Chem. Lett. 37 (2026) 111567. doi: 10.1016/j.cclet.2025.111567
7. [7]
  W. Tom, H. Carlos, P. Krijn, Nat. Catal. 2 (2019) 955–970. doi: 10.1038/s41929-019-0364-x
8. [8]
  H. Li, C. Chen, D. Yan, et al., J. Mater. Chem. A 7 (2019) 23432–23450. doi: 10.1039/c9ta04888j
9. [9]
  T. Liu, R. Lin, Y. Liu, et al., Chin. Chem. Lett. 37 (2026) 111312. doi: 10.1016/j.cclet.2025.111312
10. [10]
  S. Sun, X. Zhou, B. Cong, et al., ACS Catal. 10 (2020) 9086–9097. doi: 10.1021/acscatal.0c01273
11. [11]
  L. Zhang, K. Chen, L. Li, et al., Chin. Chem. Lett. 37 (2026) 111002. doi: 10.1016/j.cclet.2025.111002
12. [12]
  Y. Li, H. Zhang, M. Jiang, et al., Adv. Funct. Mater. 27 (2017) 1702513. doi: 10.1002/adfm.201702513
13. [13]
  G. Malta, S.A. Kondrat, S.J. Freakley, et al., Science 355 (2017) 1399–1403. doi: 10.1126/science.aal3439
14. [14]
  S. Qian, F. Xu, Y. Fan, et al., Nat. Commun. 15 (2024) 2774. doi: 10.1038/s41467-024-47061-6
15. [15]
  Y. Gao, S. Qian, H. Wang, et al., App. Catal. B: Environ. 320 (2023) 122014. doi: 10.1016/j.apcatb.2022.122014
16. [16]
  G. Zhao, K. Rui, S. Dou, et al., Adv. Funct. Mater. 28 (2018) 1803291. doi: 10.1002/adfm.201803291
17. [17]
  Y. Du, H. Lu, J. Wu, et al., Angew. Chem. Int. Ed. 64 (2025) e202420903. doi: 10.1002/anie.202420903
18. [18]
  Y. Zhang, J. Zhao, H. Wang, et al., Nat. Commun. 13 (2022) 58.
19. [19]
  Z. Jiang, X. Xu, Y. Ma, et al., Nature 586 (2020) 549–554. doi: 10.1038/s41586-020-2738-2
20. [20]
  Z. Wang, W. Xu, G. Tan, et al., Sci. Bull. 68 (2023) 613–621. doi: 10.1016/j.scib.2023.03.003
21. [21]
  S. Zhou, H. Jang, Q. Qin, et al., Angew. Chem. Int. Ed. 61 (2022) e202212196. doi: 10.1002/anie.202212196
22. [22]
  S. Qian, T. Jiang, J. Wang, et al., ACS Catal. 14 (2024) 18690–18700. doi: 10.1021/acscatal.4c05624
23. [23]
  Z. Wei, H. Wang, C. Zhang, et al., Angew. Chem. Int. Ed. 60 (2021) 16622–16627. doi: 10.1002/anie.202104856
24. [24]
  L. Zhang, W. Shang, S. Qiao, et al., ACS Catal. 14 (2024) 15827–15836. doi: 10.1021/acscatal.4c03006
25. [25]
  J. Matsubu, S. Zhang, L. DeRita, et al., Nat. Chem. 9 (2016) 120–127.
26. [26]
  X. Chang, S. Thind, A. Chen, ACS Catal. 4 (2014) 2616–2622. doi: 10.1021/cs500487a
27. [27]
  J. Wang, S. Qian, D. Jia, et al., Inorg. Chem. 64 (2025) 1532–1540. doi: 10.1021/acs.inorgchem.4c04811
28. [28]
  M. Albolkany, Y. Wang, W. Li, et al., Chem. Int. Ed. 59 (2020) 21499. doi: 10.1002/anie.202009710
29. [29]
  Y. Fan, J. Wang, S. Qian, et al., J. Colloid Interface Sci. 667 (2024) 128–135. doi: 10.1016/j.jcis.2024.04.066
30. [30]
  T. Huo, Q. Deng, F. Yu, et al., ACS Appl. Mater. Interfaces 14 (2022) 13419–13430. doi: 10.1021/acsami.2c01522
31. [31]
  X. Wang, P. Wu, Z. Wang, et al., ACS Sustainable Chem. Eng. 9 (2021) 3083–3094. doi: 10.1021/acssuschemeng.0c07292
32. [32]
  G. Nagaraju, T. Ravishankar, K. Manjunatha, et al., Mater. Lett. 109 (2013) 27–30. doi: 10.1016/j.matlet.2013.07.031
33. [33]
  S. Barman, M. Sadhukhan, J. Mater. Chem. 22 (2012) 21832–21837. doi: 10.1039/c2jm35501a
34. [34]
  X. Wu, F. Chen, X. Wang, et al., Appl. Surf. Sci. 427 (2018) 645–653. doi: 10.3727/096504017x15031557924141
35. [35]
  Y. Liu, W. Fang, Z. Yue, et al., Nat. Water 3 (2025) 430–438. doi: 10.1038/s44221-025-00419-6
36. [36]
  H. Liu, X. Lv, J. Qian, et al., ACS Nano 14 (2020) 13304. doi: 10.1021/acsnano.0c05143
37. [37]
  X. Huang, X. Xu, C. Li, et al., Adv. Energy Mater. 9 (2019) 1803970. doi: 10.1002/aenm.201803970
38. [38]
  H. Li, S. Xu, H. Yan, et al., Small 14 (2018) 1800367. doi: 10.1002/smll.201800367
39. [39]
  B. Liu, J. Du, G. Ke, et al., Adv. Funct. Mater. 32 (2021) 2111125.
40. [40]
  L. Tian, Z. Li, P. Wang, et al., J. Energy Chem. 55 (2021) 279–294. doi: 10.1016/j.jechem.2020.06.057
41. [41]
  I. Bertóti, M. Mohai, K. László, Carbon 84 (2015) 185–196. doi: 10.1016/j.carbon.2014.11.056
42. [42]
  V. Veettil, A. Vijayakumar, D. Purayil, et al., ChemElectroChem 7 (2020) 3319–3323. doi: 10.1002/celc.202000680
43. [43]
  W. Yuan, T. Jiang, X. Fang, et al., Chem. Eng. J. 439 (2022) 135743. doi: 10.1016/j.cej.2022.135743
44. [44]
  X. Yu, L. Feng, H.S. Park, J. Power Sources 390 (2018) 93–99. doi: 10.1016/j.jpowsour.2018.04.032
45. [45]
  X. Hu, M. Fan, Y. Zhu, et al., Green Chem. 21 (2019) 5274–5283. doi: 10.1039/c9gc01910c
46. [46]
  C. Xu, H. Yu, H. Huang, et al., Angew. Chem. Int. Ed. 64 (2025) e202504667. doi: 10.1002/anie.202504667
47. [47]
  Y. Li, S. Zhang, B. Li, et al., ACS Nano 19 (2025) 7401–7416. doi: 10.1021/acsnano.5c00318
48. [48]
  Y. Liu, H. You, C. Bai, et al., Adv. Energy Mater. 15 (2025) e03695. doi: 10.1002/aenm.202503695
49. [49]
  Z. Zhou, Y. Su, H. Tan, et al., J. Am. Chem. Soc. 147 (2025) 3994–4004. doi: 10.1021/jacs.4c11788
50. [50]
  S. Zhang, L. Yin, S. Wang, et al., ACS Nano 17 (2023) 23103–23114. doi: 10.1021/acsnano.3c08921
51. [51]
  P. Yan, T. Yang, M. Lin, et al., Adv. Funct. Mater. 33 (2023) 2301343. doi: 10.1002/adfm.202301343
52. [52]
  W. Chen, B. Wu, Y. Wang, et al., Energy. Environ. Sci. 14 (2021) 6428. doi: 10.1039/d1ee01395e
53. [53]
  W. Gou, Z. Xia, X. Tan, et al., Nano. Energy 104 (2022) 107960. doi: 10.1016/j.nanoen.2022.107960
54. [54]
  C. Xie, W. Chen, S. Du, et al., Nano. Energy 71 (2020) 104653. doi: 10.1016/j.nanoen.2020.104653
55. [55]
  L. Zhou, T. Wan, Y. Zhong, et al., Small 20 (2024) 2406076. doi: 10.1002/smll.202406076
56. [56]
  Q. Dai, L. Wang, K. Wang, et al., Adv. Funct. Mater. 32 (2022) 2109556. doi: 10.1002/adfm.202109556
57. [57]
  K. Sun, X. Wu, Z. Zhuang, et al., Nat. Commun. 13 (2022) 6260. doi: 10.1038/s41467-022-33984-5
58. [58]
  S. Li, M. Sun, K. Zhang, et al., Angew. Chem. Int. Ed. 64 (2025) e202508366. doi: 10.1002/anie.202508366
59. [59]
  Q. Song, J. Li, S. Wang, et al., Small 15 (2019) 1903395. doi: 10.1002/smll.201903395
1. [1]
  Shanru Feng , Ling Wen , Li Zhang , Qinyu Jiang , Bozhao Zhang , Guohao Wu , Yue Wu , Jiabin Chen , Youcai Han , Chuhao Liu , Yu-Wu Zhong , Jiannian Yao . Magnetic field controlled electrocatalysis from a multidimensional catalytic perspective: Mechanisms, applications, and prospects for energy conversion. Chinese Journal of Structural Chemistry, 2025, 44(11): 100662-100662. doi: 10.1016/j.cjsc.2025.100662
2. [2]
  Mingying Chen , Junjie Ma , Xiyong Chen , Qian Liu , Yanhong Feng , Xijun Liu . Support engineering of single-atom electrocatalysis: Mechanism analysis and application expansion. Chinese Chemical Letters, 2026, 37(4): 111637-. doi: 10.1016/j.cclet.2025.111637
3. [3]
  Xiang Ao , Fucheng Wu , Lin Yu , Kai Zhao , Muhammad Humayun , Chundong Wang . Tailoring antiperovskite carbide for electrocatalysis hydrogen evolution applications. Chinese Journal of Structural Chemistry, 2026, 45(4): 100851-100851. doi: 10.1016/j.cjsc.2025.100851
4. [4]
  Lu Zhang , Baohua Wang , Wei Yang , Lunan Ju , Zihan Fu , Lei Zhao , Yunqi Jiang , Hongyan Wang , Xiansheng Wang , Cong Lyu . CoOOH@COFs S−scheme heterojunction for efficient triclosan degradation in photocatalytic-peroxymonosulfate activation system: Enhanced interfacial electron transfer mechanism. Chinese Chemical Letters, 2026, 37(1): 111142-. doi: 10.1016/j.cclet.2025.111142
5. [5]
  Chunru Liu , Ligang Feng . Advances in anode catalysts of methanol-assisted water-splitting reactions for hydrogen generation. Chinese Journal of Structural Chemistry, 2023, 42(10): 100136-100136. doi: 10.1016/j.cjsc.2023.100136
6. [6]
  Guan-Nan Xing , Di-Ye Wei , Hua Zhang , Zhong-Qun Tian , Jian-Feng Li . Pd-based nanocatalysts for oxygen reduction reaction: Preparation, performance, and in-situ characterization. Chinese Journal of Structural Chemistry, 2023, 42(11): 100021-100021. doi: 10.1016/j.cjsc.2023.100021
7. [7]
  Shaojie Ding , Henan Wang , Xiaojing Dai , Yuru Lv , Xinxin Niu , Ruilian Yin , Fangfang Wu , Wenhui Shi , Wenxian Liu , Xiehong Cao . Mn-modulated Co–N–C oxygen electrocatalysts for robust and temperature-adaptative zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100302-100302. doi: 10.1016/j.cjsc.2024.100302
8. [8]
  Sumiya Akter Dristy , Md Ahasan Habib , Mehedi Hasan Joni , Md Najibullah , Rutuja Mandavkar , Shusen Lin , Jihoon Lee . Binder-free bimetallic vanadium-nickel-boride-phosphide spherical structure for highly efficient and stable industrial-level water splitting. Chinese Journal of Structural Chemistry, 2025, 44(12): 100747-100747. doi: 10.1016/j.cjsc.2025.100747
9. [9]
  Jinzhou Zheng , Chaozheng He , Chenxu Zhao . Rational catalyst design for N₂ electro-reduction: Regulation strategies and quick screen towards enhanced conversion efficiency. Chinese Chemical Letters, 2025, 36(7): 111056-. doi: 10.1016/j.cclet.2025.111056
10. [10]
  Quanyou Guo , Yue Yang , Tingting Hu , Hongqi Chu , Lijun Liao , Xuepeng Wang , Zhenzi Li , Liping Guo , Wei Zhou . Regulating local electron transfer environment of covalent triazine frameworks through F, N co-modification towards optimized oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(1): 110235-. doi: 10.1016/j.cclet.2024.110235
11. [11]
  Pingfan Zhang , Shihuan Hong , Ning Song , Zhonghui Han , Fei Ge , Gang Dai , Hongjun Dong , Chunmei Li . Alloy as advanced catalysts for electrocatalysis: From materials design to applications. Chinese Chemical Letters, 2024, 35(6): 109073-. doi: 10.1016/j.cclet.2023.109073
12. [12]
  Ming Yue , Yi-Rong Wang , Jia-Yong Weng , Jia-Li Zhang , Da-Yu Chi , Mingjin Shi , Xiao-Gang Hu , Yifa Chen , Shun-Li Li , Ya-Qian Lan . Multi-metal porous crystalline materials for electrocatalysis applications. Chinese Chemical Letters, 2025, 36(6): 110049-. doi: 10.1016/j.cclet.2024.110049
13. [13]
  Hong-Rui Li , Xia Kang , Rui Gao , Miao-Miao Shi , Bo Bi , Ze-Yu Chen , Jun-Min Yan . Interfacial interactions of Cu/MnOOH enhance ammonia synthesis from electrochemical nitrate reduction. Chinese Chemical Letters, 2025, 36(2): 109958-. doi: 10.1016/j.cclet.2024.109958
14. [14]
  Xuyun Lu , Yanan Chang , Shasha Wang , Xiaoxuan Li , Jianchun Bao , Ying Liu . Hydrogen peroxide electrosynthesis via two-electron oxygen reduction: From pH effect to device engineering. Chinese Chemical Letters, 2025, 36(5): 110277-. doi: 10.1016/j.cclet.2024.110277
15. [15]
  Ziang Shang , Heyu Sui , Zeyi Huang , Xueting Feng , Guanzhen Chen , Jiena Weng , Yu Xiong , Yaqiong Su , Yunhu Han . Mo, B-induced local structure and electron redistribution of RuO₂ for efficient acidic oxygen evolution. Chinese Chemical Letters, 2026, 37(6): 111016-. doi: 10.1016/j.cclet.2025.111016
16. [16]
  Anni Wu , Chengyi Hong , Hu Zheng , Wei Teng . Multi-site synergistic relay electrocatalysis with high-entropy nanoalloys for effective nitrate reduction to ammonia. Chinese Chemical Letters, 2025, 36(12): 111066-. doi: 10.1016/j.cclet.2025.111066
17. [17]
  Qi Zhang , Bin Han , Yucheng Jin , Mingrun Li , Enhui Zhang , Jianzhuang Jiang . 2D and 3D phthalocyanine covalent organic frameworks for electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2025, 36(9): 110330-. doi: 10.1016/j.cclet.2024.110330
18. [18]
  Mingrun Li , Bin Han , Lei Gong , Yucheng Jin , Mingyue Wang , Xu Ding , Dongdong Qi , Jianzhuang Jiang . 1D COFs with phthalocyanine functional building blocks and imide linkage for superior electrocatalytic nitrate reduction. Chinese Chemical Letters, 2026, 37(2): 110590-. doi: 10.1016/j.cclet.2024.110590
19. [19]
  Lan Ding , Kezhen Qi , Zimo Huang , Ying Yu , Ze Yang , Sepehr Tabibi , Alireza Khataee , Lei Hao , Qitao Zhang , Vadim Popkov , Maria Kaneva , Artem Lobinsky , Zhipeng Yu , Jun Li , Amir Sultan , Kun Zheng , Gan Qu , Dandan Ma , Jian-Wen Shi , Ahmed Ismail . 2030 roadmap on two-dimensional materials for energy storage and conversion. Chinese Chemical Letters, 2026, 37(3): 112242-. doi: 10.1016/j.cclet.2025.112242
20. [20]
  Kezhen Qi , Zhidong Wei , Haibin Wang , Hongyan Liang , Dandan Ma , Jian-Wen Shi , Yifeng Li , Xuepeng Xiang , Yan Chen , Bo Yu , Chunchun Wang , Zhuo Xing , Claudio Imparato , Aurelio Bifulco , Daniil A. Lukyanov , Elena V. Alekseeva , Oleg V. Levin , M.I. Chebanenko , V.I. Popkov , Tan Zhang , Jinping Li , Guang Liu , Wei Li , Linlin Song , Rongzheng Ren , Zhenhua Wang , Jianmin Ma . Gas-involved photo- and electro-catalysis roadmap towards 2030. Chinese Chemical Letters, 2026, 37(1): 111661-. doi: 10.1016/j.cclet.2025.111661

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(18)
HTML views(0)

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