Citation: Congzhao Dong, Yajun Zhang, Yingpu Bi, Zeyu Li, Yong Ding. Band structure engineering of phosphorus doped Ta₃N₅ for efficient photoelectrochemical water oxidation[J]. Chinese Chemical Letters, ;2025, 36(12): 111449. doi: 10.1016/j.cclet.2025.111449 shu

Band structure engineering of phosphorus doped Ta₃N₅ for efficient photoelectrochemical water oxidation

Congzhao Dong ^{a, b} ,
Yajun Zhang ^b ,
Yingpu Bi ^{b, *,} ,
Zeyu Li ^a ,
Yong Ding ^{a, *,}

a.
State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Advanced Catalysis of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
b.
State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China

yingpubi@licp.cas.cn

dingyong1@lzu.edu.cn

Received Date: 5 February 2025
Revised Date: 9 June 2025
Accepted Date: 11 June 2025
Available Online: 16 June 2025

Figures(5)

Constrained by severe bulk charge recombination, the actual photocurrent density of tantalum nitride (Ta₃N₅) photoanode is much lower than the theoretical maximum value. Herein, we report the doping of phosphorus, a non-metallic element distinct from oxygen, into Ta₃N₅, resulting in a photocurrent density 9 times higher than that of pristine Ta₃N₅. Systematic characterization reveals that the phosphorus doping simultaneously enhances the bulk charge separation efficiency and surface charge injection efficiency of Ta₃N₅, and induces favorable band energy restructuring. Specifically, a type-Ⅱ homojunction formed between phosphorus-doped near-surface region and bulk Ta₃N₅ effectively promotes the separation and transfer of photogenerated holes and electrons. Further modification with a NiFe-based cocatalyst enables the optimized photoanode to deliver a photocurrent density of 10 mA/cm² at 1.23 V versus the reversible hydrogen electrode (RHE) and an applied bias photo-to-current efficiency of 1.78% at 0.95 V versus RHE. Our work provides a foundation for the development of a broader range of non-metal doped semiconductors.
- Ta₃N₅,
- PEC water splitting,
- Photoanode,
- P-doped,
- Band structure engineering
1. [1]
  M. Grätzel, Nature 414 (2001) 338–344. doi: 10.1038/35104607
2. [2]
  P. Zhou, I.A. Navid, Y. Ma et al., Nature 613 (2023) 66–70. doi: 10.1038/s41586-022-05399-1
3. [3]
  M.G. Walter, E.L. Warren, J.R. McKone et al., Chem. Rev. 110 (2010) 6446–6473. doi: 10.1021/cr1002326
4. [4]
  S. Wang, G. Liu, L. Wang, Chem. Rev. 119 (2019) 5192–5247. doi: 10.1021/acs.chemrev.8b00584
5. [5]
  X. Cao, C. Xu, X. Liang et al., Appl. Catal. B: Environ. 260 (2020) 118136. doi: 10.1016/j.apcatb.2019.118136
6. [6]
  J.R. Bolton, S.J. Strickler, J.S. Connolly, Nature 316 (1985) 495–500. doi: 10.1038/316495a0
7. [7]
  T. Hisatomi, J. Kubota, K. Domen, Chem. Soc. Rev. 43 (2014) 7520–7535. doi: 10.1039/C3CS60378D
8. [8]
  J. Feng, H. Huang, W. Guo et al., Chem. Eng. J. 417 (2021) 128095. doi: 10.1016/j.cej.2020.128095
9. [9]
  G. Liu, S. Ye, P. Yan et al., Energy Environ. Sci. 9 (2016) 1327–1334. doi: 10.1039/C5EE03802B
10. [10]
  C. Dong, X. Zhang, Y. Ding, Y. Zhang, Y. Bi, Appl. Catal. B: Environ. 338 (2023) 123055. doi: 10.1016/j.apcatb.2023.123055
11. [11]
  H. Huang, J. Wang, Y. Liu et al., Nat. Mater. 23 (2023) 383–390.
12. [12]
  B. Zhao, X. Huang, Y. Ding, Y. Bi, Angew. Chem. Int. Ed. 62 (2022) e202213067.
13. [13]
  A. Ishikawa, T. Takata, J.N. Kondo, M. Hara, K. Domen, J. Phys. Chem. B 108 (2004) 11049–11053.
14. [14]
  W.J. Chun, A. Ishikawa, H. Fujisawa et al., J. Phys. Chem. B 107 (2003) 1798–1803. doi: 10.1021/jp027593f
15. [15]
  J. Feng, H. Huang, S. Yan et al., Nano Today 30 (2020) 100830. doi: 10.1016/j.nantod.2019.100830
16. [16]
  B. Zhang, Z. Fan, Y. Chen et al., Angew. Chem. Int. Ed. 62 (2023) e202305123. doi: 10.1002/anie.202305123
17. [17]
  M. Zhong, T. Hisatomi, Y. Sasaki, et al., Angew. Chem. Int. Ed. 56 (2017) 4739–4743. doi: 10.1002/anie.201700117
18. [18]
  Y. He, J.E. Thorne, C.H. Wu et al., Chem 1 (2016) 640–655. doi: 10.1016/j.chempr.2016.09.006
19. [19]
  S.C. Erwin, L. Zu, M.I. Haftel et al., Nature 436 (2005) 91–94. doi: 10.1038/nature03832
20. [20]
  Y. Li, L. Zhang, A. Torres-Pardo et al., Nat. Commun. 4 (2013) 2566. doi: 10.1038/ncomms3566
21. [21]
  Q. Rui, L. Wang, Y. Zhang et al., J. Mater. Chem. A 6 (2018) 7021–7026. doi: 10.1039/c8ta00556g
22. [22]
  Y. Kado, C.Y. Lee, K. Lee et al., Chem. Commun. 48 (2012) 8685–8687. doi: 10.1039/c2cc33822j
23. [23]
  S. Grigorescu, B. Bärhausen, L. Wang et al., Electrochem. Commun. 51 (2015) 85–88. doi: 10.1016/j.elecom.2014.12.019
24. [24]
  L. Pei, Z. Xu, Z. Shi et al., J. Mater. Chem. A 5 (2017) 20439–20447. doi: 10.1039/C7TA06227C
25. [25]
  L.I. Wagner, E. Sirotti, O. Brune et al., Adv. Funct. Mater. 34 (2023) 2306539.
26. [26]
  Z. Lou, Y. Yang, Y. Wang et al., Chem. Eng. J. 396 (2020) 125161. doi: 10.1016/j.cej.2020.125161
27. [27]
  J. Seo, T. Takata, M. Nakabayashi et al., J. Am. Chem. Soc. 137 (2015) 12780–12783. doi: 10.1021/jacs.5b08329
28. [28]
  Y. Xiao, C. Feng, J. Fu et al., Y. Li, Nat. Catal. 3 (2020) 932–940. doi: 10.1038/s41929-020-00522-9
29. [29]
  J. Wang, Y. Jiang, A. Ma et al., Appl. Catal. B: Environ. 244 (2019) 502–510. doi: 10.1016/j.apcatb.2018.11.076
30. [30]
  X. Zhang, H. Guo, G. Dong et al., Appl. Catal. B: Environ. 277 (2020) 119217. doi: 10.1016/j.apcatb.2020.119217
31. [31]
  C. Xia, Y. Li, H. Kim et al., Mater. 408 (2021) 124900. doi: 10.1016/j.jhazmat.2020.124900
32. [32]
  W. Fu, X. Guan, Y. Si, M. Liu, Chem. Eng. J. 410 (2021) 128391. doi: 10.1016/j.cej.2020.128391
33. [33]
  E. Nurlaela, Y. Sasaki, M. Nakabayashi et al., J. Mater. Chem. A 6 (2018) 15265–15273. doi: 10.1039/c8ta05300f
34. [34]
  X. Feng, T.J. LaTempa, J.I. Basham et al., Nano Lett. 10 (2010) 948–952. doi: 10.1021/nl903886e
35. [35]
  H. Wu, L. Zhang, A. Du et al., Nat. Commun. 13 (2022) 6231. doi: 10.3390/app12126231
36. [36]
  J. Fu, F. Wang, Y. Xiao et al., ACS Catal. 10 (2020) 10316–10324. doi: 10.1021/acscatal.0c02648
37. [37]
  A. Kawashima, T. Sato, N. Ohtsu, K. Asami, Mater. Trans. 45 (2004) 131–136. doi: 10.2320/matertrans.45.131
38. [38]
  M. Rahmati, E.M. Zahrani, M. Atapour et al., Mater. Chem. Phys. 315 (2024) 128983. doi: 10.1016/j.matchemphys.2024.128983
39. [39]
  C. Feng, B. Zhao, Y. Bi, J. Mater. Chem. A 10 (2022) 12811–12816. doi: 10.1039/d2ta02702j
40. [40]
  J.H. Swisher, M.H. Read, Metall. Trans. 3 (1972) 493–498. doi: 10.1007/BF02642054
41. [41]
  E. Watanabe, H. Ushiyama, K. Yamashita, ACS Appl. Mater. Inter. 9 (2017) 9559–9566. doi: 10.1021/acsami.6b12261
42. [42]
  X. Zhang, J. Li, Y. Yang et al., Adv. Mater. 30 (2018) 1803551. doi: 10.1002/adma.201803551
43. [43]
  J. Wang, M. Zhang, G. Yang et al., Adv. Funct. Mater. 31 (2021) 2101532. doi: 10.1002/adfm.202101532
44. [44]
  X. Ding, J. Yu, W. Huang et al., Chem. Eng. J. 451 (2023) 138550. doi: 10.1016/j.cej.2022.138550
45. [45]
  X. Hu, S. Zhang, J. Sun et al., Nano Energy 56 (2019) 109–117. doi: 10.1016/j.nanoen.2018.11.047
46. [46]
  Z. Zhang, X. Huang, B. Zhang, Y. Bi, Energy Environ. Sci. 15 (2022) 2867–2873. doi: 10.1039/d2ee00936f
47. [47]
  B. Zhang, S. Yu, Y. Dai et al., Nat. Commun. 12 (2021) 6969. doi: 10.1038/s41467-021-27299-0
1. [1]
  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
2. [2]
  Lina Wang , Hairu Wang , Qian Bu , Qiong Mei , Junbo Zhong , Bo Bai , Qizhao Wang . Al-O bridged NiFeO_x/BiVO₄ photoanode for exceptional photoelectrochemical water splitting. Chinese Chemical Letters, 2025, 36(4): 110139-. doi: 10.1016/j.cclet.2024.110139
3. [3]
  Yuhao Ma , Yufei Zhou , Hongli Li , Cheng Fang , Mingchuan Yu , Shaoxia Yang , Junfeng Niu . Photoelectrocatalytic degradation of refractory organic pollutants in water: Mechanism of active species generation by modulating the photoanode micro-interface. Chinese Chemical Letters, 2026, 37(1): 111249-. doi: 10.1016/j.cclet.2025.111249
4. [4]
  Jiqing Liu , Qi Dang , Liting Wang , Dejin Wang , Liang Tang . Applications of flexible electrochemical electrodes in wastewater treatment: A review. Chinese Chemical Letters, 2024, 35(8): 109277-. doi: 10.1016/j.cclet.2023.109277
5. [5]
  Chao-Long Chen , Rong Chen , La-Sheng Long , Lan-Sun Zheng , Xiang-Jian Kong . Anchoring heterometallic cluster on P-doped carbon nitride for efficient photocatalytic nitrogen fixation in water and air ambient. Chinese Chemical Letters, 2024, 35(4): 108795-. doi: 10.1016/j.cclet.2023.108795
6. [6]
  Entian Cui , Yulian Lu , Zhaoxia Li , Zhilei Chen , Chengyan Ge , Jizhou Jiang . Interfacial B-O bonding modulated S-scheme B-doped N-deficient C₃N₄/O-doped-C₃N₅ for efficient photocatalytic overall water splitting. Chinese Chemical Letters, 2025, 36(1): 110288-. doi: 10.1016/j.cclet.2024.110288
7. [7]
  Jun Yu , Yangping Zhang , Nannan Zhang , Jie Li , Huiyu Sun , Xinyu Gu , Changqing Ye , Tianpeng Liu , Yukou Du . The interface engineering strategy assists the 3D core-shell structure Co₃S₄/CuS@NiFe LDH nanocoral spheres to achieve significant overall water splitting. Chinese Chemical Letters, 2026, 37(2): 110830-. doi: 10.1016/j.cclet.2025.110830
8. [8]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-0. doi: 10.3866/PKU.WHXB202403005
9. [9]
  Yang Yang , Yan-Xin Chen , Ao-Sheng She , Hao-Yan Shi , Wen Chen , Wei Wang , Hai-Long Wang , Ke-Xian Li , Yi-Hu Pu , Wei-Hua Yang , Xiu-Mei Lin , Can-Zhong Lu . Nickel phosphide modified TiO2 nanotube arrays for efficient PEC water splitting H2 generation. Chinese Journal of Structural Chemistry, 2025, 44(7): 100623-100623. doi: 10.1016/j.cjsc.2025.100623
10. [10]
  Ji Chen , Yifan Zhao , Shuwen Zhao , Hua Zhang , Youyu Long , Lingfeng Yang , Min Xi , Zitao Ni , Yao Zhou , Anran Chen . Heterogeneous bimetallic oxides/phosphides nanorod with upshifted d band center for efficient overall water splitting. Chinese Chemical Letters, 2024, 35(9): 109268-. doi: 10.1016/j.cclet.2023.109268
11. [11]
  Jiaxin Su , Jiaqi Zhang , Shuming Chai , Yankun Wang , Sibo Wang , Yuanxing Fang . Optimizing Poly(heptazine imide) Photoanodes Using Binary Molten Salt Synthesis for Water Oxidation Reaction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408012-0. doi: 10.3866/PKU.WHXB202408012
12. [12]
  Shudi Yu , Jie Li , Jiongting Yin , Wanyu Liang , Yangping Zhang , Tianpeng Liu , Mengyun Hu , Yong Wang , Zhengying Wu , Yuefan Zhang , Yukou Du . Built-in electric field and core-shell structure of the reconstructed sulfide heterojunction accelerated water splitting. Chinese Chemical Letters, 2024, 35(12): 110068-. doi: 10.1016/j.cclet.2024.110068
13. [13]
  Mengzhao Liu , Jie Yin , Chengjian Wang , Weiji Wang , Yuan Gao , Mengxia Yan , Ping Geng . P doped Ni₃S₂ and Ni heterojunction bifunctional catalysts for electrocatalytic 5-hydroxymethylfurfural oxidation coupled hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(9): 111271-. doi: 10.1016/j.cclet.2025.111271
14. [14]
  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
15. [15]
  Yuchen Guo , Xiangyu Zou , Xueling Wei , Weiwei Bao , Junjun Zhang , Jie Han , Feihong Jia . Fe regulating Ni3S2/ZrCoFe-LDH@NF heterojunction catalysts for overall water splitting. Chinese Journal of Structural Chemistry, 2024, 43(2): 100206-100206. doi: 10.1016/j.cjsc.2023.100206
16. [16]
  Wenjie Jiang , Zhixiang Zhai , Xiaoyan Zhuo , Jia Wu , Boyao Feng , Tianqi Yu , Huan Wen , Shibin Yin . Revealing the reactant adsorption role of high-valence WO3 for boosting urea-assisted water splitting. Chinese Journal of Structural Chemistry, 2025, 44(3): 100519-100519. doi: 10.1016/j.cjsc.2025.100519
17. [17]
  Xinxin Zhang , Zhijian Liang , Xu Zhang , Qian Guo , Ying Xie , Lei Wang , Honggang Fu . Electronic modulation of VN on Co_5.47N as tri-functional electrocatalyst for constructing zinc-air battery to drive water splitting. Chinese Chemical Letters, 2025, 36(5): 109935-. doi: 10.1016/j.cclet.2024.109935
18. [18]
  Weilong Liu , Jipeng Dong , Luyao Zhang , Ning Li , Yangqin Gao , Lei Ge . Dynamic tuning of d-p orbital hybridization during sulfur vacancy evolution in Co9S8 toward efficient overall water splitting. Chinese Journal of Structural Chemistry, 2025, 44(9): 100661-100661. doi: 10.1016/j.cjsc.2025.100661
19. [19]
  Zhihao HE , Jiafu DING , Yunjie WANG , Xin SU . First-principles study on the structure-property relationship of AlX and InX (X=N, P, As, Sb). Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1007-1019. doi: 10.11862/CJIC.20240390
20. [20]
  Hualin Jiang , Wenxi Ye , Huitao Zhen , Xubiao Luo , Vyacheslav Fominski , Long Ye , Pinghua Chen . Novel 3D-on-2D g-C₃N₄/AgI._x._y heterojunction photocatalyst for simultaneous and stoichiometric production of H₂ and H₂O₂ from water splitting under visible light. Chinese Chemical Letters, 2025, 36(2): 109984-. doi: 10.1016/j.cclet.2024.109984

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(771)
HTML views(42)

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

Band structure engineering of phosphorus doped Ta3N5 for efficient photoelectrochemical water oxidation

Metrics

通讯作者: 陈斌, bchen63@163.com

Band structure engineering of phosphorus doped Ta₃N₅ for efficient photoelectrochemical water oxidation