Skip to main content
SpringerLink
Log in

Sodium-doped carbon nitride nanotubes for efficient visible light-driven hydrogen production

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Sodium-doped carbon nitride nanotubes (Na x -CNNTs) were prepared by a green and simple two-step method and applied in photocatalytic water splitting for the first time. Transmission electron microscopy (TEM) element mapping and X-ray photoelectron spectroscopy (XPS) measurements confirm that sodium was successfully introduced in the carbon nitride nanotubes (CNNTs), and the intrinsic structure of graphitic carbon nitride (g-C3N4) was also maintained in the products. Moreover, the porous structure of the CNNTs leads to relatively large specific surface areas. Photocatalytic tests indicate that the porous tubular structure and Na+ doping can synergistically enhance the hydrogen evolution rate under visible light (λ > 420 nm) irradiation in the presence of sacrificial agents, leading to a hydrogen evolution rate as high as 143 μmol·h−1 (20 mg catalyst). Moreover, other alkali metal-doped CNNTs, such as Li x -CNNTs and K x -CNNTs, were tested; both materials were found to enhance the hydrogen evolution rate, but to a lower extent compared with the Na x -CNNTs. This highlights the general applicability of the present method to prepare alkali metal-doped CNNTs; a preliminary mechanism for the photocatalytic hydrogen evolution reaction in the Na x -CNNTs is also proposed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Fujishima, A.; Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972, 238, 37–38.

    Article  Google Scholar 

  2. Wang, X.; Xu, Q.; Li, M. R.; Shen, S.; Wang, X. L.; Wang, Y. C.; Feng, Z. C.; Shi, J. Y.; Han, H. X.; Li, C. Photocatalytic overall water splitting promoted by an α-β phase junction on Ga2O3. Angew. Chem., Int. Ed. 2012, 51, 13089–13092.

    Article  Google Scholar 

  3. Wang, Q.; Hisatomi, T.; Jia, Q. X.; Tokudome, H.; Zhong, M.; Wang, C. Z.; Pan, Z. H.; Takata, T.; Nakabayashi, M.; Shibata, N. et al. Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%. Nat. Mater. 2016, 15, 611–615.

    Article  Google Scholar 

  4. Chen, X. B.; Liu, L.; Peter, Y. Y.; Mao, S. S. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 2011, 331, 746–750.

    Article  Google Scholar 

  5. Iwashina, K.; Iwase, A.; Ng, Y. H.; Amal, R.; Kudo, A. Z-schematic water splitting into H2 and O2 using metal sulfide as a hydrogen-evolving photocatalyst and reduced graphene oxide as a solid-state electron mediator. J. Am. Chem. Soc. 2015, 137, 604–607.

    Article  Google Scholar 

  6. Bi, Y. P.; Ouyang, S. X.; Umezawa, N.; Cao, J. Y.; Ye, J. H. Facet effect of single-crystalline Ag3PO4 sub-microcrystals on photocatalytic properties. J. Am. Chem. Soc. 2011, 133, 6490–6492.

    Article  Google Scholar 

  7. Tada, H.; Fujishima, M.; Kobayashi, H. Photodeposition of metal sulfide quantum dots on titanium(IV) dioxide and the applications to solar energy conversion. Chem. Soc. Rev. 2011, 40, 4232–4243.

    Article  Google Scholar 

  8. Xiang, Q. J.; Yu, J. G.; Jaroniec, M. Graphene-based semiconductor photocatalysts. Chem. Soc. Rev. 2012, 41, 782–796.

    Article  Google Scholar 

  9. Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, M. J.; Domen, K.; Antonietti, M. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 2009, 8, 76–80.

    Article  Google Scholar 

  10. Liu, G.; Niu, P.; Sun, C. H.; Smith, S. C.; Chen, Z. G.; Lu, G. Q.; Cheng, H. M. Unique electronic structure induced high photoreactivity of sulfur-doped graphitic C3N4. J. Am. Chem. Soc. 2010, 132, 11642–11648.

    Article  Google Scholar 

  11. Zhu, J. J.; Xiao, P.; Li, H. L.; Carabineiro, S. A. C. Graphitic carbon nitride: Synthesis, properties, and appli-cations in catalysis. ACS Appl. Mater. Interfaces 2014, 6, 16449–16465.

    Article  Google Scholar 

  12. Zheng, Y.; Lin, L. H.; Wang, B.; Wang, X. C. Graphitic carbon nitride polymers toward sustainable photoredox catalysis. Angew. Chem., Int. Ed. 2015, 54, 12868–12884.

    Article  Google Scholar 

  13. Ong, W. J.; Tan, L. L.; Ng, Y. H.; Yong, S. T.; Chai, S. P. Graphitic carbon nitride (g-C3N4)-based photocatalysts for artificial photosynthesis and environmental remediation: Are we a step closer to achieving sustainability? Chem. Rev. 2016, 116, 7159–7329.

    Article  Google Scholar 

  14. Pan, C. S.; Xu, J.; Wang, Y. J.; Li, D.; Zhu, Y. F. Dramatic activity of C3N4/BiPO4 photocatalyst with core/shell structure formed by self-assembly. Adv. Funct. Mater. 2012, 22, 1518–1524.

    Article  Google Scholar 

  15. Cao, S. W.; Low, J. X.; Yu, J. G.; Jaroniec, M. Polymeric photocatalysts based on graphitic carbon nitride. Adv. Mater. 2015, 27, 2150–2176.

    Article  Google Scholar 

  16. Lin, L. H.; Ou, H. H.; Zhang, Y. F.; Wang, X. C. Tri-s-triazine-based crystalline graphitic carbon nitrides for highly efficient hydrogen evolution photocatalysis. ACS Catal. 2016, 6, 3921–3931.

    Article  Google Scholar 

  17. Raziq, F.; Qu, Y.; Humayun, M.; Zada, A.; Yu, H. T.; Jing, L. Q. Synthesis of SnO2/B-P codoped g-C3N4 nanocom-posites as efficient cocatalyst-free visible-light photoca-talysts for CO2 conversion and pollutant degradation. Appl. Catal. B: Environ. 2017, 201, 486–494.

    Article  Google Scholar 

  18. Zada, A.; Humayun, M.; Raziq, F.; Zhang, X. L.; Qu, Y.; Bai, L. L.; Qin, C. L.; Jing, L. Q.; Fu, H. G. Exceptional visible-light-driven cocatalyst-free photocatalytic activity of g-C3N4 by well designed nanocomposites with plasmonic Au and SnO2. Adv. Energy Mater. 2016, 6, 1601190.

    Article  Google Scholar 

  19. Jun, Y. S.; Park, J.; Lee, S. U.; Thomas, A.; Hong, W. H.; Stucky, G. D. Three-dimensional macroscopic assemblies of low-dimensional carbon nitrides for enhanced hydrogen evolution. Angew. Chem., Int. Ed. 2013, 52, 11083–11087.

    Article  Google Scholar 

  20. Zhang, J. S.; Zhang, M. W.; Yang, C.; Wang, X. C. Nanospherical carbon nitride frameworks with sharp edges accelerating charge collection and separation at a soft photocatalytic interface. Adv. Mater. 2014, 26, 4121–4126.

    Article  Google Scholar 

  21. Yan, H. J. Soft-templating synthesis of mesoporous graphitic carbon nitride with enhanced photocatalytic H2 evolution under visible light. Chem. Commun. 2012, 48, 3430–3432.

    Article  Google Scholar 

  22. Chen, X. F.; Jun, Y. S.; Takanabe, K.; Maeda, K.; Domen, K.; Fu, X. Z.; Antonietti, M.; Wang, X. C. Ordered meso-porous SBA-15 type graphitic carbon nitride: A semicon-ductor host structure for photocatalytic hydrogen evolution with visible light. Chem. Mater. 2009, 21, 4093–4095.

    Article  Google Scholar 

  23. Liu, J.; Huang, J. H.; Zhou, H.; Antonietti, M. Uniform graphitic carbon nitride nanorod for efficient photocatalytic hydrogen evolution and sustained photoenzymatic catalysis. ACS Appl. Mater. Interfaces 2014, 6, 8434–8440.

    Article  Google Scholar 

  24. Guo, S. E.; Deng, Z. P.; Li, M. X.; Jiang, B. J.; Tian, C. G.; Pan, Q. J.; Fu, H. G. Phosphorus-doped carbon nitride tubes with a layered micro-nanostructure for enhanced visi-ble-light photocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2016, 55, 1830–1834.

    Article  Google Scholar 

  25. Tahir, M.; Mahmood, N.; Zhang, X. X.; Mahmood, T.; Butt, F. K.; Aslam, I.; Tanveer, M.; Idrees, F.; Khalid, S.; Shakir, I. et al. Bifunctional catalysts of Co3O4@GCN tubular nanostructured (TNS) hybrids for oxygen and hydrogen evolution reactions. Nano Res. 2015, 8, 3725–3736.

    Article  Google Scholar 

  26. Shalom, M.; Inal, S.; Fettkenhauer, C.; Neher, D.; Ant-onietti, M. Improving carbon nitride photocatalysis by supramolecular preorganization of monomers. J. Am. Chem. Soc. 2013, 135, 7118–7121.

    Article  Google Scholar 

  27. Niu, P.; Zhang, L. L.; Liu, G.; Cheng, H. M. Graphene-like carbon nitride nanosheets for improved photocatalytic activities. Adv. Funct. Mater. 2012, 22, 4763–4770.

    Article  Google Scholar 

  28. Erwin, S. C.; Zu, L. J.; Haftel, M. I.; Efros, A. L.; Kennedy, T. A.; Norris, D. J. Doping semiconductor nanocrystals. Nature 2005, 436, 91–94.

    Article  Google Scholar 

  29. Lu, S.; Li, C.; Li, H. H.; Zhao, Y. F.; Gong, Y. Y.; Niu, L. Y.; Liu, X. J.; Wang, T. The effects of nonmetal dopants on the electronic, optical and chemical performances of monolayer g-C3N4 by first-principles study. Appl. Surf. Sci. 2017, 392, 966–974.

    Article  Google Scholar 

  30. Zhu, Y. N.; Cao, C. Y.; Jiang, W. J.; Yang, S. L.; Hu, J. S.; Song, W. G.; Wan, L. J. Nitrogen, phosphorus and sulfur co-doped ultrathin carbon nanosheets as a metal-free catalyst for selective oxidation of aromatic alkanes and the oxygen reduction reaction. J. Mater. Chem. A 2016, 4, 18470–18477.

    Article  Google Scholar 

  31. Ye, L. J.; Wang, D.; Chen, S. J. Fabrication and enhanced photoelectrochemical performance of MoS2/S-doped g-C3N4 heterojunction film. ACS Appl. Mater. Interfaces 2016, 8, 5280–5289.

    Article  Google Scholar 

  32. Lin, Z. Z.; Wang, X. C. Nanostructure engineering and doping of conjugated carbon nitride semiconductors for hydrogen photosynthesis. Angew. Chem., Int. Ed. 2013, 52, 1735–1738.

    Article  Google Scholar 

  33. Hong, J. D.; Xia, X. Y.; Wang, Y. S.; Xu, R. Mesoporous carbon nitride with in situ sulfur doping for enhanced photocatalytic hydrogen evolution from water under visible light. J. Mater. Chem. 2012, 22, 15006–15012.

    Article  Google Scholar 

  34. Yue, B.; Li, Q. Y.; Iwai, H.; Kako, T.; Ye, J. H. Hydrogen production using zinc-doped carbon nitride catalyst irradiated with visible light. Sci. Technol. Adv. Mater. 2011, 12, 034401.

    Article  Google Scholar 

  35. Beheshtian, J.; Baei, T. M.; Bagheri, Z.; Peyghan, A. A. Carbon nitride nanotube as a sensor for alkali and alkaline earth cations. Appl. Surf. Sci. 2013, 264, 699–706.

    Article  Google Scholar 

  36. Hu, S. Z.; Chen, X.; Li, Q.; Li, F. Y.; Fan, Z. P.; Wang, H.; Wang, Y. J.; Zheng, B. H.; Wu, G. Fe3+ doping promoted N2 photofixation ability of honeycombed graphitic carbon nitride: The experimental and density functional theory sim-ulation analysis. Appl. Catal. B: Environ. 2017, 201, 58–69.

    Article  Google Scholar 

  37. Xiong, T.; Cen, W. L.; Zhang, Y. X.; Dong, F. Bridging the g-C3N4 interlayers for enhanced photocatalysis. ACS Catal. 2016, 6, 2462–2472.

    Article  Google Scholar 

  38. Gao, H. L.; Yan, S. C.; Wang, J. J.; Huang, Y. A.; Wang, P.; Li, Z. S.; Zou Z. G. Towards efficient solar hydrogen production by intercalated carbon nitride photocatalyst. Phys. Chem. Chem. Phys. 2013, 15, 18077–18084.

    Article  Google Scholar 

  39. Zhang, M.; Bai, X. J.; Liu, D.; Wang, J.; Zhu, Y. F. Enhanced catalytic activity of potassium-doped graphitic carbon nitride induced by lower valence position. Appl. Catal. B: Environ. 2015, 164, 77–81.

    Article  Google Scholar 

  40. Wu, M.; Yan, J. M.; Tang, X. N.; Zhao, M.; Jiang, Q. Synthesis of potassium-modified graphitic carbon nitride with high photocatalytic activity for hydrogen evolution. ChemSusChem 2014, 7, 2654–2658.

    Article  Google Scholar 

  41. Jiang, L. B.; Yuan, X. Z.; Pan, Y.; Liang, J.; Zeng, G. M.; Wu, Z. B.; Wang, H. Doping of graphitic carbon nitride for photocatalysis: A review. Appl. Catal. B: Environ. 2017, 217, 388–406.

    Article  Google Scholar 

  42. Long, B. H.; Lin, J. L.; Wang, X. C. Thermally-induced desulfurization and conversion of guanidine thiocyanate into graphitic carbon nitride catalysts for hydrogen photosynthesis. J. Mater. Chem. A 2014, 2, 2942–2951.

    Article  Google Scholar 

  43. Fan, X. Q.; Xing, Z.; Shu, Z.; Zhang, L. X.; Wang, L. Z.; Shi, J. L. Improved photocatalytic activity of g-C3N4 derived from cyanamide-urea solution. RSC Adv. 2015, 5, 8323–8328.

    Article  Google Scholar 

  44. Dong, F.; Ou, M. Y.; Jiang, Y. K.; Guo, S.; Wu, Z. B. Efficient and durable visible light photocatalytic perfor-mance of porous carbon nitride nanosheets for air puri-fication. Ind. Eng. Chem. Res. 2014, 53, 2318–2330.

    Article  Google Scholar 

  45. Le, S. K.; Jiang, T. S.; Li, Y. W.; Zhao, Q.; Li, Y. Y.; Fang, W. B.; Gong, M. Highly efficient visible-light-driven mesoporous graphitic carbon nitride/ZnO nanocomposite photocatalysts. Appl. Catal. B: Environ. 2017, 200, 601–610.

    Article  Google Scholar 

  46. Han, Q.; Wang, B.; Gao, J.; Cheng, Z. H.; Zhao, Y.; Zhang, Z. P.; Qu, L. T. Atomically thin mesoporous nanomesh of graphitic C3N4 for high-efficiency photocatalytic hydrogen evolution. ACS Nano 2016, 10, 2745–2751.

    Article  Google Scholar 

  47. Sharma, J.; Gora, T.; Rimstidt, J. D.; Staley, R. X-ray photoelectron spectra of the alkali azides. Chem. Phys. Lett. 1972, 15, 232–235.

    Article  Google Scholar 

  48. Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; Pierotti, R. A.; Rouquérol, J.; Siemieniewska, T. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure Appl. Chem. 1985, 57, 603–619.

    Article  Google Scholar 

  49. Zheng, D. D.; Cao, X. N.; Wang, X. C. Precise formation of a hollow carbon nitride structure with a Janus surface to promote water splitting by photoredox catalysis. Angew. Chem., Int. Ed. 2016, 55, 11512–11516.

    Article  Google Scholar 

  50. Zhang, J. K.; Yu, Z. B.; Gao, Z.; Ge, H. B.; Zhao, S. C.; Chen, C. Q.; Chen, S.; Tong, X. L.; Wang, M. H.; Zheng, Z. F. et al. Porous TiO2 nanotubes with spatially separated platinum and CoOx cocatalysts produced by atomic layer deposition for photocatalytic hydrogen production. Angew. Chem., Int. Ed. 2017, 56, 816–820.

    Article  Google Scholar 

  51. Tong, Z. W.; Yang, D.; Li, Z.; Nan, Y. H.; Ding, F.; Shen, Y. C.; Jiang, Z. Y. Thylakoid-inspired multishell g-C3N4 nanocapsules with enhanced visible-light harvesting and electron transfer properties for high-efficiency photoca-talysis. ACS Nano 2017, 11, 1103–1112.

    Article  Google Scholar 

  52. Chen, Y.; Wang, B.; Lin, S.; Zhang, Y. F.; Wang, X. C. Activation of n →π* transitions in two-dimensional conjugated polymers for visible light photocatalysis. J. Phys. Chem. C 2014, 118, 29981–29989.

    Article  Google Scholar 

  53. Jorge, A. B.; Martin, D. J.; Dhano, M. T. S.; Rahman, A. S.; Makwan, N.; Tang, J. W.; Sella, A.; Corà, F.; Firth, S.; Marr, A. J. et al. H2 and O2 evolution from water half-splitting reactions by graphitic carbon nitride materials. J. Phys. Chem. C 2013, 117, 7178–7185.

    Article  Google Scholar 

  54. Scholes, G. D.; Rumbles, G. Excitons in nanoscale systems. Nat. Mater. 2006, 5, 683–696.

    Article  Google Scholar 

  55. Liang, Q. H.; Li, Z.; Huang, Z. H.; Kang, F. Y.; Yang, Q. H. Holey graphitic carbon nitride nanosheets with carbon vacancies for highly improved photocatalytic hydrogen production. Adv. Funct. Mater. 2015, 25, 6885–6892.

    Article  Google Scholar 

  56. Zhang, G. G.; Zhang, M. W.; Ye, X. X.; Qiu, X. Q.; Lin, S.; Wang, X. C. Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution. Adv. Mater. 2014, 26, 805–809.

    Article  Google Scholar 

  57. Sano, T.; Tsutsui, S.; Koike, K.; Hirakawa, T.; Teramoto, Y.; Negishi, N.; Takeuchi, K. Activation of graphitic carbon nitride (g-C3N4) by alkaline hydrothermal treatment for photocatalytic NO oxidation in gas phase. J. Mater. Chem. A 2013, 1, 6489–6496.

    Article  Google Scholar 

  58. Guo, F.; Chen, J. L.; Zhang, M. W.; Gao, B. F.; Lin, B. Z.; Chen, Y. L. Deprotonation of g-C3N4 with Na ions for efficient nonsacrificial water splitting under visible light. J. Mater. Chem. A 2016, 4, 10806–10809.

    Article  Google Scholar 

  59. Zhang, Q.; Liu, S. Z.; Zhang, Y. C.; Zhu, A. P.; Li, J.; Du, X. H. Enhancement of the photocatalytic activity of g-C3N4 via treatment in dilute NaOH aqueous solution. Mater. Lett. 2016, 171, 79–82.

    Article  Google Scholar 

Download references

Acknowledgements

The authors would like to thank the financial support from Sakura Science Program (Japan Science and Technology Agency), National Natural Science Foundation of China (Nos. 51627803, 51402348, 11474333, 91433205, 51421002, and 51372270) and the Knowledge Innovation Program of the Chinese Academy of Sciences.

Author information

Authors and Affiliations

  1. Key Laboratory for Renewable Energy, Chinese Academy of Sciences (CAS), Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, CAS, Beijing, 100190, China

    Longshuai Zhang, Ning Ding, Yuzhuan Xu, Jiangjian Shi, Huijue Wu, Yanhong Luo, Dongmei Li & Qingbo Meng

  2. Photocatalysis International Research Center, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba, 278-0022, Japan

    Muneaki Hashimoto, Koudai Iwasaki, Noriyasu Chikamori, Kazuya Nakata & Akira Fujishima

  3. School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China

    Longshuai Zhang, Ning Ding, Yuzhuan Xu, Jiangjian Shi, Huijue Wu, Yanhong Luo, Dongmei Li & Qingbo Meng

Authors
  1. Longshuai Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ning Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Muneaki Hashimoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Koudai Iwasaki
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Noriyasu Chikamori
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Kazuya Nakata
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yuzhuan Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jiangjian Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Huijue Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Yanhong Luo
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Dongmei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Akira Fujishima
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Qingbo Meng
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Dongmei Li, Akira Fujishima or Qingbo Meng.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, L., Ding, N., Hashimoto, M. et al. Sodium-doped carbon nitride nanotubes for efficient visible light-driven hydrogen production. Nano Res. 11, 2295–2309 (2018). https://doi.org/10.1007/s12274-017-1853-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-017-1853-3

Keywords

Search

Navigation