Citation: Huang Juanjuan, Du Jianmei, Du Haiwei, Xu Gengsheng, Yuan Yupeng. Control of Nitrogen Vacancy in g-C₃N₄ by Heat Treatment in an Ammonia Atmosphere for Enhanced Photocatalytic Hydrogen Generation[J]. Acta Physico-Chimica Sinica, ;2020, 36(7): 190505. doi: 10.3866/PKU.WHXB201905056 shu

Control of Nitrogen Vacancy in g-C₃N₄ by Heat Treatment in an Ammonia Atmosphere for Enhanced Photocatalytic Hydrogen Generation

School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, P. R. China

Corresponding author: Du Haiwei, haiwei.du@ahu.edu.cn Yuan Yupeng, yupengyuan@ahu.edu.cn

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Received Date: 15 May 2019
Revised Date: 28 June 2019
Accepted Date: 28 June 2019
Available Online: 5 July 2019
Fund Project: the National Natural Science Foundation of China 551872003the Anhui Provincial Natural Science Foundation, China 1908085J21The project was supported by the National Natural Science Foundation of China (51872003, 51572003) and the Anhui Provincial Natural Science Foundation, China (1908085J21, 1908085QB83)the National Natural Science Foundation of China 51572003the Anhui Provincial Natural Science Foundation, China 1908085QB83

Graphite phase carbon nitride (g-C₃N₄) has shown excellent potential when applied to photocatalytic hydrogen (H₂) generation upon exposure to visible light. However, the photocatalytic activity during hydrogen generation remains very low because of the high recombination rate of photogenerated electron-hole pairs and poor conductivity. Of the various strategies to improve H₂ generation efficiency, N vacancies have proven to be effective at increasing the photocatalytic performance of g-C₃N₄. However, creating a N vacancy is primarily dependent on the post-heating of g-C₃N₄ in air at an elevated temperature, which generates a high concentration of N vacancies and consequent decreased crystallinity of g-C₃N₄. Thus, as-produced g-C₃N₄ offers low photocatalytic efficiency owing to the high recombination rate of photogenerated electron-hole pairs. Currently, controlling the concentration of N vacancy in g-C₃N₄ is an immense challenge. Herein, we report an effective means of achieving controllable N vacancies in g-C₃N₄ via urea in-situ generated NH₃ at an elevated temperature. Specifically, g-C₃N₄ was first prepared with dicyandiamide as a precursor and subjected to rapid post-thermal treatment at 650 ℃ in a tubular furnace for 10 min, in which a desired amount of urea was mixed with g-C₃N₄ as the source material for NH₃. X-ray diffraction analysis showed increased crystallinity and an unchanged crystal structure as compared to pristine g-C₃N₄. X-ray photoelectron spectroscopy and elemental analysis verified the reduced levels of N-vacancy concentration with urea added as the NH₃ source when compared to the g-C₃N₄ post-heated in air without the addition of urea. In addition, UV-Vis spectra displayed an increased visible light absorption due to the generated N vacancies. Moreover, the specific surface area of g-C₃N₄ was progressively enlarged with an increase in the amount of urea added. The high crystallinity, low N-vacancy concentration, increased light absorption, and enlarged surface area translated into markedly increased photocatalytic H₂ generation. The highest H₂ generation rate from the optimized added amount of urea was 6.5 μmol·h^-1, which was three times higher than that when using a g-C₃N₄ sample thermally treated without urea addition. The H₂ generation enhancement was also the result of the increased separation efficiency of photogenerated electron-hole pairs as exemplified by the significantly decreased photoluminescence spectra and large transient photocurrent. The results of this study demonstrate the simultaneous production of highly crystalline g-C₃N₄ and controllable creation of N vacancy by in-situ generated NH₃ through thermal decomposition of urea. This study reveals the immense potential of NH₃ at controlling the N-vacancy concentration of g-C₃N₄ for increased photocatalytic H₂ generation.
- Semiconductor,
- Carbon nitride,
- Photocatalytic water splitting,
- NH₃,
- Nitrogen vacancy
1. [1]
  Naseri, A.; Samadi, M.; Pourjavadi, A.; Moshfegh, A. Z.; Ramakrishna, S. J. Mater. Chem. A 2017, 5, 23406. doi: 10.1039/C7TA05131J doi: 10.1039/C7TA05131J
2. [2]
  Zhang, J. S.; Wang, B.; Wang, X. C. Acta Phys. -Chim. Sin. 2013, 29(9), 1865. doi: 10.3866/PKU.WHXB201306173
3. [3]
  Ye, S.; Wang, R.; Wu, M. Z.; Yuan, Y. P. Appl. Surf. Sci. 2015, 358, 15. doi: 10.1016/j.apsusc.2015.08.173 doi: 10.1016/j.apsusc.2015.08.173
4. [4]
  Dong, F.; Wu, L.; Sun, Y.; Fu, M.; Wu, Z.; Lee, S. C. J. Mater. Chem. 2011, 21, 15171. doi: 10.1039/c1jm12844b doi: 10.1039/c1jm12844b
5. [5]
  Zhao, Y. C.; Yu, D. L.; Yanagisawa, O.; Matsugi, K.; Tian, Y. J. Diam. Relat. Mater. 2005, 14(10), 1700. doi: 10.1016/j.diamond.2005.06.017 doi: 10.1016/j.diamond.2005.06.017
6. [6]
  Cui, Y. J.; Zhang, J. S.; Zhang, G. G, ; Huang, J. H.; Liu, P.; Antonietti, M.; Wang, X. C. J. Mater. Chem. 2011, 21, 13032. doi: 10.1039/C1JM11961C doi: 10.1039/C1JM11961C
7. [7]
  Kang, Y. Y.; Yang, Y. Q.; Yin L. C.; Kang, X. D.; Wang, L. Z.; Liu, G.; Cheng, M. H. Adv. Mater. 2016, 28(30), 6471. doi: 10.1002/adma.201601567 doi: 10.1002/adma.201601567
8. [8]
  Xu, J.; Wu, H. T.; Wang, X.; Xue, B.; Li, Y. X.; Cao, Y. Phys. Chem. Chem. Phys. 2013, 15, 4510. doi: 10.1039/C3CP44402C doi: 10.1039/C3CP44402C
9. [9]
  Chai, B.; Peng, T. Y.; Mao, J.; Li, K.; Zan, L. Phys. Chem. Chem. Phys. 2012, 14, 16745. doi: 10.1039/C2CP42484C doi: 10.1039/C2CP42484C
10. [10]
  Chen, Y. F.; Huang, W. X.; He, D. L.; Situ, Y.; Huang, H. ACS Appl. Mater. Interfaces 2014, 6, 14405. doi: 10.1021/am503674e doi: 10.1021/am503674e
11. [11]
  Kumar, S.; Tonda, S.; Baruah, A.; Kumar, B.; Shanker, V. Dalton Trans. 2014, 43, 16105. doi: 10.1039/C4DT01076K doi: 10.1039/C4DT01076K
12. [12]
  Zhang, S. W.; Li, J. X.; Zeng, M. Y.; Li, J.; Xu, J. Z.; Wang, X. K. Chem. Eur. J. 2014, 20, 9805. doi: 10.1002/chem.201400060 doi: 10.1002/chem.201400060
13. [13]
  Niu, P.; Qiao, M.; Li, Y. F.; Huang, L.; Zhai, T. Y. Nano Energy 2018, 44, 73. doi: 10.1016/j.nanoen.2017.11.059 doi: 10.1016/j.nanoen.2017.11.059
14. [14]
  Wu, J. J.; Li, N.; Fang, H. B.; Li, X. T.; Zheng, Y. Z.; Tao, X. Chem. Eng. J. 2019, 358, 20. doi: 10.1016/j.cej.2018.09.208 doi: 10.1016/j.cej.2018.09.208
15. [15]
  Chen, J. L.; Hong, Z. H.; Chen, Y. L.; Lin, B. Z.; Gao, B. F. Mater. Lett. 2015, 145, 129. doi: 10.1016/j.matlet.2015.01.073 doi: 10.1016/j.matlet.2015.01.073
16. [16]
  Niu, P.; Liu, G.; Cheng, H. M. J. Phys. Chem. C 2012, 116, 11013. doi: 10.1021/jp301026y doi: 10.1021/jp301026y
17. [17]
  Sun, N.; Liang, Y.; Ma, X. J.; Chen, F. Chem. Eur. J. 2017, 23, 15466. doi: 10.1002/chem.201703168 doi: 10.1002/chem.201703168
18. [18]
  Niu, P.; Li, H. Q.; Ma, Y.; Zhai, T. Y. J. Phys. Chem. C 2018, 122(36), 20717. doi: 10.1021/acs.jpcc.8b04849 doi: 10.1021/acs.jpcc.8b04849
19. [19]
  Lei, J. T.; Sisson T. M.; Lamparski, H. G.; O'Brien, D. F. Macromolecules 1998, 32(1), 73. doi: 10.1021/ma9810363 doi: 10.1021/ma9810363
20. [20]
  Yuan, Y. P.; Xu, W. T.; Yin, L. S.; Chao, X. W.; Liao, Y. X.; Ting, Y. Q.; Xue, C. Int. J. Hydrog. Energy 2013, 38(30), 13159. doi: 10.1016/j.ijhydene.2013.07.104 doi: 10.1016/j.ijhydene.2013.07.104
21. [21]
  Zhang, Y. H.; Pan, Q. W.; Chai, G. Q.; Liang, M.; Dong, G.; Zhang, Q.; Qiu, J. Sci. Rep. 2013, 3, 1943. doi: 10.1038/srep01943 doi: 10.1038/srep01943
22. [22]
  Ye, P.; Liu X. L.; Iocozzia, J.; Yuan, Y. P.; Gu, L. N.; Xu, G. S.; Lin, Z. Q. J. Mater. Chem. A 2017, 5, 8493. doi: 10.1039/C7TA01031A doi: 10.1039/C7TA01031A
23. [23]
  Pawar, R. C.; Kang, S. Park J. H.; Kim, J. H.; Ahn, S.; Lee, C. S. Sci. Rep. 2016, 6, 31147. doi: 10.1038/srep31147 doi: 10.1038/srep31147
24. [24]
  Li, J.; Wu, D. D.; Iocozzia, J.; Du, H. W.; Liu, X. Q.; Yuan, Y. P.; Zhou, W.; Li, Z.; Xue, Z. M.; Lin, Z. Q. Angew. Chem. Int. Ed. 2019, 58 (7), 1985. doi: 10.1002/anie.201813117 doi: 10.1002/anie.201813117
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Control of Nitrogen Vacancy in g-C3N4 by Heat Treatment in an Ammonia Atmosphere for Enhanced Photocatalytic Hydrogen Generation

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通讯作者: 陈斌, bchen63@163.com

Control of Nitrogen Vacancy in g-C₃N₄ by Heat Treatment in an Ammonia Atmosphere for Enhanced Photocatalytic Hydrogen Generation