Doping-induced metal-N active sites and bandgap engineering in graphitic carbon nitride for enhancing photocatalytic H2 evolution performance

doi:10.1016/S1872-2067(21)63849-4

Abstract

Abstract:

Durable and inexpensive graphitic carbon nitride (g-C₃N₄) demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction (HER). To further improve its activity, g-C₃N₄ was subjected to atomic-level structural engineering by doping with transition metals (M = Fe, Co, or Ni), which simultaneously induced the formation of metal-N active sites in the g-C₃N₄ framework and modulated the bandgap of g-C₃N₄. Experiments and density functional theory calculations further verified that the as-formed metal-N bonds in M-doped g-C₃N₄ acted as an “electron transfer bridge”, where the migration of photo-generated electrons along the bridge enhanced the efficiency of separation of the photogenerated charges, and the optimized bandgap of g-C₃N₄ afforded stronger reduction ability and wider light absorption. As a result, doping with either Fe, Co, or Ni had a positive effect on the HER activity, where Co-doped g-C₃N₄ exhibited the highest performance. The findings illustrate that this atomic-level structural engineering could efficiently improve the HER activity and inspire the design of powerful photocatalysts.

Key words: g-C₃N₄, Photocatalytic H₂ generation, Metal-N active sites, Transition metal doping, Band gap engineering

Xiaohui Yu, Haiwei Su, Jianping Zou, Qinqin Liu, Lele Wang, Hua Tang. Doping-induced metal-N active sites and bandgap engineering in graphitic carbon nitride for enhancing photocatalytic H₂ evolution performance[J]. Chinese Journal of Catalysis, 2022, 43(2): 421-432.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63849-4

https://www.cjcatal.com/EN/Y2022/V43/I2/421

Figures/Tables 14

Fig. 1. Photocatalytic H2 evolution performance (a,c,e,g) and H2 evolution rates (b,d,f,h) of CN and doped-samples.

Fig. 2. XRD patterns (a); FT-IR spectra (b); XPS spectra (c); high-resolution XPS spectra of C 1s (d); and N 1s; (e) of CN, CNFe, CNNi and CNCo samples, and high-resolution XPS spectra of Fe 2p of CNFe (f); Co 2p of CNCo (g) and Ni 2p of CNNi (h).

Fig. 3. SEM pictures (a-d), AFM images (e-h) and thickness (i-l) of CN, CNFe, CNCo, CNNi samples.

Fig. 4. TEM pictures of CNFe (a,b), CNCo (d,e), CNNi (g,h); element mapping of CNFe (c), CNCo (f), and CNNi (i) samples.

Fig. 5. N2 adsorption-desorption curves (a) and pore-size distribution (b) of CN and doped-samples.

Fig. 6. (a) Recycle experiment of CNCo sample; AQY at 420, 450, 550, and 650 nm over CNFe (b), CNCo (c), and CNNi (d) samples.

Fig. 7. TRPC spectra (a), EIS spectra (b), PL spectra (c) and LSV curves (d) of CN, CNFe, CNCo and CNNi samples.

Fig. 8. (a) ESR signals labeled by TEMPO-e- for CNCo sample under irradation with different times; (b) ESR signals labeled by TEMPO-e- for CN, CNFe, CNCo and CNNi samples.

Fig. 9. Mulliken charge distribution (a) and electron density difference maps (b) for Fe, Co and Ni in the interstitial site of CN based on the DFT calculation.

Fig. 10. HOMO and LUMO of the doped-samples based on the DFT calculation.

Fig. 11. Optimal geometry structures and adsorption energies of H* atom.

Fig. 12. UV-vis spectra (a), band gaps (b), Motts-schottky curves of CN, CNFe (c), CNCo and CNNi (d) samples.

Fig. 13. The energy band structures of CN, CNFe, CNCo and CNNi samples.

Fig. 14. The mechanism of photocatalytic H2 generation.

References

[1]	X. Gao, D. Zeng, J. Yang, W.-J. Ong, T. Fujita, X. He, J. Liu, Y. Wei, Chin. J. Catal., 2021,42, 1137-1146.
[2]	G. Zhao, S. H. Hao, J. H. Guo, Y. P. Xing, L. Zhang, X. J. Xu, Chin. J. Catal., 2021,42, 501-509.
[3]	H. T. Xu, R. Xiao, J. R. Huang, Y. Jiang, C. X. Zhao, X. F. Yang Chin. J. Catal., 2021,42, 107-114.
[4]	D. K. Sun, J.-W. Shi, D. D. Ma, Y. J. Zou, G. T. Sun, S. M. Mao, L. W. Sun, Y. H. Cheng, Chin. J. Catal., 2020,41, 1421-1429.
[5]	Z. Z. Liang, R. C. Shen, Y. H. Ng, P. Zhang, Q. J. Xiang, X. Lin, J. Mater. Sci. Technol., 2020,56, 89-121.
[6]	R. C. Shen, D. D. Ren, Y. G. Ding, Y. T. Guan, Y. H. Ng, P. Zhang, X. Li, Sci. China Mater., 2020,63, 2153-2188.
[7]	P. Kuang, M. Sayed, J. Fan, B. Cheng, J. Yu, Adv. Energy Mater., 2020,10, 1903802.
[8]	C. Prasad, H. Tang, Q. Q. Liu, I. Bahadur, S. Karlapudi, Y. J. Jiang, Int. J. Hydrogen Energy, 2020,45, 337-379.
[9]	R. C. Shen, K. L. He, A. P. Zhang, N. Li, Y. H. Ng, P. Zhang, J. Hu, X. Li, Appl. Catal. B, 2021,291, 120104.
[10]	Q. Q. Liu, J. X. Huang, L. L. Wang, X. H. Yu, J. F. Sun, H. Tang, Solar RRL, 2020,2000504.
[11]	Y. T. Gao, F. Chen, Z. Chen, H. F. Shi, J. Mater. Sci. Technol., 2020,56, 227-235.
[12]	D. D. Ren, Z. Z. Liang, Y. H. Ng, P. Zhang, Q. J. Xiang, X. Li, Chem. Eng. J., 2020,390, 124496.
[13]	Y. F. Li, M. H. Zhou, B. Cheng, Y. Shao, J. Mater. Sci. Technol., 2020,56, 1-17.
[14]	Y. F. Li, M. Zhang, L. Zhou, S. J. Yang, Z. S. Wu, Y. H. Ma, Acta Phys.-Chim. Sin., 2021,37, 2009030.
[15]	D. Q. Zeng, T. Zhou, W.-J. Ong, M. D. Wu, X. G. Duan, W. J. Xu, Y. Z. Chen, Y.-A. Zhu, D.-L. Peng, ACS Appl. Mater. Interfaces, 2019,11, 5651-5660.
[16]	H. Tang, Z. H. Xia, R. Chen, Q. Q. Liu, T. H. Zhou, Chem. Asian J., 2020,15, 3456-3461.
[17]	Y. Li, X. Li, H. W. Zhang, J. J. Fan, Q. J. Xiang, J. Mater. Sci. Technol., 2020,56, 69-88.
[18]	C. M. Li, Y. H. Du, D. P. Wang, S. M. Yin, W. G. Tu, Z. Chen, M. Kraft, G. Chen, R. Xu, Adv. Funct. Mater., 2017,27, 1604328.
[19]	H. C. Li, C. Shan, B. C. Pan, Environ. Sci. Technol., 2018,52, 2197-2205.
[20]	Y. H. Li, M. L. Gu, T. Shi, W. Cui, X. M. Zhang, F. Dong, J. S. Cheng, J. J. Fan, K. L. Lv, Appl. Catal. B, 2020,262, 118281.
[21]	H. G. Yu, H. Q. Ma, X. H. Wu, X. F. Wang, J. J. Fan, J. G. Yu, Solar RRL, 2021,2000372.
[22]	J. S. Hu, P. F. Zhang, W. J. An, L. Liu, Y. H. Liang, W. Q. Cui, Appl. Catal. B, 2019,245, 130-142.
[23]	Z. Zhu, X. Tang, T. S. Wang, W. Q. Fan, Z. Liu, C. X. Li, P. W. Huo, Y. S. Yan, Appl. Catal. B, 2019,241, 319-328.
[24]	W.-D. Oh, V. W. C. Chang, Z.-T. Hu, R. Goei, T.-T. Lim, Chem. Eng. J., 2017,323, 260-269.
[25]	M. Xie, J. C. Tang, L. S. Kong, W. H. Lu, V. Natarajan, F. Zhu, J. H. Zhan, Chem. Eng. J., 2019,360, 1213-1222.
[26]	M. L. Ren, Y. H. Ao, P. F. Wang, C. Wang, Chem. Eng. J., 2019,378, 122122.
[27]	L. L. Wang, X. Guo, Y. Y. Chen, S. S. Ai, H. M. Ding, Appl. Surf. Sci., 2019,467, 954-962.
[28]	B. Lin, Y. Zhou, B. R. Xu, C. Zhu, W. Tang, Y. C. Niu, J. Di, P. Song, J. D. Zhou, X. Luo, L. X. Kang, R. H. Duan, Q. D. Fu, H. S. Liu, R. H. Jin, C. Xue, Q. Chen, G. D. Yang, K. Varga, Q. Xu, Y. H. Li, Z. Liu, F. C. Liu, Mater. Horiz., 2021,8, 612-618.
[29]	L. Y. Wang, Y. Z. Hong, E. L. Liu, X. X. Duan, X. Lin, J. Y. Shi, Carbon, 2020,163, 234-243.
[30]	Y. G. Xu, F. Y. Ge, Z. G. Chen, S. Q. Huang, W. Wei, M. Xie, H. Xu, H. M. Li, Appl. Surf. Sci., 2019,469, 739-746.
[31]	Z. Li, C. Kong, G. X. Lu, J. Phys. Chem. C, 2015,120, 56-63.
[32]	J. X. Xu, Y. H. Qi, C. Wang, L. Wang, Appl. Catal. B, 2019,241, 178-186.
[33]	T. Ma, Q. Q. Shen, B. Zhao, J. B. Xue, R. F. Guan, X. G. Liu, H. S. Jia, B. S. Xu, Inorg. Chem. Commun., 2019,107, 107451.
[34]	Y. Chu, L. Gu, H. M. Du, K. G. Qu, Y. Zhang, J. S. Zhao, Y. Xie, Int. J. Hydrogen Energy, 2018,43, 21810-21823.
[35]	Y. Yang, G. M. Zeng, D. L. Huang, C. Zhang, D. H. He, C. Y. Zhou, W. J. Wang, W. P. Xiong, B. Song, H. Yi, S. J. Ye, X. Y. Ren, Small, 2020,16, 200163.
[36]	C. Z. Sun, H. Zhang, H. Liu, X. X. Zheng, W. X. Zou, L. Dong, L. Qi, Appl. Catal. B, 2018,235, 66-74.
[37]	W. N. Xing, W. G. Tu, M. Ou, S. Y. Wu, S. M. Yin, H. J. Wang, G, Chen, R. Xu, ChemSusChem, 2019,12, 2029-2034.
[38]	L. Y. Xu, L. Y. Zhang, B. Cheng, J. G. Yu, A. A. Al-Ghamdi, S. Wageh, J. Mater. Sci. Technol., 2021,78, 100-109.
[39]	X.-S. Wang, C. Zhou, R. Shi, Q.-Q. Liu, T.-R. Zhang, Rare Metals, 2019,38, 397-403.
[40]	Q. Q. Liu, J. X. Huang, H. Tang, X. H. Yu, J. Shen, J. Mater. Sci. Technol., 2020,56, 196-205.
[41]	H. G. Yu, J. C. Xu, D. D. Gao, J. J. Fan, J. G. Yu, Sci. China Mater., 2020,63, 2215-2227.
[42]	Z. L. Wang, Y. F. Chen, L. Y. Zhang, B. Cheng, J. G. Yu, J. J. Fan, J. Mater. Sci. Technol., 2020,56, 143-150.
[43]	F. Y. Xu, K. Meng, B. Cheng, S. Y. Wang, J. S. Xu, J. G. Yu, Nat. Commun., 2020,11, 4613.
[44]	Q. Q. Liu, X. D. He, J. N. Tao, H. Tang, Z.-Q. Liu, ChemNanoMat, 2020,7, 44-49.
[45]	Z. W. Zhao, J. Y. Fan, X. Y. Deng, J. Liu, Chem. Eng. J., 2019,360, 1517-1529.
[46]	R. Wang, M. S. Shi, F. Y. Xu, Y. Qiu, P. Zhang, K. L. Shen, Q. Zhao, J. G. Yu, Y. F. Zhang, Nat. Commun., 2020,11, 4465.
[47]	G. M. Liu, G. H. Dong, Y. B. Zeng, C. Y. Wang, Chin. J. Catal., 2020,41, 1564-1572.
[48]	Y. X. Zeng, X. Liu, C. B. Liu, L. L. Wang, Y. C. Xia, S. Q. Zhang, S. L. Luo, Y. Pei, Appl. Catal. B, 2018,224, 1-9.
[49]	Y. D. Hu, Y. T. Qu, Y. S. Zhou, Z. Y. Wang, H. J. Wang, B. Yang, Z. Q. Yu, Y. E. Wu, Chem. Eng. J., 2021,412, 128749.
[50]	K. H. Sun, J. Shen, Q. Q. Liu, H. Tang, M. Y. Zhang, S. Zulfiqar, C. Lei, Chin. J. Catal., 2020,41, 72-81.
[51]	P. F. Xia, S. W. Cao, B. C. Zhu, M. J. Liu, M. S. Shi, J. G. Yu, Y. F. Zhang, Angew. Chem. Int. Ed., 2020,59, 13, 5218-5225.
[52]	G. Wu, S. Hu, Z. Han, C. Liu, Q. Li, New J. Chem., 2017,41, 15289-15297.
[53]	Q. Q. Liu, J. Y. Shen, X. H. Yu, X. F. Yang, W. Liu, J. Yang, H. Tang, H. Xu, H. M. Li, Y. Y. Li, J. S. Xu, Appl. Catal. B, 2019,248, 84-94.
[54]	S. Z. Hu, X. Y. Qu, P. Li, F. Wang, Q. Li, L. J. Song, Y. F. Zhao, X. X. Kang, Chem. Eng. J., 2018,334, 410-418.
[55]	B. C. Zhu, L. Y. Zhang, B. Cheng, Y. Yu, J. G. Yu, Chin. J. Catal., 2021,42, 115-122.
[56]	X. F. Yang, L. Tian, X. L. Zhao, H. Tang, Q. Q. Liu, G. S. Li, Appl. Catal. B, 2019,244, 240-249.
[57]	J. J. Peng, J. Shen, X. H. Yu, H. Tang, Zulfiqar, Q. Q. Liu, Chin. J. Catal., 2021,42, 87-96.

Doping-induced metal-N active sites and bandgap engineering in graphitic carbon nitride for enhancing photocatalytic H₂ evolution performance

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