Design of p-n homojunctions in metal-free carbon nitride photocatalyst for overall water splitting

doi:10.1016/S1872-2067(20)63670-1

Abstract

Abstract:

Two-dimensional (2D) carbon nitride (CN) photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties. In this study,we successfully prepared CN materials with heterogeneous structures via hydrothermal treatment,high-temperature roasting,ball milling,sintering,and other processes. Benefitting from interface interactions in hybrid architectures,the CN photocatalysts exhibited high photocatalytic activity. The rate of hydrogen production using these CN photocatalysts reached 17028.82 μmol h-1 g-1,and the apparent quantum efficiency was 11.2% at 420 nm. The ns-level time-resolved photoluminescence (PL) spectra provided information about the time-averaged lifetime of fluorescence charge carriers; the lifetime of the charge carriers causing the fluorescence of CN reached 9.99 ns. Significantly,the CN photocatalysts displayed satisfactory results in overall water splitting without the addition of sacrificial agents. The average hydrogen and oxygen production rates were 270.95 μmol h-1 g-1 and 115.21 μmol h-1 g-1 in 7 h,respectively,which were promising results for the applications of the catalysts in overall water splitting processes. We investigated the high efficiency of the prepared CN photocatalysts via a series of tests (UV-vis diffuse reflectance spectroscopy,photocurrent response measurements,PL emission spectroscopy,time-resolved PL spectroscopy,and Brunauer-Emmett-Teller analysis). Furthermore,the Mott-Schottky plot and current-voltage curve were acquired via electrochemical tests. The fabricated CN photocatalyst had a small p-n junction in its heterogeneous structure,which further enhanced its photocatalytic efficiency. Therefore,this work can promote the development of CN photocatalysts.

Key words: Heterogeneous structure, 2D Metal-free photocatalyst, Carbon nitride, Overall water splitting, Time-resolved photoluminescence, spectra, Density-functional theory, Heterogeneous structure

Gang Zhao, Shuhua Hao, Jinghua Guo, Yupeng Xing, Lei Zhang, Xijin Xu. Design of p-n homojunctions in metal-free carbon nitride photocatalyst for overall water splitting[J]. Chinese Journal of Catalysis, 2021, 42(3): 501-509.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63670-1

https://www.cjcatal.com/EN/Y2021/V42/I3/501

Figures/Tables 9

Fig. 1. Process flow diagram of the preparation of CN photocatalyst with a heterogeneous structure.

Fig. 2. SEM images of CN nanotubes (a),CN nanosheets (b),CN photocatalyst (c) with heterogeneous structure,and ordinary g-C3N4 photocatalyst (d); IR spectra (e) and XRD patterns (f) of photocatalysts.

Fig.3. (a) Typical time course of H2 production from aqueous solution (100 mL) containing triethanolamine (20 vol%) as a sacrificial electron donor and 50 mg of 1 wt% Pt-loaded catalyst under 300 W Xe lamp with an optical cut-off filter (λ > 420 nm); (b) Hydrogen evolution rates with different CN photocatalysts; (c) Wavelength dependent AQE by this work-CN; (d) H2 and O2 production from aqueous solution (100 mL) and 50 mg of 1 wt% Pt-loaded catalyst under 300 W Xe lamp; (e) H2 and O2 evolution rates based on this work-CN photocatalyst; (f) H2 and O2 evolution cycling curves of this work-CN photocatalyst.

Fig.4. (a) UV-vis diffuse reflectance spectra of different CN photocatalysts; (b) Plot of (AEphoton)2-Ephoton; (c) Photocurrent response of samples to on-off cycles of illumination; (d) PL emission spectra.

Fig. 5. ns-Level time-resolved PL spectra monitored at 450 nm under 420 nm excitation for CN nanotubes (a),CN nanosheets (b),and this work-CN (c)

Fig. 6. Typical nitrogen adsorption-desorption isotherms of different CN photocatalysts. (a) CN nanotubes; (b) CN nanosheets; (c) this work-CN; (d) g-C3N4.

Fig. 7. High-resolution XPS spectra of different CN photocatalysts. (a,c,e) C1s; (b,d,f) N1s.

Fig. 8. Optimized structures of C2.83N (a) and C0.82N (b); carbon atoms are gray and nitrogen atoms are blue. Electronic band structures of C2.83N (c) and C0.82N (d). The energy at the Fermi level was set to zero. (e,f) Mott-Schottky plots for determining CN nanotubes and nanosheets.

Fig. 9. (a) Characteristic current-voltage curve of CN (this work). (b) Schematic diagram showing the production of hydrogen and oxygen,energy band structure,and electron-hole pair separation in this CN photocatalyst containing a p-n heterojunction.

References

[1]	G. Zhang, G. Li, T. Heil, S. Zafeiratos, A. Savateev, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2019,58, 3433-3437.
[2]	Y. Li, T. Kong, S. Shen, Small, 2019,15, 1900772.
[3]	I. Y. Kim, S. Kim, X. Jin, S. Premkumar, G. Chandra, N. Lee, G. P. Mane, S. Hwang, S. Umapathy, A. Vinu, Angew. Chem. Int. Ed., 2018,57, 17135-17140.
[4]	Y. P. Pang, M. N. Uddin, W. Chen, S. Javaid, E. Barker, Y. G. Li, A. Suvorova, M. Saunders, Z. Y. Yin, G. H. Jia, Adv. Mater., 2019,31, 1905540.
[5]	G. Zhang, L. Lin, G. Li, Y. Zhang, A. Savateev, S. Zafeiratos, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2018,57, 9372-9376.
[6]	G. H. Jia, Y. P. Pang, J. J. Ning, U. Banin, B. T. Ji, Adv. Mater., 2019,31, 1900781.
[7]	Z. Wang, Y. Inoue, T. Hisatomi, R. Ishikawa, Q. Wang, T. Takata, S. Chen, N. Shibata, Y. Ikuhara, K. Domen, Nat. Catal., 2018,1, 756-763.
[8]	D. C. Chen, H. Y. Zhang, Y. G. Li, Z. Y. Yin, H. Q. Sun, L. C. Zhang, S. B. Wang, M. Saunders, E. Barker, G. H. Jia, Adv. Mater., 2018,30, 1803351.
[9]	Y. J. Ren, D. Q. Zeng, W. J. Ong, Chin. J. Catal., 2019,40, 289-319.
[10]	Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhong, C. Wang, Z. Pan, T. Takata, M. Nakabayashi, N. Shibata, Y. Li, I. Sharp, A. Kudo, T. Yamada, K. Domen, Nat. Mater., 2016,15, 611-615.
[11]	X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson, K. Domen, M. Antonietti, Nat. Mater., 2009,8, 76-80.
[12]	Y. Kang, Y. Yang, L. Yin, X. Kang, L. Wang, G. Liu, H. Cheng, Adv. Mater., 2016,28, 6471-6477.
[13]	Y. Zheng, L. Lin, B. Wang, X. Wang, Angew. Chem. Int. Ed., 2015,54, 12868-12884.
[14]	R. C. Shen, J. Xie, Q. J. Xiang, X. B. Chen, J. Z. Jiang, X. Li, Chin. J. Catal., 2019,40, 240-288.
[15]	X. Li, W. Bi, L. Zhang, S. Tao, W. Chu, Q. Zhang, Y. Luo, C. Wu, Y. Xie, Adv. Mater., 2016,28, 2427-2431.
[16]	H. Q. Xu, J. Hu, D. Wang, Z. Li, Q. Zhang, Y. Luo, S. H. Yu, H. L. Jiang, J. Am. Chem. Soc., 2015,137, 13440-13443.
[17]	D. Ren, W. Zhang, Y. Ding, R. Shen, Z. Jiang, X. Lu, X. Li, Sol. RRL., 2020,doi: 10.1002/solr.201900423.
[18]	X. She, J. Wu, H. Xu, J. Zhong, Y. Wang, Y. Song, K. Nie, Y. Liu, Y. Yang, M. T. F. Rodrigues, R. Vajtai, J. Lou, D. Du, H. Li, P. M. Ajayan, Adv. Energy Mater., 2017,7, 1700025.
[19]	S. Cao, J. Low, J. Yu, M. Jaroniec, Adv. Mater., 2015,27, 2150-2176.
[20]	N. Xiao, S. S. Li, S. Liu, B. R. Xu, Y. D. Li, Y. Q. Gao, L. Ge, G. W. Lu, Chin. J. Catal., 2019,40, 352-361.
[21]	J. Mahmood, E. K. Lee, M. Jung, D. Shin, H. J. Choi, J. M. Seo, S. M. Jung, D. W. Kim, F. Li, M. S. Lah, N. Park, H. J. Shin, J. H. Oh, J. B. Baek, Proc. Natl. Acad. Sci. USA, 2016,113, 7414-7419.
[22]	J. Q. Wen, J. Xie, X. B. Chen, X. Li, Appl. Surf. Sci., 2017,391, 72-123.
[23]	J. Mahmood Lee,K. E. M. Jung, D. Shin, I. Y. Jeon, S. M. Jung, H. J. Choi, J. M. Seo, S. Y. Bae, S. D. Sohn, N. Park, J. H. Oh, H. J. Shin, J. B. Baek,, Nat. Commun., 2015,6, 6486.
[24]	C. Y. Wen, J. Tersoff, K. Hillerich, M. C. Reuter, J. H. Park, S. Kodambaka, E. A. Stach, F. M. Ross, Phys. Rev. Lett., 2011,107, 025503.
[25]	M. Z. Rahman, J. Moffatt, N. A. Spooner, Mater. Horiz., 2018,5, 553-559.
[26]	D. Tsivion, M. Schvartzman, R. Popovitz-Biro P. von Huth, E. Joselevich,, Science, 2011,333, 1003-1007.
[27]	J. Zhang, L. Qi, J. Ran, J. Yu, S. Qiao, Adv. Energy Mater., 2014,4, 1301925.
[28]	Y. Pei, H. Wang, G. J. Snyder, Adv. Mater., 2012,24, 6125-6135.
[29]	X. B. Huang, Z. Y. Wu, H. Y. Zheng, W. J. Dong, G. Wang, Green Chem., 2018,20, 664-670.
[30]	F. K. Kessler, Y. Zheng, D. Schwarz, C. Merschjann, W. G. Schnick, X. Wang, M. J. Bojdys, Nat. Rev. Mater., 2017,2, 17030.
[31]	G. X. Zhao, G. G. Liu, H. Pang, H. M. Liu, H. B. Zhang, K. Chang, X. G. Meng, X. J. Wang, J. H. Ye, Small, 2016,12, 6160-6166.
[32]	J. V. Holm, H. I. Jørgensen, P. Krogstrup, J. Nygård, H. Liu, M. Aagesen, Nat. Commun., 2013,4, 1498.
[33]	G. Zhang, G. Li, Z. Lan, L. Lin, A. Savateev, T. Heil, S. Zafeiratos, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2017,56, 13445-13449.
[34]	Y. Sakurai, A. A. Kolokoltsov, C.-C. Chen, M. W. Tidwell, W. E. Bauta, N. Klugbauer, C. Grimm, C. Wahl-Schott, M. Biel, R. A. Davey, Science, 2015,347, 995-998.
[35]	D. J. Martin, K. Qiu, S. A. Shevlin, A. D. Handoko, X. Chen, Z. Guo, J. Tang, Angew. Chem. Int. Ed., 2014,53, 9240-9245.
[36]	X. H. Li, J. S. Zhang, X. F. Chen, A. Fischer, A. Thomas, M. Antonietti, X. C. Wang, Chem. Mater., 2011,23, 4344-4348.
[37]	G. Liu, T. Wang, H. Zhang, X. Meng, D. Hao, K. Chang, P. Li, T. Kako, J. Ye, Angew. Chem. Int. Ed., 2015,54, 13561-13565.
[38]	Q. Liang, Z. Li, X. Yu, Z. Huang, F. Kang, Q. H. Yang, Adv. Mater., 2015,27, 4634-4639.
[39]	Z. Li, Y. N. Ma, X. Y. Hu, E. Z. Liu, J. Fan, Chin. J. Catal., 2019,40, 434-445.
[40]	N. P. Dasgupta, J. Sun, C. Liu, S. Brittman, S. C. Andrews, J. W. Lim, H. Gao, R. Yan, P. Yang, Adv. Mater., 2014,26, 2137-2184.
[41]	M. Shalom, S. Inal, C. Fettkenhauer, D. Neher, M. Antonietti, J. Am. Chem. Soc., 2013,135, 7118-7121.
[42]	J. X. Sun, Y. P. Yuan, L. G. Qiu, X. Jiang, A. J. Xie, Y. H. Shen, J. F. Zhu, Dalton Trans., 2012,41, 6756-6763.
[43]	G. Zhao, Y. Cheng, Y. Wu, X. Xu, X. Hao, Small, 2018,14, 1704138.
[44]	H. Huang, K. Xiao, N. Tian, F. Dong, T. Zhang, X. Du, Y. Zhang, J. Mater. Chem. A, 2017,5, 17452-17463.
[45]	L. Lin, H. Ou, Y. Zhang, X. Wang, ACS Catal., 2016,6, 3921-3931.
[46]	Y. S. Jun, E. Z. Lee, X. Wang, W. H. Hong, G. D. Stucky, A. Thomas, Adv. Funct. Mater., 2013,23, 3661-3667.
[47]	Y. Cui, Z. Ding, X. Fu, X. Wang, Angew. Chem. Int. Ed., 2012,51, 11814-11818.
[48]	Q. Liu, X. Wang, Q. Yang, Z. Zhang, X. Fang, Appl. Catal. B, 2018,225, 22-29.
[49]	J. W. Zhang, S. Gong, N. Mahmood, L. Pan, X. Zhang, J. Zou, Appl. Catal. B, 2018,221, 9-16.
[50]	Z. Lin, X. Wang, ChemSusChem, 2014,7, 1547-1550.
[51]	J. Zhang, M. Zhang, C. Yang, X. Wang, Adv. Mater., 2014,26, 4121-4126.
[52]	J. Sun, J. Zhang, M. Zhang, M. Antonietti, X. Fu, X. Wang, Nat. Commun., 2012,3, 2152.
[53]	G. Zhao, T. Wang, Y. Shao, Y. Wu, B. Huang, X. Hao, Small, 2017,13, 1602243.
[54]	Z. Lin, X. Wang, Angew. Chem. Int. Ed., 2013,52, 1735-1738.
[55]	M. Z. Rahman, C. B. Mullins, Acc. Chem. Res., 2019,52, 248-257.
[56]	M. Z. Rahman, Y. Tang, P. Kwong, Appl. Phys. Lett., 2018,112, 253902.
[57]	M. Z. Rahman, K. Davey, Phys. Rev. Mater., 2018,2, 125402.
[58]	G. Zhang, G. Li, Z. Lan, L. Lin, A. Savateev, T. Heil, S. Zafeiratos, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2017,56, 13445-13449.
[59]	N. Tian, Y. Zhang, X. Li, K. Xiao, X. Du, F. Dong, G. I. N. Waterhouse, T. Zhang, H. Huang, Nano Energy, 2017,38, 72-81.
[60]	M. Z. Rahman, P. C. Tapping, T. W. Kee, R. Smernik, N. Spooner, J. Moffatt, Y. Tang, K. Davey, S. Qiao, Adv. Funct. Mater., 2017,27, 1702384.
[61]	F. Dong, Z. Zhao, T. Xiong, Z. Ni, W. Zhang, Y. Sun, W. K. Ho, ACS Appl. Mater. Interfaces, 2013,5, 11392-11401.
[62]	X. Li, J. G. Yu, M. Jaroniec, X. B. Chen, Chem. Rev., 2019,119, 3962-4179.
[63]	M. Rahman, K. Davey, S. Z. Qiao, Small, 2017,13, 1700376.
[64]	Y. B. Li, Z. L. Jin, L. J. Zhang, K. Fan, Chin. J. Catal., 2019,40, 390-402.
[65]	M. Z. Rahman, K. Davey, S. Z. Qiao, J. Mater. Chem. A, 2018,6, 1305-1322.
[66]	M. Z. Rahman, C. B. Mullins, K. Davey, Adv. Sci., 2018,5, 1800820.
[67]	D. Ren, Z. Liang, Y. H. Ng, P. Zhang, Q. Xiang, X. Li, Chem. Eng. J., 2020,390, 124496.
[68]	H. Wang, L. Zhang, Z. Chen, J. Hu, S. Li, Z. Wang, J. Liu, X. Wang, Chem. Soc. Rev., 2014,43, 5234-5244.
[69]	S. Javaid, X. J. Li, F. Wang, W. Chen, S. B. Wang, G. H. Jia, F. Jones,. J. Mater. Chem. C, 2019,7, 14517.
[70]	L. Jiang, G. Zhou, J. Mi, Z. Wu, Catal. Commun., 2012,24, 48-51.
[71]	G. Zhao, Y. L. Cheng, P. X. Sun, W. X. Ma, S. H. Hao, X. K. Wang, X. J. Xu, Q. Q. Xu, M. Q. Liu, Electrochim. Acta, 2020,331, 135262.
[72]	W. Chen, X. J. Li, F. Wang, S. Javaid, Y. P. Pang, J. Y. Chen, Z. Y. Yin, S. B. Wang, Y. G. Li, G. H. Jia, Small, 2020,16, 1902231.