Metal-free π-conjugated hybrid g-C3N4 with tunable band structure for enhanced visible-light photocatalytic H2 production

doi:10.1016/j.jmst.2021.01.045

Abstract

Abstract:

Development of low-cost and efficient photocatalytic materials with visible-light response is of urgent need for solving energy and environmental problems. Here, a metal-free two-dimensional (2D) π-conjugated hybrid g-C₃N₄ photocatalyst with tunable band structure was prepared by a novel one-pot bottom-up method based on a supersaturated precipitation process of urea and triethanolamine (TEOA) solution. The microstructure of the hybrid g-C₃N₄ is revealed to be a compound of periodic tri-s-triazine units grafted with N-doped graphene (GR) fragments. From experimental evidence and theoretical calculations, the two different π-conjugated fragments in the hybrid g-C₃N₄ material are proved to construct a 2D in-plane junction structure, thereby expanding the light absorption range and accelerating the interface charge transfer. The π-conjugated electron coupling in the 2D photocatalyst eliminates the grain boundary effect, and the coupled highest occupied molecular orbital (HOMO) effectively promotes the separation of photo-induced charge carriers. Compared with the g-C₃N₄ prepared by the conventional method, the visible-light H₂ production activity of the optimized sample is enhanced by 253 %. This work provides a new strategy of constructing metal-free g-C₃N₄ hybrids for efficient photocatalytic water splitting.

Key words: Metal-free, Hybrid g-C₃N₄, Band structure, Photocatalyst, Hydrogen

Hengming Huang, Kan Hu, Chen Xue, Zhiliang Wang, Zhenggang Fang, Ling Zhou, Menglong Sun, Zhongzi Xu, Jiahui Kou, Lianzhou Wang, Chunhua Lu. Metal-free π-conjugated hybrid g-C₃N₄ with tunable band structure for enhanced visible-light photocatalytic H₂ production[J]. J. Mater. Sci. Technol., 2021, 87: 207-215.

Figures/Tables 7

Scheme 1. Schematic diagram of the preparation process for the hybrid g-C3N4 nanosheets.

Fig. 1. (a) Absorption spectra and (b) Tauc plots of sample CN-T0 - CN-T1 (Inset: Optical photograph). (c) XRD patterns of CN and CN-T0 - CN-T1. (d) FTIR spectra of CN and CN-T0 - CN-T1 (Inset: Schematic diagram of tri-s-triazine structural units).

Fig. 2. TEM images of (a) CN-T0 and (b) CN-T005 with corresponding C, N, and O element specific gravity from EDX spectra. (c)-(e) TEM images of CN-T005 at different magnifications.

Fig. 3. Raman and XPS spectra of CN-T0, CN-T005, and CN-T1: (a) Raman spectra for excitation wavelength λex =325 nm; (b) Raman spectra for excitation wavelength λex =514 nm; Fine XPS spectra of (c) N and (d) C elements.

Scheme 2. Schematic diagram of the possible reaction pathways for the hybrid g-C3N4 nanosheets. (a) Possible reaction pathways for synthesizing N-doped GR fragments during the thermal polymerization process of TEOA. (b) Reaction pathways for synthesizing tri-s-triazine unit structure during thermal polymerization process of urea. (c) Hybrid g-C3N4 polymerized by N-doped GR fragment and tri-s-triazine unit structure.

Fig. 4. (a) Comparison of photocatalytic H2 production performance of g-C3N4, CN-T0, and CN-T005 in 4 h. (b) Comparison of photocatalytic H2 production performance of g-C3N4 and CN-T0 - CN-T1 in unit time. (c) Steady-state PL spectra and (d) time-resolved PL decay of g-C3N4, CN-T0, and CN-T005.

Fig. 5. Structure model and band structure analysis of hybrid g-C3N4. (a) Structure model of hybrid g-C3N4. (b) Band structure of hybrid g-C3N4: PDOS of different atoms. (c) Band structure of hybrid g-C3N4: PDOS of different fragments. (d) Band structure of the hybrid g-C3N4 and the separation pathways of the photo-induced carriers.

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Metal-free π-conjugated hybrid g-C₃N₄ with tunable band structure for enhanced visible-light photocatalytic H₂ production

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