Donor-acceptor carbon nitride with electron-withdrawing chlorine group to promote exciton dissociation

doi:10.1016/S1872-2067(20)63733-0

Abstract

Abstract:

Carbon nitride (C₃N₄) is promising for photocatalytic hydrogen production, but photogenerated electrons and holes in C₃N₄ usually tend to exist as excitons due to intrinsic Coulomb interactions making its photocatalytic activity unsatisfactory. Herein, a well-designed intramolecular C₃N₄-based donor-acceptor (D-A) photocatalytic system was constructed to promote exciton dissociation. Due to its good chemical compatibility with melamine and appropriate sublimation property, 2-amino-4,6-dichloropyrimidine unit was chosen as the monomer to react with melamine to construct intramolecular D-A system (CNCl_x). The hydrogen evolution rate of CNCl_0.15 is 15.3 times higher than that of bulk C₃N₄ under visible light irradiation, with apparent quantum efficiency of 13.6% at 420 nm. The enhanced activity is attributed to introduced electron-withdrawing -Cl group as terminal group in the resulted CNCl_x samples, which can build internal electric field to promote the exciton dissociation into free electron and hole. In addition, lower work function value of CNCl_x samples indicates that internal electric field can help free electrons and holes transfer to the surface of CNCl_x samples for photocatalytic reaction.

Key words: Carbon nitride, Donor-acceptor, Internal electric field, Exciton, Hydrogen production

Jing-Wen Zhang, Lun Pan, Xiangwen Zhang, Chengxiang Shi, Ji-Jun Zou. Donor-acceptor carbon nitride with electron-withdrawing chlorine group to promote exciton dissociation[J]. Chinese Journal of Catalysis, 2021, 42(7): 1168-1175.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63733-0

https://www.cjcatal.com/EN/Y2021/V42/I7/1168

Figures/Tables 7

Fig. 1. (a) The XRD pattern BCN and CNClx; SEM images of BCN (b), CNCl0.05 (c), CNCl0.1 (d), CNCl0.15 (e), and CNCl0.2 (f).

Fig. 2. The TEM images of BCN (a), CNCl0.05 (b), CNCl0.1 (c), CNCl0.15 (d), CNCl0.2 (e); (f) BET surface area of bulk C3N4 and CNClx.

Fig. 3. (a) The FT-IR spectra and NMR spectra of bulk C3N4 and CNClx; (b) NMR spectra of bulk C3N4 and CNCl0.15.

Fig. 4. (a,b) High-resolution XPS spectra of the BCN and CNClx; (c) The structure of CNClx copolymer.

Fig. 5. (a) UV-vis absorption spectra; (b) Room-temperature EPR spectrum; (c) Time-resolution fluorescence spectra; (d) Electrochemical impedance spectroscopy of BCN and CNClx.

Fig. 6. (a) Photocatalytic hydrogen evolution rates of CN and CNClx samples under visible light irradiation; cycling stability test (b) and wavelength-dependent apparent quantum yield (c) of CNCl0.15; (d) Degradation of organic pollutants of CN and CNClx samples under visible light irradiation.

Fig. 7. Schematic illustration of proposed charge transfer in CNClx under visible-light irradiation.

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