Precursor-modified strategy to synthesize thin porous amino-rich graphitic carbon nitride with enhanced photocatalytic degradation of RhB and hydrogen evolution performances

doi:10.1016/S1872-2067(21)63873-1

Abstract

Abstract:

The photocatalytic activity of carbon nitride (CN) materials is mainly limited to small specific surface areas, limited solar absorption, and low separation and mobility of photoinduced carriers. In this study, we developed a precursor-modified strategy for the synthesis of graphitic CN with highly efficient photocatalytic performance. The precursor dicyandiamide reformed by different acids undergoes a basic structural change and transforms into diverse new precursors. The thin porous amino-rich HNO₃-CN (5H-CN) was calcined by dicyandiamidine nitrate, formed by concentrated nitric acid modified dicyandiamide, and presented the best photocatalytic degradation rate of RhB, more than 34 times that of bulk graphitic CN. Moreover, the photocatalytic hydrogen evolution rate of 5H-CN significantly improved. The TG-DSC-FTIR analyses indicated that the distinguishing thermal polymerization process of 5H-CN led to its thin porous amino-rich structure, and the theoretical calculations revealed that the negative conduction band potential of 5H-CN was attributed to its amino-rich structure. It is anticipated that the thin porous structure and the negative conduction band position of 5H-CN play important roles in the improvement of the photocatalytic performance. This study demonstrates that precursor modification is a promising project to induce a new thermal polycondensation process for the synthesis of CN with enhanced photocatalytic performance.

Key words: Precursor-modified strategy, Graphitic carbon nitride, Photocatalytic degradation, hydrogen evolution, Amino-rich structure

Ting Huang, Jiaqi Chen, Lili Zhang, Alireza Khataee, Qiaofeng Han, Xiaoheng Liu, Jingwen Sun, Junwu Zhu, Shugang Pan, Xin Wang, Yongsheng Fu. Precursor-modified strategy to synthesize thin porous amino-rich graphitic carbon nitride with enhanced photocatalytic degradation of RhB and hydrogen evolution performances[J]. Chinese Journal of Catalysis, 2022, 43(2): 497-506.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63873-1

https://www.cjcatal.com/EN/Y2022/V43/I2/497

Figures/Tables 5

Fig. 1. FTIR spectra (a,b) and XRD patterns (c) of dicyandiamide and different acid modified dicyandiamides. (1) C2H4N4-HNO3; (2) C2H4N4-H3PO4; (3) C2H4N4-C2H5COOH; (4) C2H4N4-HCl; (5) C2H4N4. (d,e) SEM images of the bulk CN and HNO3-CN (5H-CN); (f,g) TEM images of the bulk CN and HNO3-CN (5H-CN); (h,i) TG-FTIR spectra of dicyandiamide (C2H4N4) and dicyandiamidine nitrate (C2H6N4O·HNO3) (C9-C49 represent 90-490, respectively); (j) Structure diagram of HNO3-CN (5H-CN).

Fig. 2. FTIR spectra (a) and XRD patterns (b) of the bulk CN, HCl-CN, C2H5COOH-CN, H3PO4-CN, and HNO3-CN (5H-CN); (c) XPS survey spectra; high resolution C 1s (d) and N 1s (e) spectra of the bulk CN and 5H-CN; (f) (NHx)/(N3c) peak area ratio and the C/N atomic ratio of the bulk CN and 5H-CN; (g) Solid-state 15N NMR spectra of the bulk CN and 5H-CN; XRD patterns (h) and FTIR spectra (i) of the bulk CN and xH-CN.

Fig. 3. (a) Bar plot showing the remaining RhB in solution after reaching the adsorption-desorption equilibrium in the dark; (b) Time-dependent UV-vis absorption spectra for the photocatalytic degradation of RhB with 5H-CN under visible-light irradiation (λ > 420 nm); (c,d) Plots of C/C0 against reaction time and ln(C/C0) against reaction time for the photocatalytic degradation of RhB over bulk CN and xH-CN catalysts under visible-light irradiation (λ > 420 nm); (e,f) Plots of C/C0 and ln(C/C0) against reaction time for the photocatalytic degradation of RhB over bulk CN, H3PO4-CN, C2H5COOH-CN, HCl-CN, and HNO3-CN; (g) Photocatalytic H2 production for the bulk CN and 5H-CN under visible light irradiation (λ > 420 nm) and cycling runs for the photocatalytic H2 production activity over 20 h; (h) Bar plot showing the photodegradation activity of RhB after 10 cycles for 5H-CN; (i) XRD patterns of 5H-CN before and after photocatalytic degradation of RhB.

Fig. 4. Nitrogen adsorption-desorption isotherms (a), UV-vis DRS (b), Mott-Schottky plots (c), and photocurrent transient responses (d) of bulk CN and 5H-CN; (e,f) Influence of various trapping agents on RhB photocatalytic degradation with 5H-CN catalyst under visible-light irradiation.

Fig. 5. Possible photocatalytic mechanism for the 5H-CN material.

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