Negative inductive effect enhances charge transfer driving in sulfonic acid functionalized graphitic carbon nitride with efficient visible-light photocatalytic performance

doi:10.1016/S1872-2067(21)63872-X

Abstract

Abstract:

Efficient photogenerated carrier migration/separation plays a critical role in increasing the photocatalytic performance of g-C₃N₄. Herein, sulfonic acid group-functionalized g-C₃N₄ (SACN) was synthesized and then synchronously strengthened by a facile-solid-state thermal reaction of g-C₃N₄ and sulfamic acid. As a solid strong acid, sulfamic acid can be used to achieve acid etching on the surface of g-C₃N₄ with the assistance of thermal treatment, leading to an enlarged specific surface area and increased surface catalytic reaction sites. More importantly, our experiments and density functional theory calculations indicate that the driving force generated by the negative inductive effect of sulfonic acid groups significantly improves the charge transfer dynamics and effectively inhibits their recombination. Moreover, the negative inductive effect can induce charge redistribution, which reduces the conduction band potential of g-C₃N₄ to enhance the reduction ability of photo-induced electrons. As a result, the SACN-400 sample showed excellent photocatalytic performance in H₂ generation with an apparent quantum efficiency of 11.03% at 420 ± 15 nm, as well as an efficient photodegradation rate for organic pollutants.

Key words: Photocatalysis, g-C₃N₄, Negative inductive effect, Sulfamic acid, Charge transfer

Min Zhang, Yunfeng Li, Wei Chang, Wei Zhu, Luohong Zhang, Renxi Jin, Yan Xing. Negative inductive effect enhances charge transfer driving in sulfonic acid functionalized graphitic carbon nitride with efficient visible-light photocatalytic performance[J]. Chinese Journal of Catalysis, 2022, 43(2): 526-535.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63872-X

https://www.cjcatal.com/EN/Y2022/V43/I2/526

Figures/Tables 11

Fig. 1. Schematic of the design and preparation of sulfonic acid group-functionalized g-C3N4. (a) Simulated molecular structure of GCN; (b) Simulated molecular structure of SACN; (c) Differential charge density of SACN.

Fig. 2. XRD patterns (a) and FT-IR spectra (b) of the as-prepared samples.

Fig. 3. XPS survey spectra (a) and the corresponding high-resolution XPS profiles (b-i) for GCN, SACN-0, and SACN-400 samples

Fig. 4. SEM images of GCN (a), SACN-0 (b), and SACN-400 (c) samples; Elemental mapping images of C (d), N (e), O (f), and S (g) for SACN-400 sample; TEM images of GCN (h), SACN-0 (i), and SACN-400 (j). Inset of (j) is the SAED image of SACN-400.

Fig. 5. N2 adsorption-desorption isotherms and corresponding pore size distribution curves of GCN and SACN-400 samples.

Fig. 6. UV-Vis DRS spectra (a) and Kubelka-Munk plots (b) of the as-prepared samples; Mott-Schottky plot (c) and band structure (d) of GCN and SACN-400 samples.

Fig. 7. Band structure of GCN (a) and SACN-400 (b) samples based on DFT calculation; The density of states of GCN (c) and SACN-400 (d) samples.

Fig. 8. (a) Photocatalytic degradation of RhB; (b) The corresponding degradation kinetics for the as-prepared samples; (c) Photocatalytic H2 production of GCN, SACN-0, and SACN-400 samples; (d) Apparent quantum efficiency of SACN-400 at different wavelengths of visible light; (e) Stability test of SACN-400 for H2 generation.

Fig. 9. (a) Steady-state PL spectra of the as-prepared samples; Time-resolved PL spectra (b), EIS tests (c), and LSV curves (d) of GCN, SACN-0, and SACN-400 samples.

Fig. 10. EPR spectra of DMPO-·O2- adducts (a) and DMPO-·OH adducts (b) for GCN, SACN-0 and SACN-400 samples; (c) Trapping experiment of RhB degradation by SACN-400; (d) Differential charge density of SACN-400, yellow and green colors indicate the increase and decrease in electron distributions, respectively.

Fig. 11. Schematic illustration for degradation of organic pollutants and photocatalytic H2 evolution using SACN photocatalysts.

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