Sulfur-doped g-C3N4/TiO2 S-scheme heterojunction photocatalyst for Congo Red photodegradation

doi:10.1016/S1872-2067(20)63634-8

Abstract

Abstract:

Constructing step-scheme (S-scheme) heterojunctions has been confirmed as a promising strategy for enhancing the photocatalytic activity of composite materials. In this work, a series of sulfur-doped g-C₃N₄ (SCN)/TiO₂ S-scheme photocatalysts were synthesized using electrospinning and calcination methods. The as-prepared SCN/TiO₂ composites showed superior photocatalytic performance than pure TiO₂ and SCN in the photocatalytic degradation of Congo Red (CR) aqueous solution. The significant enhancement in photocatalytic activity benefited not only from the 1D well-distributed nanostructure, but also from the S-scheme heterojunction. Furthermore, the XPS analyses and DFT calculations demonstrated that electrons were transferred from SCN to TiO₂ across the interface of the SCN/TiO₂ composites. The built-in electric field, band edge bending, and Coulomb interaction synergistically facilitated the recombination of relatively useless electrons and holes in hybrid when the interface was irradiated by simulated solar light. Therefore, the remaining electrons and holes with higher reducibility and oxidizability endowed the composite with supreme redox ability. These results were adequately verified by radical trapping experiments, ESR tests, and in situ XPS analyses, suggesting that the electron immigration in the photocatalyst followed the S-scheme heterojunction mechanism. This work can enrich our knowledge of the design and fabrication of novel S-scheme heterojunction photocatalysts and provide a promising strategy for solving environmental pollution in the future.

Key words: TiO₂ nanofiber, Sulfur-doped g-C₃N₄, Step-scheme heterojunction, photocatalysis, In situ XPS, S-scheme mechanism

Juan Wang, Guohong Wang, Bei Cheng, Jiaguo Yu, Jiajie Fan. Sulfur-doped g-C₃N₄/TiO₂ S-scheme heterojunction photocatalyst for Congo Red photodegradation[J]. Chinese Journal of Catalysis, 2021, 42(1): 56-68.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63634-8

https://www.cjcatal.com/EN/Y2021/V42/I1/56

Figures/Tables 10

Fig. 1. Schematic for the preparation of SCN/TiO2 hybrid nanofibers.

Fig. 2. (a) XRD patterns of g-C3N4, SCN, TiO2, and SCN/TiO2 composites; (b) FT-IR spectra of SCN, TiO2, and SCN/TiO2 composites; (c) Nitrogen adsorption-desorption isotherms and pore size distribution curves (inset) of SCN, TiO2, and SCN/TiO2 composites; (d) TG curves for SCN, TiO2, and SCN/TiO2 composites.

Table 1 Porosity and surface properties of the prepared samples.

Samples	S_BET (m²/g)	Pore volume (cm³/g)	Pore size (nm)
TiO₂	16	0.08	19.4
SCNT5	29	0.10	14.1
SCNT6	51	0.17	13.2
SCNT7	33	0.10	12.3
SCNT8	28	0.11	15.2
SCN	20	0.05	10.2

Fig. 3. (a) XPS survey spectra of TiO2, SCN, and SCNT6 samples; High-resolution XPS spectra of Ti 2p (b), O 1s (c) in TiO2 and SCNT6, C 1s (d), N 1s (e), and S 2p (f) in SCN and SCNT6.

Fig. 4. FESEM images of TiO2 (a) and SCNT6 (b); insets on left bottom are the corresponding low-magnification SEM images; TEM (c) and HRTEM (d) images of SCNT6; (e) EDX elemental mappings of O, Ti, N, C and S.

Fig. 5. (a) UV-vis diffused reflectance of SCN, g-C3N4, TiO2, and SCN/TiO2 composites; (b) Tauc plots of SCN, g-C3N4, and TiO2.

Fig. 6. (a) Photocatalytic activity curves of SCN, TiO2, and SCN/TiO2 composites for the degradation of CR aqueous solution under xenon lamp irradiation; (b) Comparison of the apparent rate constants k (10-3 min-1) of the SCN, TiO2, and SCN/TiO2 composites of the degradation of CR under xenon lamp irradiation; (c) Adsorption peaks of CR aqueous solution in the presence of the SCNT6 sample with increasing irradiation time under xenon lamp irradiation; (d) Circulating runs in the decomposition of CR for the SCNT6 sample under xenon lamp irradiation; (e) FT-IR patterns of the SCNT6 sample before and after 5 circulating runs.

Fig. 7. (a) PL spectra of TiO2, SCN, and SCNT6 under 320 nm excitation; (b) Time-resolved transient PL decay of SCN and SCNT6; (c) Transient photocurrent responses of TiO2, SCN, and SCNT6 under xenon lamp irradiation; (d) EIS spectra of TiO2, SCN, and SCNT6 under xenon lamp irradiation; (e) MS plots for TiO2 and SCN; (f) MS plot for g-C3N4.

Fig. 8. (a) Photocatalytic activities of the SCNT6 sample for CR degradation with disparate scavengers; ESR spectra of SCNT6 under dark and simulated solar light: DMPO ?O2- (b) in methanol dispersions and DMPO ?OH (c) in aqueous dispersions.

Fig. 9. (a) Calculated electrostatic potentials for the (101) face of TiO2 and (b) SCN. The blue and red dashed lines denote the Fermi level and vacuum energy level, respectively. In the geometric structures of TiO2 and SCN, the cyan, red, blue, orange, and yellow spheres stand for Ti, O, C, N, and S atoms, respectively. (c) Proposed step-scheme heterojunction photocatalytic mechanism for SCN/TiO2.

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Sulfur-doped g-C₃N₄/TiO₂ S-scheme heterojunction photocatalyst for Congo Red photodegradation

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