Facile electrospinning synthesis of S-scheme heterojunction CoTiO3/g-C3N4 nanofiber with enhanced visible light photocatalytic activity

doi:10.1016/S1872-2067(23)64566-8

Abstract

Abstract:

Photocatalysts featuring S-scheme heterojunctions offer considerable potential for both the photocatalytic CO₂ conversion and the degradation of antibiotics, providing practical solutions for energy crises and environmental challenges. In this work, 1D/2D CoTiO₃/g-C₃N₄ (CTO/CN) S-scheme heterojunction is synthesized through electrospinning and calcination. The close interweaving of g-C₃N₄ nanosheets around CoTiO₃ nanofibers creates ample contact areas and active sites, resulting in exceptional photocatalytic CO production capability. The optimal mass ratio of CoTiO₃ to g-C₃N₄ is 2%, and the CO and CH₄ yields are 46.5 and 0.825 μmol g^-1 h^-1. Moreover, comparing with monomeric g-C₃N₄, this composite achieves a better CO yield with 43.5 times and displays an impressive product selectivity of 98.3% for CO₂-CO photoreduction. In addition, the 2% CTO/CN photocatalyst demonstrates outstanding photocatalytic degradation efficiency, with degradation rates of 95.88%, 95.53%, and 71.23% for tetracycline hydrochloride, oxytetracycline, and ofloxacin, respectively. These enhanced photocatalytic properties are attributed to the S-scheme system constructed by CoTiO₃ with g-C₃N₄, maintaining strong oxidation-reduction capabilities while efficiently segregating photogenerated charges, with the existence of S-scheme heterojunction confirmed through various analyses. Furthermore, in situ studies and ¹³C calibration experiments reveal that CO and CH₄ originate from the photocatalytic CO₂conversion, further highlighting the potential of this work in advancing CO₂ photoreduction. This study offers novel insights into designing effective S-scheme heterojunction photocatalysts for practical applications to address environmental and energy challenges.

Key words: Electrospinning, S-scheme, g-C₃N₄, Photocatalytic degradation, Photocatalytic CO₂ reduction

Lingkun Yang, Zongjun Li, Xin Wang, Lingling Li, Zhe Chen. Facile electrospinning synthesis of S-scheme heterojunction CoTiO₃/g-C₃N₄ nanofiber with enhanced visible light photocatalytic activity[J]. Chinese Journal of Catalysis, 2024, 59: 237-249.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64566-8

https://www.cjcatal.com/EN/Y2024/V59/I4/237

Figures/Tables 15

Scheme 1. Schematic of the formation process for CTO/CN composites.

Fig. 1. XRD patterns (a) and FTIR spectra (b) of CoTiO3, g-C3N4, and 2% CTO/CN.

Fig. 2. SEM (a), TEM (b), and HRTEM (c) images and EDS spectra (d-i) of CTO/CN.

Fig. 3. (a) Full spectra of the prepared samples. High-resolution XPS spectra of C 1s (b), N 1s (C), Co 2p (d), Ti 2p (e), and O 1s (f).

Fig. 4. (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves for g-C3N4, CoTiO3, and 2% CTO/CN.

Fig. 5. (a) CO and CH4 yields of as-prepared catalysts. (b) Cyclic CO2 photoreduction performance using 2% CTO/CN as the catalyst. (c) XRD pattern of 2% CTO/CN after photocatalytic cycling. (d) TEM image of 2% CTO/CN after cycling in photocatalytic reactions. (e) Photocatalytic degradation rates of TCH, OTC, and OFX antibiotics and their corresponding degradation kinetics (f) for the as-prepared samples.

Fig. 6. (a) In situ FTIR results of CO2 absorption and photocatalytic CO2 reduction on 2% CTO/CN under light of 420 nm. (b) GC-MS results of 13CO2 isotope calibration test.

Fig. 7. Gibbs free energy diagrams of CO2 photoreduction to CO/CH4 over CTO/CN.

Fig. 8. UV-Vis DRS (a), Tauc plot for bandgap (b), PL spectra (c), and TRPL decay curve (d) of g-C3N4, CoTiO3 and 2% CTO/CN.

Fig. 9. (a) EIS tests of as-prepared samples. (b) Transient photocurrent of the as-prepared samples. Mott-Schottky curve of (c) of g-C3N4 and (d) CoTiO3.

Fig. 10. Structure models of g-C3N4 (a) and CoTiO3 (d). Corresponding DOS of g-C3N4 (b) and CoTiO3 (e). Work function of g-C3N4 (c) and CoTiO3 (f).

Fig. 11. Planar-averaged charge density difference for (a) and (b) 2% CTO/CN as a function of position in the z-direction. A positive value indicates electron accumulation; a negative value indicates electron depletion.

Fig. 12. (a) Full spectra of prepared samples. In situ irradiation XPS spectra of C 1s (b), N 1s (c), Co 2p (d), Ti 2p (e), and O 1s (f).

Fig. 13. DMPO-?O2- (a) and DMPO-?OH (b) signal peaks of pure g-C3N4, CoTiO3, and 2% CTO/CN.

Fig. 14. Schematic of light-induced carrier transfer in the CTO/CN composite.

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Facile electrospinning synthesis of S-scheme heterojunction CoTiO₃/g-C₃N₄ nanofiber with enhanced visible light photocatalytic activity

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