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. 2024 Jun 22;25(13):6871.
doi: 10.3390/ijms25136871.

Constructing Direct Z-Scheme Y2TmSbO7/GdYBiNbO7 Heterojunction Photocatalyst with Enhanced Photocatalytic Degradation of Acetochlor under Visible Light Irradiation

Liang Hao  1 , Jingfei Luan  1   2
Affiliations

Constructing Direct Z-Scheme Y2TmSbO7/GdYBiNbO7 Heterojunction Photocatalyst with Enhanced Photocatalytic Degradation of Acetochlor under Visible Light Irradiation

Liang Hao et al. Int J Mol Sci. .

Abstract

This study presents a pioneering synthesis of a direct Z-scheme Y2TmSbO7/GdYBiNbO7 heterojunction photocatalyst (YGHP) using an ultrasound-assisted hydrothermal synthesis technique. Additionally, novel photocatalytic nanomaterials, namely Y2TmSbO7 and GdYBiNbO7, were fabricated via the hydrothermal fabrication technique. A comprehensive range of characterization techniques, including X-ray diffractometry, Fourier-transform infrared spectroscopy, Raman spectroscopy, UV-visible spectrophotometry, X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray energy-dispersive spectroscopy, fluorescence spectroscopy, photocurrent testing, electrochemical impedance spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance, was employed to thoroughly investigate the morphological features, composition, chemical, optical, and photoelectric properties of the fabricated samples. The photocatalytic performance of YGHP was assessed in the degradation of the pesticide acetochlor (AC) and the mineralization of total organic carbon (TOC) under visible light exposure, demonstrating eximious removal efficiencies. Specifically, AC and TOC exhibited removal rates of 99.75% and 97.90%, respectively. Comparative analysis revealed that YGHP showcased significantly higher removal efficiencies for AC compared to the Y2TmSbO7, GdYBiNbO7, or N-doped TiO2 photocatalyst, with removal rates being 1.12 times, 1.21 times, or 3.07 times higher, respectively. Similarly, YGHP demonstrated substantially higher removal efficiencies for TOC than the aforementioned photocatalysts, with removal rates 1.15 times, 1.28 times, or 3.51 times higher, respectively. These improvements could be attributed to the Z-scheme charge transfer configuration, which preserved the preferable redox capacities of Y2TmSbO7 and GdYBiNbO7. Furthermore, the stability and durability of YGHP were confirmed, affirming its potential for practical applications. Trapping experiments and electron spin resonance analyses identified active species generated by YGHP, namely •OH, •O2-, and h+, allowing for comprehensive analysis of the degradation mechanisms and pathways of AC. Overall, this investigation advances the development of efficient Z-scheme heterostructural materials and provides valuable insights into formulating sustainable remediation strategies for combatting AC contamination.

Keywords: GdYBiNbO7; Y2TmSbO7; Y2TmSbO7/GdYBiNbO7 heterojunction photocatalyst; acetochlor; degradation mechanism; degradation pathway; direct Z-scheme; photocatalytic activity; visible light exposure.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
XRD images: (a) YGHP, (b) Y2TmSbO7, and (c) GdYBiNbO7.
Figure 2
Figure 2
(a) XRD pattern and Rietveld refinement and (b) the atomic architecture (red atom: O; cyan atom: Y; purple atom: Tm or Sb) of Y2TmSbO7.
Figure 3
Figure 3
(a) XRD pattern and Rietveld refinement and (b) the atomic architecture (red atom: O; cyan atom: Gd or Y; purple atom: Bi or Nb) of GdYBiNbO7.
Figure 4
Figure 4
FTIR spectra of Y2TmSbO7, GdYBiNbO7, and YGHP.
Figure 5
Figure 5
Raman spectra of (a) YGHP, (b) Y2TmSbO7, and (c) GdYBiNbO7.
Figure 6
Figure 6
(a) TEM image and (b) HRTEM image of YGHP.
Figure 7
Figure 7
EDS elemental mapping of YGHP (Y, Tm, Sb, and O from Y2TmSbO7 and Gd, Y, Bi, Nb, and O from GdYBiNbO7).
Figure 8
Figure 8
The EDS spectrum of YGHP.
Figure 9
Figure 9
The full XPS spectrum of synthesized YGHP, Y2TmSbO7, and GdYBiNbO7.
Figure 10
Figure 10
The high-resolution XPS spectra of (a) Y 3d and Bi 4f; (b)Tm 4d; (c) Gd 4d; (d) Nb 3d, and (e) O 1s and Sb 3d of YGHP, Y2TmSbO7, and GdYBiNbO7.
Figure 10
Figure 10
The high-resolution XPS spectra of (a) Y 3d and Bi 4f; (b)Tm 4d; (c) Gd 4d; (d) Nb 3d, and (e) O 1s and Sb 3d of YGHP, Y2TmSbO7, and GdYBiNbO7.
Figure 11
Figure 11
(a) The UV-Vis diffuse reflectance spectra and (b) correlative diagram of (αhν)1/2 and hν of the fabricated YGHP, Y2TmSbO7, and GdYBiNbO7.
Figure 12
Figure 12
Saturation fluctuation charts of (a) AC and (b) TOC during photodegradation of AC with YGHP, Y2TmSbO7, GdYBiNbO7, N-T or without photocatalyst as the catalytic sample under VLTE.
Figure 13
Figure 13
Saturation fluctuation images of (a) AC and (b) TOC during photodegradation of AC in pesticide-containing wastewater with YGHP as a photocatalyst under VLTE for successive degradation trials.
Figure 14
Figure 14
Impact of different radical scavengers on (a) AC saturation and (b) removal efficiency of AC.
Figure 15
Figure 15
EPR spectrum for DMPO·O2− and DMPO·OH over YGHP.
Figure 16
Figure 16
(a) PL spectrum of YGHP, Y2TmSbO7, and GdYBiNbO7, and TRPL spectra of (b) YGHP, (c) Y2TmSbO7, and (d) GdYBiNbO7.
Figure 17
Figure 17
(a) Transient photocurrent and (b) EIS plots of YGHP, Y2TmSbO7, and GdYBiNbO7.
Figure 18
Figure 18
UPS spectra of (a) Y2TmSbO7 and (b) GdYBiNbO7 (the intersections of the black dash lines indicated by the black arrows indicated the onset (Ei) and cutoff (Ecutoff) binding energy).
Figure 19
Figure 19
Plausible photodegradation mechanism of AC with YGHP as photocatalyst under VLTE: (a) conventional type II and (b) direct Z-scheme.
Figure 20
Figure 20
Feasible photodegradation pathway scheme for AC under VLTE with YGHP as catalyst.
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