Systematic assessment of emerging contaminants elimination using an S-scheme Mn0.5Cd0.5S/In2S3 photocatalyst: Degradation pathways, toxicity evaluation and mechanistic analysis

doi:10.1016/S1872-2067(25)64723-1

Abstract

Abstract:

Emerging contaminants in water sources present serious environmental and health risks, creating an urgent need for efficient and reliable treatment strategies. Photocatalytic advanced oxidation processes (AOPs) provide rapid reaction rates and strong oxidation capabilities, however, comprehensive evaluations of wastewater treatment, including degradation pathways, toxicity assessments and mechanistic insights, remain underexplored in the literature. This study presents novel S-scheme Mn_0.5Cd_0.5S/In₂S₃ (MCS/IS) photocatalysts for efficient degradation of antibiotic pollutants, with a particular focus on tetracycline hydrochloride (TCH). The optimized MCS/IS photocatalyst demonstrates exceptional degradation efficiency and robust resistance to inorganic anions. Additionally, a continuous-flow wastewater treatment system, using an MCS/IS membrane, demonstrates outstanding stability in TCH photodegradation. Utilizing response surface methodology and Fukui function analysis, the effects of various parameters on photocatalytic degradation rates, along with the associated pathways and intermediate products, have been thoroughly investigated. Toxicity assessments confirm the environmental safety of the treated effluents. Mechanistic studies show that the S-scheme heterojunction in the MCS/IS photocatalyst improves electron-hole separation, thereby enhancing photocatalytic performance. It is expected that this study will serve as a model for advancing the removal of emerging contaminants, further enhancing photocatalytic AOPs as sustainable water purification technologies.

Key words: S-scheme heterojunction, Mn_0.5Cd_0.5S/In₂S₃, Antibiotic degradation, Biotoxicity, Reaction mechanism

Ai Yating, A. C. Carabineiro Sónia, Xiong Xianqiang, Zhu Huayue, Wang Qi, Weng Bo, Yang Min-Quan. Systematic assessment of emerging contaminants elimination using an S-scheme Mn_0.5Cd_0.5S/In₂S₃ photocatalyst: Degradation pathways, toxicity evaluation and mechanistic analysis[J]. Chinese Journal of Catalysis, 2025, 75: 147-163.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64723-1

https://www.cjcatal.com/EN/Y2025/V75/I8/147

Figures/Tables 9

Fig. 1. (a) Illustration of the preparation process of MCS/IS. SEM images of IS (b), MCS (c), and 40%-MCS/IS (d). TEM (e), HRTEM (f), SAED (g) and elemental mapping images (h-l) of 40%-MCS/IS.

Fig. 2. XRD patterns (a), N2 adsorption-desorption isotherms (b), and pore size distribution curves (c) of IS, MCS and x%-MCS/IS. XPS spectra of IS, MCS and 40%-MCS/IS: survey (d), In 3d (e), S 2p (f), Mn 2p (g) and Cd 3d (h).

Fig. 3. (a) Adsorption kinetics of various samples for TCH. (b) Photocatalytic degradation efficiency of TCH using different MCS/IS samples. (c) Pseudo-first-order reaction kinetics for TCH degradation. (d) Photocatalytic performance of 40%-MCS/IS in the degradation of TCH in various water matrices (seawater, river water, lake water, tap water and deionized water). (e) Photocatalytic degradation of different antibiotics: TCH, OTCH, LEV and OFL by 40%-MCS/IS in deionized water. (f) Recycling experiments demonstrating the stability of 40%-MCS/IS for TCH degradation. (g) local volumetric rate of photon absorption (LVRPA) at different catalyst concentrations. (h) Total radiation power absorbed (TRPA) per unit surface area under visible light irradiation as a function of catalyst loading. (i) Correlation of degradation performance with optical thickness of the catalyst layer.

Fig. 4. 3D surface response maps and 2D contour maps of different factor interactions in the MCS/IS degradation model. (a,b) Effects of catalyst ratio and different water quality (DW - deionized water, TW - tap water, SW - sea water, with C fixed as TCH). (c,d) Effects of catalyst ratio and different pollutants (B fixed as DW). (e,f) Effects of different water quality and different pollutants (A fixed as 40%).

Fig. 5. (a) Schematic diagram of the continuous flow experimental equipment. (b) Photograph of the experimental setup. (c) Degradation performance of TCH in IS/PVDF, MCS/PVDF and 40%-MCS/IS/PVDF systems (PVDF - polyvinylidene fluoride).

Fig. 6. Potential degradation pathways and intermediate products of TCH.

Fig. 7. Developmental toxicity (a), mutagenicity factor (b) and Daphnia magna test results (c) for TCH and its intermediates. (d,e) Photographs of E. coli colonies formed on LB-agar plates with and without the addition of the 40%-MCS/IS heterojunction leaching solution. (f-h) Photographs of E. coli colonies formed on LB-agar plates with the addition of TCH solutions treated in the presence of 40%-MCS/IS heterojunction under visible light at different time intervals (0, 60 and 120 min). (i) Mean length and growth of mung bean seeds before and after photocatalytic degradation in deionized water and solution.

Fig. 8. (a) M-S plots of IS and MCS. (b,c) Band structure of the prepared samples (the electrode potential is measured in Volts, V, with the normal hydrogen electrode, NHE, as the reference). EPR spectra of DMPO-?O2? (adduct formed between 5,5-dimethyl-1-pyrroline N-oxide and the superoxide anion radical) (d), DMPO-?OH (adduct formed between DMPO and the hydroxyl radical) (e) and TEMPO-h+ (adduct formed between 2,2,6,6-tetramethylpiperidine-1-oxyl and a hydrogen atom) (f). (g,h) Work functions of MCS and IS. (i) 3D averaged charge for the MCS/IS composite.

Fig. 9. High-resolution XPS spectra of the 40%-MCS/IS composite with and without light irradiation: In 3d (a) and Mn 2p (b). AFM images (c1,d1), KPFM potential images(c2, c3, d2, d3) and corresponding contact potential difference curves (c4,d4) along the line in the dark and under illumination for IS (c1-c4) and 40%-MCS/IS (d1-d4), respectively. (e) Time-resolved PL decay spectra of IS and 40%-MCS/IS. Surface photovoltage spectra of the photocatalysts (f) and electrochemical impedance diagrams (g). (h) Schematic representation of the charge transfer mechanism.

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Systematic assessment of emerging contaminants elimination using an S-scheme Mn_0.5Cd_0.5S/In₂S₃ photocatalyst: Degradation pathways, toxicity evaluation and mechanistic analysis

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