Next Article in Journal
Effect of Oyster Mushroom Addition on Improving the Sensory Properties, Nutritional Value and Increasing the Antioxidant Potential of Carp Meat Burgers
Next Article in Special Issue
Transient Absorption Spectroscopic Investigation of the Photocyclization–Deprotection Reaction of 3′,5′-Dimethoxybenzoin Fluoride
Previous Article in Journal
Synthesis and Characterization of New Spirooxindoles Including Triazole and Benzimidazole Pharmacophores via [3+2] Cycloaddition Reaction: An MEDT Study of the Mechanism and Selectivity
Previous Article in Special Issue
Strategies for Improving Selectivity and Sensitivity of Schiff Base Fluorescent Chemosensors for Toxic and Heavy Metals
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 28
Issue 19
10.3390/molecules28196977
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Communication

The Use of Iron-Doped Anatase TiO2 Nanofibers for Enhanced Photocatalytic Fenton-like Reaction to Degrade Tylosin

by
Xiao Wang
1,2,3,*,
Wei Lu
1,2,*,
Shangui Zhang
1,2,
Changqing Guo
1,2,
Kai Yang
1,2,
Yan Sun
1,2,
Yashi Shao
1,2,
Qiyuan Li
1,2,
Mingsheng Bu
1,2,
Lianfeng Wu
1,2,
Bo Wang
1,2 and
Dongjiang Yang
3
1
State Key Laboratory of Marine Coatings, Qingdao 266071, China
2
Marine Chemical Research Institute Co., Ltd., Qingdao 266071, China
3
School of Environmental Science and Engineering, Qingdao University, Qingdao 266071, China
*
Authors to whom correspondence should be addressed.
Molecules 2023, 28(19), 6977; https://doi.org/10.3390/molecules28196977
Submission received: 7 September 2023 / Revised: 1 October 2023 / Accepted: 4 October 2023 / Published: 8 October 2023
(This article belongs to the Special Issue Feature Papers in Photochemistry and Photocatalysis)
Browse Figures
Versions Notes

Abstract

:
The removal of antibiotics from wastewater to prevent their environmental accumulation is significant for human health and ecosystems. Herein, iron (Fe)-atom-doped anatase TiO2 nanofibers (Fe-TNs) were manufactured for the photocatalytic Fenton-like decomposition of tylosin (TYL) under LED illumination. Compared with the pristine TiO2 nanofibers (TNs), the optimized Fe-TNs exhibited improved visible-light-driven photocatalytic Fenton-like activity with a TYL degradation efficiency of 98.5% within 4 h. The effective TYL degradation could be attributed to the expanded optical light absorption and accelerated separation and migration of photogenerated electrons and holes after the introduction of Fe. The photogenerated electrons were highly conducive to the generation of active SO4•− radicals as they facilitated Fe(III)/Fe(II) cycles, and to oxidizing TYL. Moreover, the holes could be involved in TYL degradation. Thus, a significant enhancement in TYL degradation could be achieved. This research verifies the use of iron-doped anatase nanofibers as an effective method to synthesize novel photocatalytic Fenton-like catalysts through surface engineering for wastewater remediation.

Graphical Abstract

1. Introduction

Antibiotic accumulation in water environments could produce drug-resistant bacteria and resistance genes, posing great threats to ecosystems and human health [1,2]. Therefore, efficient and environmentally friendly measures are urgently needed to remove antibiotics before they are discharged into natural water environments. Traditional biochemical treatment has limitations in treating antibiotics in wastewater due to its inhibitory effect on microbial growth [3]. Through physical treatment methods such as adsorption, the membrane could concentrate and transfer pollutants, but they face the problem of further processing to completely eliminate contamination [4,5]. Fenton-like technology based on advanced oxidation processes (AOPs) has been demonstrated to be an efficient strategy to mineralize antibiotics by reacting with the produced reactive oxygen species [6,7,8,9,10]. Furthermore, the light-assisted photocatalytic Fenton-like reaction approach, combining the advantages of photocatalysis and Fenton-like reactions, shows great promise in the elimination of antibiotic pollutants in wastewater [11,12].
Heterogeneous Fenton-like photocatalysts play a decisive role in this oxidation process [13,14,15,16]. TiO2, possessing a band gap of about 3.0–3.2 eV, has been extensively investigated as a photocatalyst to degrade pollutants because of its bio-safety, low price, and chemical stability [17,18]. In particular, one-dimensional TiO2 nanofibers (TNs) have better photogenerated charge separation and transport performance than nanoparticles, leading to higher photocatalytic activity [19]. However, the critical problems, such as a limited light absorption edge, and massive charge carrier recombination and deactivation, need to be resolved to achieve high activity [20]. Thus, researchers have attempted to modify TiO2 with the purpose of inhibiting the recombination and deactivation of charge carriers or enhancing the response to visible light of TiO2 [21,22]. Among various types of modification methods, doping a transition metal into TiO2 is a good strategy. The stabilized M-O(OH) structure and the interaction between transition metal atoms and TiO2 could promote catalytic activity [23]. In addition, Fe is considered an environmentally friendly element in wastewater purification treatment. Fe atom-doped substrates could catalyze oxidizing agents such as H2O2 and peroxymonosulfate (PMS) to produce reactive oxygen species, which possess strong oxidation capabilities to mineralize contaminants [24,25,26,27,28,29]. Yin et al. [30] developed Fe-doped carbon-based catalysts for boosting Fenton-like reactions. Guo et al. [31] doped Fe atom-modified g-C3N4 and discovered that different kinds of pollutants could be degraded by photocatalytic Fenton-like reactions driven by visible light. Thus, the coupling of Fe atoms and TiO2 is assumed to be an appropriate approach to obtain photocatalytic Fenton-like catalysts with high efficiency to degrade antibiotic pollutants by adjusting the visible-light absorption range and photoinduced charge transfer.
Herein, Fe atom-anchored anatase TiO2 nanofibers (Fe-TNs) were prepared for photocatalytic Fenton-like antibiotic tylosin (TYL) degradation driven by white LED illumination. Compared with the pristine TiO2, Fe-TNs obviously displayed enhanced TYL degradation performance. TYL could be degraded by 98.5% within 4 h for optimal Fe-TN catalysis. The confined Fe atom on TiO2 could extend the visible-light absorption region and increase the charge transport efficiency, guaranteeing that more photoinduced electrons would be involved in the Fe(III)/Fe(II) cycle to facilitate PMS activation. And the formed active species could accelerate TYL degradation. Moreover, the photoinduced holes could participate in TYL degradation.

2. Results and Discussion

2.1. Structural and Morphological Characterization

X-ray diffraction (XRD) patterns and Raman spectra were used to examine the crystalline forms of TNs and Fe-TN catalysts prepared with varying iron loading amounts. According to the XRD results shown in Figure 1A, the TNs and Fe-TN catalysts all displayed typical diffraction peaks at 25.28°, 37.80°, 48.05°, 53.89°, 62.30°, and 75.03°, which are indexed to the (101), (004), (200), (105), (204), and (215) crystal facets of anatase TiO2 [32]. Diffraction peaks of Fe-related compounds were not found, suggesting that the crystalline form of TNs remains unchanged after Fe modification. Furthermore, the TNs and all Fe-TN samples revealed the same Raman spectra (Figure 1B). The Fe-TN samples had similar Raman spectra to the TNs, with bands centered at 141 cm−1, 394 cm−1, 514 cm−1, and 636 cm−1 corresponding to anatase TiO2 Raman vibration modes.
The morphology and the elemental distribution of the produced TNs and Fe-TN catalysts were characterized via SEM and TEM coupled with energy-dispersive X-ray spectroscopy (EDX). Apparently, the TNs and all the Fe-TN samples appeared as a one-dimensional fibrous structures, as shown in the SEM (Figure 2A–C) and TEM (Figure 2D) images. The modification of TiO2 though Fe doping did not alter the one-dimensional fibrous structure. And the aggregation of crystalline-phase substances and Fe-related nanoparticles was not detected on the surface of the Fe-TNs, which was attributed to the dispersion of Fe at an atomic level. The lattice fringe with a spacing of 0.35 nm is due to the (101) plane of anatase TiO2 (Figure 2E). The N2 adsorption–desorption experiments suggested that the SBET values of the TNs and Fe-TNs 5% were 26 and 18 m2/g. The introduction of Fe atoms slightly reduced the specific surface area (Figures S1 and S2). As shown in the HRTEM images (Figure 2F), the regular lattice fringe with a distance of 3.5 Å was attributed to the (101) crystal face of anatase TiO2. Moreover, Figure 2F and Figure S3 further confirmed that Fe-related nanoparticle aggregation was not detected on the surface of the Fe-TNs. The well-distributed elements of Ti, O, and Fe in the associated EDX elemental mapping images (Figure 2G–I) reveal the successful introduction of Fe on TNs.
The XPS full-scan spectrum (Figure 3A) of Fe-TNs 5% before and after the reaction shows the existence of Fe, Ti, O, and C elements in the Fe-TNs. The appearance of an Fe 2p signal in the Fe-TN sample proves the successful introduction of Fe into the TNs. The Ti 2p XPS spectrum (Figure 3B) consists of two major peaks at 458.4, 464.1 eV assigned to the binding energies of Ti 2p5/2 and Ti 2p3/2 of Ti4+, respectively. Both the surface adsorbed oxygen (Oads) and lattice oxygen (Olatt) are clearly observed at binding energies of 531.4 eV and 529.7 eV in the Fe-TNs (Figure 3C). The Fe 2p spectra (Figure 3D) are deconvoluted into peaks centered at 713.6 eV and 728.3 eV for Fe 2p3/2 and Fe 2p1/2 of Fe(III), and the peaks at 710.3 eV and 724.1 eV for Fe 2p3/2 and Fe 2p1/2 of Fe(II). The fitted results suggest that the valence states of both Fe(III) and Fe(II) existed in the Fe-TNs. The proportions of Fe(III) to Fe(II) in Fe-TNs 5% after the reactions are higher than that before the reactions, indicating that Fe(II) was transformed into Fe(III) in the PMS activation process. The Fe(III)/Fe(II) cycle could realize PMS activation to generate radicals to degrade pollutants.

2.2. Tylosin Degradation Performance via Photocatalytic Fenton-like Reactions

The photocatalytic Fenton-like degradation of TYL by Fe-TNs in the presence of PMS was studied with TYL as the objective pollutant. The influence of Fe modification with different loadings on the degradation performance of TYL was investigated and the results are shown in Figure 4A. It shows that the Fe-TNs with 5% loading had the best performance in TYL degradation. And the degradation performance of Fe-TNs with 5% Fe loading was similar to those with 6% Fe loading, indicating that the further increase in Fe loading had no effect on TYL removal. The influences of PMS concentration, catalyst dosage, and TYL concentration on TYL degradation performance in this photocatalytic Fenton-like reaction catalyzed by TNs and Fe-TNs were separately investigated. As displayed in Figure 4B, as the PMS dosage increases, the TYL removal rate increased due to the generation of more SO4•− species. Figure 4C shows that as the dosage of Fe-TNs increases, both the degradation efficiency and rate for TYL are significantly improved. As the TYL concentration increases, the degradation efficiency decreases (Figure 4D) because the photocatalyst’s limited active sites can be consumed by TYL by-products. Therefore, 0.5 g/L of Fe-TN catalysts and 1 mM PMS were chosen for the degradation of 20 mg/L TYL solution in the subsequent studies. Under these conditions, the optimized Fe-TNs 5% catalyst exhibits improved visible-light-driven photocatalytic Fenton-like activity with TYL degradation efficiency of 98.5% within 4 h, which is more advantageous than the other previous reported catalysts [13,14,20,33,34,35] (Table S1). Moreover, the TEM image (Figure S4) shows that there is no change in the morphology of Fe-TNs 5% after the reaction, indicating its structural stability.
The radical capture experiments were carried out to examine the primary reactive species involved in TYL degradation in this photocatalytic Fenton-like process catalyzed by Fe-TNs [36,37,38]. Methanol (MeOH) was utilized as an •OH and SO4•− scavenger, and potassium dichromate (K2Cr2O7) as an electronic trapping agent. Tert-butanol (TBA) could quench •OH, and p-benzoquinone (BQ) could capture •O2−, •OH, and •O2−. As illustrated in Figure 5A, SO4•−, electrons, and •OH contributed to the degradation of TYL and SO4•− and also play a significant role in this process. Furthermore, the electron paramagnetic resonance (EPR) spectra (Figure 5B) show that no radical signals appear under dark conditions. When PMS, catalysts, and LED light coexisted in the system, clearly, EPR signal peaks were presented, showing that radicals of SO4•− and •OH could be produced under the condition of visible-light radiation.
The light absorption properties of TNs and Fe-TNs 5% were surveyed by assessing their UV-Vis absorption spectra (Figure 6A). Compared with TNs, the Fe-TNs revealed obvious extended and enhanced visible light absorption, proving that they promoted visible light absorption capacity after the introduction of Fe atoms. Based on the Tauc plots shown in Figure S5, the optical band gap values of the TNs and Fe-TNs 5% are 3.36 and 3.31 eV, suggesting that Fe doping reduced the optical band gap of TiO2. Furthermore, the migration and recombination performance of photoinduced e− and h+ was measured via PL measurement. As shown in Figure 6B, the PL intensity of Fe-TNs was reduced obviously compared with that of TNs, demonstrating that the introduction of Fe sites in TNs was favorable for the generation and separation of photogenerated e− and h+, thus accelerating the Fe(III)/Fe(II) oxidation–reduction cycle in the Fenton-like reactions. According to the above results, the photo-assisted Fenton-like reaction mechanism for TYL degradation is illustrated in Figure 6C. The photogenerated e− from TiO2 migrated along the Ti–O–Fe bonds to the Fe sites. Then, the produced Fe(II) generated from the reduction of Fe(III) could easily react with PMS to generate SO4•− and Fe(III). The Fe(III) continued to receive photogenerated e− to complete the Fe(III)/Fe(II) oxidation–reduction cycle. Simultaneously, the photogenerated h+, possessing strong oxidation, would also react with TYL directly or oxidize H2O to produce •OH to degrade TYL. In conclusion, SO4•− •OH, h+, and e− are active species involved in TYL degradation. By splitting the C–O, C–N, and C–C bonds in the molecular structure of TYL, CO2 and H2O were generated to realize the final mineralization and achieve degradation (Figures S6 and S7).

3. Materials and Methods

3.1. Synthesis of Fe-TNs

The used chemicals of analytical grade were commercially purchased and directly applied without further purification. First, the precursor H2Ti3O7 nanofibers were obtained via hydrothermal treatment of the mixture solution of anatase TiO2 powder and NaOH, and subsequently, the H+ ion-exchange process. Detailed preparation information for H2Ti3O7 nanofibers is shown in the Supplementary Materials. Subsequently, 1.0 g H2Ti3O7 and a certain amount of FeCl2∙4H2O (0.2~0.5 g) were put into 200 mL of distilled water. The mixture was exposed to agitation for 2 h, collected via centrifugation, and washed with deionized water three times. After drying, the materials were sealed in a quartz ampoule and heated in a tube furnace at 500 °C for 4 h. The TNs doped with Fe atoms (Fe-TNs) at different ratios were donated as Fe-TNs 2%, Fe-TNs 3%, Fe-TNs 4%, Fe-TNs 5%, and Fe-TNs 6%.

3.2. Structural Characterization

XRD (DX2700) was used to survey the composition and the crystalline phase of TNs and Fe-TNs. The surface chemical composition, valence state and chemical bond of Fe-TNs were characterized via X-ray Photoelectron Spectroscopy (XPS, Escalab 250, Thermo Fisher Scientific, Waltham, MA, USA). The morphology and element compositions were surveyed using scanning transmission electron microscopy (STEM, JSM-7001F, Tokyo, Japan). Raman spectra analysis was performed using Thermo Scientific DXR2 equipment at an excitation wavelength of 532 nm. The kinds of radicals were recorded via electron paramagnetic resonance spectroscopy. N2 adsorption–desorption experiments were performed using a specific surface area analyzer (BSD-PS2). The optical properties were obtained using a UV-Vis-NIR spectrophotometer (Agilent Cary 5000, Santa Clara, CA, USA). The photoluminescence (PL) spectra were tested using a fluorescence spectrophotometer (FLS9800).

3.3. Photocatalytic Fenton-like Degradation for TYL

The catalytic performance of TNs and Fe-TN catalysts for TYL degradation was evaluated in a photocatalytic Fenton-like system. Specifically, 50 mg of materials were weighed and added into 100 mL of TYL solution with an initial concentration of 20 mg/L under dark conditions. Before catalytic reactions took place, the adsorption process proceeded for 1.5 h to reach adsorption equilibrium. Subsequently, 1 mM of PMS was added and the above mixtures were exposed to white LED (300 mW/cm2) illumination. The reaction equipment was outfitted with circulating cooling water to keep the solution at 20 °C. In the process of the degradation reaction, 2.0 mL of the samples were taken out at a predetermined time and filtered through a 0.22 μm filter membrane. The remaining TYL concentration in the filtrate was measured via high-performance liquid chromatography (HPLC, EClassical3100). The intermediates of NOR degradation were detected via liquid chromatography (Thermo U3000) and coupled mass spectromery (maXis, Q-TOF, Bruker, Billerica, MA, USA).

4. Conclusions

In summary, Fe atom-anchored anatase TiO2 nanofibers were fabricated through a hydrothermal process, proton exchange, and an annealing treatment process. The obtained Fe-TN catalyst displayed significantly enhanced TYL degradation performance compared with the pristine TiO2 nanofibers in the photocatalytic Fenton-like system. The optimized Fe-TNs-5% catalyst could reach 98.5% TYL degradation efficiency within 4 h. Overall, the introduction of Fe atom sites can extend the light response of TiO2 to the visible region and improve the separation of photoexcited electrons and holes. The electrons could transfer to Fe atom sites, realize the Fe(III)/Fe(II) oxidation–reduction cycle, and improve the generation of more SO4•− species to degrade TYL. Moreover, the photoinduced holes could be involved in oxidizing TYL, thus significantly enhancing TYL degradation performance efficiency. Therefore, this research proposed a practical strategy to design high-performance and environmentally friendly photocatalytic Fenton-like catalysts for eliminating antibiotic pollution in environmental water.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules28196977/s1, Figure S1. (A) N2 adsorption and desorption of Fe-TNs; (B) Pore size distribution of Fe-TNs. Figure S2. (A) N2 adsorption and desorption of TNs; (B) Pore size distribution of TNs. Figure S3. TEM images of Fe-TNs. Figure S4. TEM images of Fe-TNs 5% after reactions. Figure S5. Tauc plots for TNs and Fe-TNs 5%. Figure S6. LCMS results of TYL in the reactions (0 and 20 min). Figure S7. Degradation pathway of TYL. Table S1. Comparison of several catalysts for degradation of TYL.

Author Contributions

X.W.: Data curation, Investigation, Writing—original draft; W.L.: Formal analysis, Investigation, Supervision; S.Z.: Methodology, Resources; C.G.: Formal analysis, Resources; K.Y.: Investigation, Methodology; Y.S. (Yan Sun): Validation, Visualization; Y.S. (Yashi Shao): Methodology, Validation; Q.L.: Resources, Software; M.B.: Methodology, Software; L.W.: Formal analysis, Visualization; B.W.: Methodology, Investigation; D.Y.: Project administration, Supervision, Writing—review & editing. This manuscript was written with contributions from all authors. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

All data included in this study are available upon request by contact with the corresponding author.

Acknowledgments

We thank Yu Hu from Zhongkexin Engineering Consulting (Beijng, China) Co., Ltd., for analyzing the degradation data, Jie Xu from the China Ship Development and Design Center (Wuhan, China) for the analysis of the catalyst properties, and Junyue Sheng from No. 58 Middle School (Shandong Province, Qingdao, China) for assisting with the degradation experiments.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Bao, C.; Wang, H.; Wang, C.; Zhang, X.; Zhao, X.; Dong, C.-L.; Huang, Y.-C.; Chen, S.; Guo, P.; She, X.; et al. Cooperation of oxygen vacancy and FeIII/FeII sites in H2-reduced Fe-MIL-101 for enhanced Fenton-like degradation of organic pollutants. J. Hazard. Mater. 2023, 441, 129922. [Google Scholar]
  2. Wang, C.; Wang, X.; Wang, H.; Zhang, L.; Wang, Y.; Dong, C.-L.; Huang, Y.-C.; Guo, P.; Cai, R.; Haigh, S.J.; et al. Low-coordinated Co-N3 sites induce peroxymonosulfate activation for norfloxacin degradation via high-valent cobalt-oxo species and electron transfer. J. Hazard. Mater. 2023, 455, 131622. [Google Scholar] [PubMed]
  3. Pang, S.; Zhou, C.; Sun, Y.; Zhang, K.; Ye, W.; Zhao, X.; Cai, L.; Hui, B. Natural wood-derived charcoal embedded with bimetallic iron/cobalt sites to promote ciprofloxacin degradation. J. Clean. Prod. 2023, 414, 137569. [Google Scholar]
  4. Hou, X.; Huang, X.; Ai, Z.; Zhao, J.; Zhang, L. Ascorbic acid/Fe@Fe2O3: A highly efficient combined Fenton reagent to remove organic contaminants. J. Hazard. Mater. 2016, 310, 170–178. [Google Scholar] [PubMed]
  5. Vorontsov, A.V. Advancing Fenton and photo-Fenton water treatment through the catalyst design. J. Hazard. Mater. 2019, 372, 103–112. [Google Scholar]
  6. Liu, X.; Zhou, Y.; Zhang, J.; Luo, L.; Yang, Y.; Huang, H.; Peng, H.; Tang, L.; Mu, Y. Insight into electro-Fenton and photo-Fenton for the degradation of antibiotics: Mechanism study and research gaps. Chem. Eng. J. 2018, 347, 379–397. [Google Scholar]
  7. Weng, X.; Owens, G.; Chen, Z. Synergetic adsorption and Fenton-like oxidation for simultaneous removal of ofloxacin and enrofloxacin using green synthesized Fe NPs. Chem. Eng. J. 2020, 382, 122871. [Google Scholar]
  8. Dong, H.; Zou, Y.; Zhang, K.; Sun, Y.; Hui, B.; Yang, D.; Cai, L.; Li, J. Biomimetic design of wood carbon-based heterogeneous catalysts for enhanced organic pollutants degradation. Chem. Eng. J. 2023, 451, 138568. [Google Scholar]
  9. Cai, H.; Li, X.; Ma, D.; Feng, Q.; Wang, D.; Liu, Z.; Wei, X.; Chen, K.; Lin, H.; Qin, S.; et al. Stable Fe3O4 submicrospheres with SiO2 coating for heterogeneous Fenton-like reaction at alkaline condition. Sci. Total Environ. 2021, 764, 144200. [Google Scholar]
  10. Zhang, X.; Liu, Y.; Zhai, Y.; Yu, Y.; Guo, Y.; Hao, S. An optimization strategy for photo-Fenton-like catalysts: Based on crystal plane engineering of BiVO4 and electron transfer properties of 0D CQDs. Environ. Res. 2023, 222, 115347. [Google Scholar]
  11. Zhang, M.-H.; Dong, H.; Zhao, L.; Wang, D.-X.; Meng, D. A review on Fenton process for organic wastewater treatment based on optimization perspective. Sci. Total Environ. 2019, 670, 110–121. [Google Scholar] [PubMed]
  12. Brillas, E.; Garcia-Segura, S. Benchmarking recent advances and innovative technology approaches of Fenton, photo-Fenton, electro-Fenton, and related processes: A review on the relevance of phenol as model molecule. Sep. Purif. Technol. 2020, 237, 116337. [Google Scholar]
  13. Xu, Y.; Zhang, Y.; Wang, X.; Wang, Z.; Huang, L.; Wu, H.; Ren, J.; Gu, C.; Chen, Z. Enhanced photodegradation of tylosin in the presence of natural montmorillonite: Synergistic effects of adsorption and surface hydroxyl radicals. Sci. Total Environ. 2023, 855, 158750. [Google Scholar]
  14. Zhang, Q.; Li, Y.; Ma, W.; Bai, X.; Ru, X.; Zhang, L.; Zhong, S.; Shu, X. Three-dimensional recyclable FeS2/reduced graphene oxide aerogel with high porosity reticulated structure for efficient removal of tylosin tartrate. Sep. Purif. Technol. 2023, 324, 124463. [Google Scholar]
  15. Lee, S.; Bayarkhuu, B.; Han, Y.; Kim, H.-W.; Jeong, S.; Boo, C.; Byun, J. Multifunctional photo-Fenton-active membrane for solar-driven water purification. J. Membr. Sci. 2022, 660, 120832. [Google Scholar]
  16. Dong, S.; Chen, X.; Su, L.; Wen, Y.; Wang, Y.; Yang, Q.; Yi, L.; Xu, W.; Yang, Q.; He, P.; et al. Integration of atomically dispersed Cu-N4 sites with C3N4 for enhanced photo-Fenton degradation over a nonradical mechanism. ACS EST Eng. 2023, 3, 150–164. [Google Scholar]
  17. Wang, A.; Zheng, Z.; Wang, H.; Chen, Y.; Luo, C.; Liang, D.; Hu, B.; Qiu, R.; Yan, K. 3D hierarchical H2-reduced Mn-doped CeO2 microflowers assembled from nanotubes as a high-performance Fenton-like photocatalyst for tetracycline antibiotics degradation. Appl. Catal. B Environ. 2020, 277, 119171. [Google Scholar]
  18. Yin, R.; Chen, Y.; He, S.; Li, W.; Zeng, L.; Guo, W.; Zhu, M. In situ photoreduction of structural Fe(III) in a metal–organic framework for peroxydisulfate activation and efficient removal of antibiotics in real wastewater. J. Hazard. Mater. 2020, 388, 121996. [Google Scholar]
  19. Zhang, L.; Zhang, Q.; Xie, H.; Guo, J.; Lyu, H.; Li, Y.; Sun, Z.; Wang, H.; Guo, Z. Electrospun titania nanofibers segregated by graphene oxide for improved visible light photocatalysis. Appl. Catal. B Environ. 2017, 201, 470–478. [Google Scholar]
  20. Zhao, P.; Yang, Y.; Pei, Y.; Luo, X. TEMPO-oxidized cellulose beads embedded with Au-doped TiO2 nanoparticles for photocatalytic degradation of Tylosin. Cellulose 2023, 30, 1133–1147. [Google Scholar]
  21. Li, K.; Zhang, S.; Li, Y.; Fan, J.; Lv, K. MXenes as noble-metal-alternative co-catalysts in photocatalysis. Chin. J. Catal. 2021, 42, 3–14. [Google Scholar]
  22. Liu, C.; Feng, Y.; Han, Z.; Sun, Y.; Wang, X.; Zhang, Q.; Zou, Z. Z-scheme N-doped K4Nb6O17/g-C3N4 heterojunction with superior visi-ble-light-driven photocatalytic activity for organic pollutant removal and hydrogen production. Chin. J. Catal. 2021, 42, 164–174. [Google Scholar]
  23. Lang, R.; Du, X.; Huang, Y.; Jiang, X.; Zhang, Q.; Guo, Y.; Liu, K.; Qiao, B.; Wang, A.; Zhang, T. Single-atom catalysts based on the metal-oxide interaction. Chem. Rev. 2020, 120, 11986–12043. [Google Scholar]
  24. Cheng, C.; Ren, W.; Miao, F.; Chen, X.; Chen, X.; Zhang, H. Generation of FeIV=O and its contribution to Fenton-like reactionson a single-atom iron NC catalyst. Angew. Chem. Int. Ed. 2023, 62, e2022185. [Google Scholar]
  25. Zhang, L.-S.; Jiang, X.-H.; Zhong, Z.-A.; Tian, L.; Sun, Q.; Cui, Y.-T.; Lu, X.; Zou, J.-P.; Luo, S.-L. Carbon nitride supported high-loading Fe single-atom catalyst for activation of peroxymonosulfate to generate 1O2 with 100% selectivity. Angew. Chem. Int. Ed. 2021, 60, 21751–21755. [Google Scholar]
  26. Li, Y.; Chen, J.; Ji, Y.; Zhao, Z.; Cui, W.; Sang, X.; Cheng, Y.; Yang, B.; Li, Z.; Zhang, Q.; et al. Single-atom iron catalyst with biomimetic active center to accelerate proton spillover for medical-level elec-trosynthesis of H2O2 disinfectant. Angew. Chem. Int. Ed. 2023, 62, e202306491. [Google Scholar]
  27. Xu, X.; Zhan, F.; Pan, J.; Zhou, L.; Su, L.; Cen, W.; Li, W.; Tian, C. Engineering single-atom Fe-Pyridine N4 sites to boost peroxymonosulfate activation for antibiotic degradation in a wide pH range. Chemosphere 2022, 294, 133735. [Google Scholar]
  28. Song, W.; Xiao, X.; Wang, G.; Dong, X.; Zhang, X. Highly efficient peroxymonosulfate activation on Fe-N-C catalyst via the collaboration of low-coordinated Fe-N structure and Fe nanoparticles for enhanced organic pollutant degradation. J. Hazard. Mater. 2023, 455, 131596. [Google Scholar]
  29. Wang, P.; Liu, X.; Qiu, W.; Wang, F.; Jiang, H.; Chen, M.; Zhang, W.; Ma, J. Catalytic degradation of micropollutant by peroxymonosulfate activation through Fe(III)/Fe(II) cycle confined in the nanoscale interlayer of Fe(III)-saturated montmorillonite. Water Res. 2020, 182, 116030. [Google Scholar]
  30. Yin, K.; Peng, L.; Chen, D.; Liu, S.; Zhang, Y.; Gao, B.; Fu, K.; Shang, Y.; Xu, X. High-loading of well dispersed single-atom catalysts derived from Fe-rich marine algae for boosting Fenton-like reaction: Role identification of iron center and catalytic mechanisms. Appl. Catal. B Environ. 2023, 336, 122951. [Google Scholar]
  31. An, S.F.; Zhang, G.H.; Wang, T.W.; Zhan, W.N.; Li, K.Y.; Song, C.S.; Miller, J.T.; Miao, S.; Wang, J.H.; Guo, X.W. High-density ultra-small clusters and single-atom Fe sites embedded in graphitic carbon nitride (g-C3N4) for highly efficient catalytic advanced oxidation processes. ACS Nano 2018, 12, 9441–9450. [Google Scholar]
  32. Liu, Y.; Wang, X.; Ye, W.; Butenko, D.S.; Lu, P.; Chen, Q.; Cai, R.; Sun, J.; Zhu, Y.; Yang, D. FeOx nanoclusters decorated TiO2 for boosting white LED driven photocatalytic Fenton-like norfloxacin degradation. Sep. Purif. Technol. 2022, 303, 122194. [Google Scholar]
  33. Ling, F.; Xiao, X.; Li, Y.; Li, W. A Zn/Co bimetal zeolitic imidazolate framework material as a catalyst to activate persulfates to degrade tylosin in aqueous solutions. New J. Chem. 2022, 46, 18917–18925. [Google Scholar] [CrossRef]
  34. Zhang, G.; Huang, G.; Yang, C.; Chen, S.; Xu, Y.; Zhang, S.; Lu, P.; Sun, J.; Zhu, Y.; Yang, D. Efficient photoelectrocatalytic degradation of tylosin on TiO2 nanotube arrays with tunable phosphorus dopants. J. Environ. Chem. Eng. 2021, 9, 104742. [Google Scholar]
  35. Tizhoosh, L.Y.; Khataee, A.; Hassandoost, R.; Soltani, R.D.C.; Doustkhah, E. Ultrasound-engineered synthesis of WS2@CeO2 heterostructure for sonocatalytic degradation of tylosin. Ultrason. Sonochem. 2020, 67, 105114. [Google Scholar]
  36. Tong, Y.-H.; Wu, Y.-Z.; Xu, Z.-L.; Luo, L.-H.; Xu, S.-J. Photocatalytic self-cleaning EVAL membrane by incorporating bio-inspired functionalized MIL-101(Fe) for dye/salt separation. Chem. Eng. J. 2022, 444, 136507. [Google Scholar]
  37. Wang, X.; Ma, Y.; Jiang, J.; Li, M.; Li, T.; Li, C.; Dong, S. Cl-based functional group modification MIL-53(Fe) as efficient photocatalysts for degradation of tetracycline hydrochloride. J. Hazard. Mater. 2022, 434, 128864. [Google Scholar] [CrossRef]
  38. Jiang, Y.; Ran, J.; Mao, K.; Yang, X.; Zhong, L.; Yang, C.; Feng, X.; Zhang, H. Recent progress in Fenton/Fenton-like reactions for the removal of antibiotics in aqueous environments. Ecotoxicol. Environ. Saf. 2022, 236, 113464. [Google Scholar]
Molecules 28 06977 g001
Figure 1. XRD patterns (A) and Raman spectra (B) of TNs and Fe-TNs with different iron amounts.
Figure 1. XRD patterns (A) and Raman spectra (B) of TNs and Fe-TNs with different iron amounts.
Molecules 28 06977 g001
Molecules 28 06977 g002
Figure 2. SEM images of (A) TNs and (B,C) Fe-TNs 5%. TEM (D–F) and EDX elemental mapping images (G–I) of Fe-TNs 5%.
Figure 2. SEM images of (A) TNs and (B,C) Fe-TNs 5%. TEM (D–F) and EDX elemental mapping images (G–I) of Fe-TNs 5%.
Molecules 28 06977 g002
Molecules 28 06977 g003
Figure 3. XPS spectra of Fe-TNs 5%. (A) Survey and high-resolution graphs of elements of (B) Ti 2p, (C) O 1s, and (D) Fe 2p before and after reactions.
Figure 3. XPS spectra of Fe-TNs 5%. (A) Survey and high-resolution graphs of elements of (B) Ti 2p, (C) O 1s, and (D) Fe 2p before and after reactions.
Molecules 28 06977 g003
Molecules 28 06977 g004
Figure 4. Photocatalytic Fenton-like degradation of TYL by TNs and Fe-TNs driven by visible light and the effect of the reaction parameter. (A) Fe loading amount, (B) PMS concentration, (C) catalyst dosage, (D) TYL concentration (conditions: 0.5 g/L catalyst, 20 mg/L TYL, 1 mM PMS unless otherwise stated).
Figure 4. Photocatalytic Fenton-like degradation of TYL by TNs and Fe-TNs driven by visible light and the effect of the reaction parameter. (A) Fe loading amount, (B) PMS concentration, (C) catalyst dosage, (D) TYL concentration (conditions: 0.5 g/L catalyst, 20 mg/L TYL, 1 mM PMS unless otherwise stated).
Molecules 28 06977 g004
Molecules 28 06977 g005
Figure 5. (A) Influence of different capture agents on TYL degradation (conditions: 0.5 g/L catalyst, 20 mg/L TYL, 1 mM PMS). (B) EPR spectra of DMPO adducts in this photocatalytic Fenton-like system catalyzed by Fe-TNs under the conditions of white LED light illumination and darkness.
Figure 5. (A) Influence of different capture agents on TYL degradation (conditions: 0.5 g/L catalyst, 20 mg/L TYL, 1 mM PMS). (B) EPR spectra of DMPO adducts in this photocatalytic Fenton-like system catalyzed by Fe-TNs under the conditions of white LED light illumination and darkness.
Molecules 28 06977 g005
Molecules 28 06977 g006
Figure 6. (A) UV–vis absorption, (B) PL spectra of TNs and Fe-TN catalysts, (C) proposed mechanism of TYL degradation over Fe-TNs.
Figure 6. (A) UV–vis absorption, (B) PL spectra of TNs and Fe-TN catalysts, (C) proposed mechanism of TYL degradation over Fe-TNs.
Molecules 28 06977 g006
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Wang, X.; Lu, W.; Zhang, S.; Guo, C.; Yang, K.; Sun, Y.; Shao, Y.; Li, Q.; Bu, M.; Wu, L.; et al. The Use of Iron-Doped Anatase TiO2 Nanofibers for Enhanced Photocatalytic Fenton-like Reaction to Degrade Tylosin. Molecules 2023, 28, 6977. https://doi.org/10.3390/molecules28196977

AMA Style

Wang X, Lu W, Zhang S, Guo C, Yang K, Sun Y, Shao Y, Li Q, Bu M, Wu L, et al. The Use of Iron-Doped Anatase TiO2 Nanofibers for Enhanced Photocatalytic Fenton-like Reaction to Degrade Tylosin. Molecules. 2023; 28(19):6977. https://doi.org/10.3390/molecules28196977

Chicago/Turabian Style

Wang, Xiao, Wei Lu, Shangui Zhang, Changqing Guo, Kai Yang, Yan Sun, Yashi Shao, Qiyuan Li, Mingsheng Bu, Lianfeng Wu, and et al. 2023. "The Use of Iron-Doped Anatase TiO2 Nanofibers for Enhanced Photocatalytic Fenton-like Reaction to Degrade Tylosin" Molecules 28, no. 19: 6977. https://doi.org/10.3390/molecules28196977

Article Metrics

Back to TopTop