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Article

Degradation of Tetracycline (TC) by ZrO2-3DG/PMS System: Revealing the Role of Defects in the Conditions of Light Irradiation and Sulfate Accumulation

by
Jixiang Duan
1,
Xin Wang
2,3,*,
Zhihong Ye
1 and
Fuming Chen
1,4,5,*
1
School of Physics, South China Normal University, Guangzhou 510006, China
2
Research Institute of Frontier Science, Southwest Jiao tong University, Chengdu 610031, China
3
College of Material Science and Engineering, Yantai Nanshan University, Yantai 265713, China
4
School of Electronics and Information Engineering, South China Normal University, Foshan 528225, China
5
Collaborative Innovation Center of Ecological Civilization, School of Chemistry and Chemical Engineering, Hainan University, Haikou 570228, China
*
Authors to whom correspondence should be addressed.
Catalysts 2024, 14(12), 846; https://doi.org/10.3390/catal14120846
Submission received: 16 October 2024 / Revised: 13 November 2024 / Accepted: 21 November 2024 / Published: 23 November 2024
(This article belongs to the Special Issue Catalysts for Water and Air Pollution Control: Present and Future, 2nd Edition)
Browse Figures
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Abstract

:
The application of advance oxidation processes (AOPs) based on the activation of peroxymonosulfate (PMS) is a great concern for wastewater treatment. Herein, ZrO2-3DG was constructed using a hydrothermal method for the degradation of tetracycline (TC) with PMS. The defective ZrO2-3DG materials were also prepared with plasma treatment. SEM and XPS results show that the ZrO2-3DG composite and the corresponding defective materials were successfully fabricated. The ZrO2 particles are distributed uniformly on the substrate material. Plasma can induce defects on the composite materials and create highly active sites. TC degradation results show that the ZrO2-3DG/PMS system can achieve a degradation efficiency of 92.9% for TC. The influences of defects on materials, light irradiation and sulfate accumulation were investigated. It has been found that defects can induce an inhibiting effect on the degradation process, which can be tuned by plasma time. The defective ZrO2-3DG/PMS system exhibits excellent resistance to the accumulation of sulfate, even showing enhanced degradation performances in specific conditions. The light irradiation has led to a higher degradation efficiency with the accumulation of sulfate compared with a dark environment. These findings give great guidance to the application of the ZrO2-3DG/PMS system for environmental protection.

Graphical Abstract

1. Introduction

The rapid development of society and modern industries give rise to the problem of emerging pollutants in the water [1]. These emerging pollutants usually have chemical stability and strong biotoxicity, which brings challenges to wastewater treatment processes using microorganisms [2]. Among these emerging pollutants, antibiotics widely used in healthcare and stockbreeding and have become an intractable issue in water treatment [3]. Due to their resistance to conventional wastewater treatment processes, many attempts have been made to aid the removal of antibiotics using advanced oxidation processes (AOPs) [4].
In recent years, the activation of peroxymonosulfate (PMS), which can produce powerful radicals such as sulfate radicals (•SO4−) and hydroxyl radicals (•OH) to degrade organic pollutants, has drawn increasing attention [5,6]. Compared with the conventional AOPs, PMS-AOPs can produce long-lasting radicals in different environmental conditions, leading to a high efficiency in the degradation process. The activating agent is proven to be the key in the PMS-AOPs [7]. Metal oxides (MO) are considered as efficient activating agents to induce the PMS-AOPs [8,9]. However, the application of the MO/PMS system still faces two important limitations: (1) the secondary pollution of metal ion leaching [10]; and (2) the difficulty in recovering the activating agents [11,12].
In order to overcome the problem of metal ion leaching, chemically stable metal oxidates are preferred in constructing the PMS activation system [13]. Differing from other metal oxidates, ZrO2 is not only an effective activator but also has strong stability in rigorous environments [14]. Considering the recovery of activating agents, metal oxidates are usually immobilized on porous carriers, forming metal oxidate composites. Graphene, as an excellent two-dimensional material, is often used for constructing catalytic composites or carriers [15]. In order to increase catalyst loading, graphene materials with a high specific surface area are preferred [16]. Three-dimensional graphene (3DG) has a porous structure with a high specific surface area, thereby showing great potential in the fabrication of composite materials [17]. Considering the above, the construction of the ZrO2-3DG composite may overcome the limitations of PMS-AOPs, thus becoming a promising activating agent [18]. Unfortunately, the investigation of using ZrO2-3DG for PMS-AOPs is still lacking, especially for practical applications [19].
As for the application of the ZrO2-3DG/PMS system, three important factors that should be considered but are often neglected in previous studies include the following: (1) Defects can form in materials [20] and affect the inactivation ability of the agent material [21]. (2) Light irradiation can impose an effect on the activation agent material, thus affecting the PMS activation system [22]. Additionally, the influence of defect-coupled light irradiation still lacks investigation [23]. (3) Sulfate ions can be accumulated in the process of PMS-AOPs [24]. In this case, the effect of the accumulation of sulfate ions on ongoing PMS-AOPs should be evaluated [25].
In this study, ZrO2-3DG composites are prepared with a hydrothermal method to construct a ZrO2-3DG/PMS system. Tetracycline (TC) is chosen as the typical antibiotic pollutant. The degradation properties of the ZrO2-3DG/PMS system are evaluated. Moreover, the defects are introduced to the ZrO2-3DG composites by plasma etching. The influences of defects, light irradiation and sulfate ions on the TC degradation process are investigated.

2. Results and Discussion

SEM images show the porous microstructures of the ZrO2-3DG material and the plasma-treated material (D-ZrO2-3DG). Figure 1a,b show the three-dimensional architecture of ZrO2-3DG with large porous channels [24]. Upon deeper observation, it can be found that spherical ZrO2 particles are distributed on the surface (Figure 1c) [26]. The EDS mapping images have confirmed the presence of the elements C, O and Zr, which are attributed to the substrate carbon material and ZrO2 particles, respectively (Figure 1d–f). In contrast, the plasma-treated sample exhibits much smaller pores and some debris on the surface, indicating a possible defective structure. On one hand, the defective structure can increase the specific surface area of the materials through the creation of small pore channels. On the other hand, the defective structure can induce vacancies with unique electronic structures on the materials, which are proven to be highly efficient in redox reactions. However, both the SEM and EDS mapping images suggest that the basic graphene framework and chemical composition of ZrO2-3DG have not been changed (Figure 1g–l) (for details see Table S1 of the Supporting Materials).
The chemical properties of the ZrO2-3DG and D-ZrO2-3DG structures were further investigated with XPS, as illustrated in Figure 2. The XPS analysis provides insights into the chemical states and binding energies of the elements present on the surface of these materials. Figure 2a exhibits the XPS survey spectra for both ZrO2-3DG and D-ZrO2-3DG, which reveal distinct peaks corresponding to the binding energies of Zr 3d, C 1s, and O 1s approximately at 181.7 eV, 284.6 eV, and 530.1 eV, respectively [27]. The high-resolution C 1s XPS spectrum is divided into the peaks at 284.7 eV and 287.3 eV, which are ascribed to the C-C/C=C (sp2 carbon) and HO-C=O (carbonyl/hydroxyl) functional groups, respectively [28]. This suggests the presence of both graphitic and oxidized carbon species for the substrate material of graphene (Figure 2b). The high-resolution XPS spectrum of O 1s for the ZrO2-3DG material displays two clear peaks at 529.7 eV and 533.8 eV, which are attributed to the lattice oxygen within the ZrO2 crystal structure and the C-O structure in the substrate, respectively. Plasma treatment can induce the split of the peak at 529.7 eV and creation of the peak at 532.7 eV, which is attributed to the O-vacancies in ZrO2 crystal. The O-vacancies can further react with H2O to form the Zr-OH structure (Figure 2c) [29]. This indicates that plasma treatment can introduce additional hydroxyl groups on the surface, which can not only enhance the hydrophilicity and adsorptive properties of the materials, but also reinforce the interaction with the graphene substrate. The high-resolution XPS spectrum of Zr 3d, as shown in Figure 2d, is deconvoluted into two peaks with binding energies of 181.9 eV and 184.2 eV, corresponding to the Zr 3d5/2 and Zr 3d3/2 electronic states of Zr (IV). These peaks are indicative of the presence of both tetragonal (t-ZrO2) and monoclinic (m-ZrO2) phases of zirconia [30]. In sum, the XPS results confirmed the successful synthesis of ZrO2-3DG and its plasma-treated derivative, providing evidence of the chemical composition and electronic states of the elements on the surface. Plasma treatment had induced changes in the surface chemistry, particularly in the oxygen and carbon species. It also indicates the potential electronic interactions between ZrO2 and 3DG, especially for chemical bonding at the interface between ZrO2 and 3DG. This interaction is crucial for the synergistic enhancement of the material of photocatalytic performance [31].
Subsequently, a series of experiments were meticulously designed to assess the activation and degradation efficiency of ZrO2-3DG. Initially, an experiment was conducted to degrade TC in the absence of light. As depicted in Figure 3, the degradation efficiency of ZrO2-3DG was evaluated using different PMS concentrations. The initial concentration of TC was standardized at 10 mg/L. The results, as illustrated in Figure 3a, demonstrate that the degradation efficiency of TC in the absence of an activator is markedly inferior to that achieved with the introduction of ZrO2-3DG (the pseudo-first-order kinetic fittings see Figure S2). Specifically, without an activator, the degradation efficiency of TC plateaued at a maximum of 46.4% within a 60 min timeframe. In contrast, the incorporation of ZrO2-3DG increased the degradation efficiency to 92.9% (Figure 3b). This finding suggests that the prepared activation material possesses superior efficacy in enhancing the activation process. The enhancement in degradation efficiency may be attributed to the effective generation of sulfate radicals via the ZrO2-3DG activator. The Zr(IV) sites and functional groups on the graphene substrate show cooperation in the activation of PMS into reactive radicals. In sum, the results indicate the pivotal role of ZrO2-3DG in activating PMS and expediting the degradation of TC. The superior performance of ZrO2-3DG, as an activator, highlights its potential as a robust candidate for environmental remediation applications, particularly in the context of wastewater treatment and the degradation of persistent organic pollutants.
Based on our knowledge of the ZrO2-3DG activator with PMS in TC degradation, we subsequently explored the influence of the defects of the activator on the degradation process with or without light irradiation. Figure 4 displays the TC degradation with the plasma-treated activator under dark conditions, varying the durations of plasma treatment and PMS concentrations (see Table S2). It is found that the introduction of defects may modulate the generation of sulfate radicals under dark conditions. This result indicates that the plasma-induced surface defects could potentially alter the capacity of the activator to generate reactive species, thereby affecting the degradation process. In general, the introduction of defects can impose an inhibiting effect on TC degradation. The inhibiting effect on TC degradation is shown to be duration-dependent on plasma treatment (the pseudo-first-order kinetic fittings see Figure S3). Specifically, the D-ZrO2-3DG (60 s) activator shows the most significant inhibiting effect, implying that the optimal plasma treatment duration may be critical in achieving the desired surface properties to balance the activation and degradation processes. Furthermore, the prolonging of the plasma treatment duration from 60 s to 300 s led to a progressive enhancement in TC degradation efficiency. This trend suggests that the increase in plasma time may mitigate the initial inhibiting effect by further modifying the surface chemistry, possibly through the saturation of surface states or the formation of additional reactive sites. In summary, the plasma treatment of the ZrO2-3DG activator introduces defects that significantly influence the degradation of TC. While the initial plasma treatment suppresses the degradation efficiency, an optimal treatment duration that maximizes the activator of performance can be identified. These findings indicate the importance of tailoring the surface properties of activation materials through plasma treatment. It could be a strategy to improve environmental remediation outcomes.
Moreover, the effect of defects on TC degradation under visible light irradiation has also been evaluated (see Table S3). Figure 5 presents the degradation of TC with non-defective ZrO2-3DG and plasma-treated ZrO2-3DG in different PMS environments coupled with visible light irradiation. It is found that the degradation efficiency of TC was obviously increased with the D-ZrO2-3DG/PMS system (the pseudo-first-order kinetic fittings see Figure S4). The degradation efficiency increased from 73.9% to 82.9% with the increase in PMS concentration. The composite has a high specific surface area with 3DG substrate, which can form the intermediate band on the composite, leading to the easier activation of ZrO2 under light irradiation. In addition, the hybrid structure is conducive in minimizing the recombination of photo-carriers, thus promoting the concentration of active species. Consequently, the photogenerated electrons (e−) and holes (h+) play a pivotal role in the generation of reactive oxygen species (ROS) within the reaction system. These ROS are the primary agents responsible for the photodegradation of TC. However, it is important to note that visible light, due to its lower energy compared to UV light, does not generate photoelectrons with energies as high as the latter. This limitation restricts the extent to which visible light can enhance TC degradation, as the energy of the photoelectrons is a critical factor in driving the photocatalytic process. The experiments under visible light conditions reaffirm the positive impact of defects on the photocatalytic activity of the ZrO2-3DG/PMS system. The plasma-treated ZrO2-3DG activator, with its increased surface area and altered electronic properties, is considered as a promising material for the degradation of TC under visible light. These findings pave the way for the further optimization of the photocatalytic system, potentially leading to more efficient and sustainable solutions for the treatment of organic pollutants in aquatic environments.
Furthermore, the TC degradation results under visible light conditions were analyzed using mathematical modeling to elucidate the degradation kinetics. Figure 6 presents the results of these simulations, which were employed to assess the influence of both the ZrO2-3DG and D-ZrO2-3DG/PMS systems through the pseudo-first-order kinetic behavior of TC degradation. It is found that the increase in the plasma treatment duration significantly enhances the potential degradation efficiency. This finding indicates that the plasma treatment duration is a critical parameter in optimizing the photocatalytic performance of the D-ZrO2-3DG/PMS system. The simulations reveal a marked enhancement in the degradation of TC with the cooperation of the activator in different PMS concentrations. This variation suggests the synergistic interaction between PMS and the plasma-treated ZrO2-3DG in the photocatalytic degradation process. The mathematical simulations corroborate the experimental results and emphasize the critical role of plasma treatment in modulating the surface properties of the activator. These simulations also highlight the importance of PMS concentration in the photocatalytic degradation process, providing valuable insights for the optimization of the D-ZrO2-3DG/PMS system for the applications in environmental remediation.
The concentration of sulfate ions was investigated for a possible influence on the degradation process. Figure 7 presents the effects of sulfate accumulation on the degradation efficiency of TC in the dark and the corresponding pseudo-first-order kinetic modeling (the apparent rate constant (kapp) see Figure S5). It can be seen that compared with the non-defective ZrO2-3DG, the defective ZrO2-3DG activators show advantages in the resistance to the accumulation of sulfate. Interestingly, for the D-ZrO2-3DG materials, the degradation efficiency for TC has been improved with the accumulation of sulfate, and the defective ZrO2-3DG activator with 60 s plasma treatment shows the best degradation efficiency of TC. Specifically, the degradation efficiency increased from 69.8%, in the absence of additional sulfate, to 82.9%, with an additional sulfate concentration of 50 mmol/L, representing an enhancement effect of 13.1%. As for the kapp values, the kapp of D-ZrO2-3DG increased to ~0.24, compared with that of ZrO2-3DG (~0.16). However, the sulfate accumulation also shows a marginal effect on the degradation rate enhancement. The degradation efficiency of TC decreased with a high concentration of sulfate ions.
Upon conclusion of the aforementioned experiments, which indicated a modest enhancement in the degradation efficiency under dark conditions through the effects of defects, coupled with the accumulation of sulfate, we extended our investigation to visible light conditions to evaluate the TC degradation performances. Figure 8 presents the impact of visible light conditions on the degradation of TC with the accumulation of sulfate (see Figure S6). The activation capacity of the D-ZrO2-3DG/PMS activator, particularly following a 60 s plasma treatment, was found to exhibit remarkable degradation performance in a succession of experiments. The results indicate that the degradation efficacy of the material with defects is indeed augmented compared with the ZrO2-3DG/PMS system under visible light irradiation. The negative effect of sulfate accumulation in the PMS activation process has been reversed with the defective structure of ZrO2-3DG and light irradiation. In the comparison of light and dark conditions, it is found that the TC degradation can achieve better performances with lower accumulation concentrations of sulfate under light irradiation, while the defective structure under dark conditions can induce better degradation performances for TC. Also, with the increase in the sulfate concentration, the degradation efficiency was decreased. The introduction of visible light conditions reveals a nuanced relationship between sulfate accumulation and the degradation efficiency of the D-ZrO2-3DG/PMS system. These insights are instrumental in guiding future research and applications aimed at maximizing the photocatalytic potential of such systems in environmental remediation processes.

3. Materials and Methods

3.1. Chemical Reagents

Zirconium hypochlorite was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. (Shanghai, China). GO was purchased from Nanjing Xianfeng Nanomaterials Technology Co., Ltd. (Nanjing, China). All chemical reagents were of analytical grade and used as is without further purification.

3.2. Preparation of ZrO2-3DG

Firstly, 0.1 g of graphene oxidate (GO) was added into 100 mL of deionized water and sonicated for 40 min to obtain a uniform mixture. 0.1 mmol zirconium chloride was added to the mixture and stirred at a constant speed for 1 h. At the end of the stirring, the obtained solution was placed into a Teflon lining. The hydrothermal reaction was carried out for 12 h, and the temperature was set to 120 °C. After the procedure, the samples were cooled overnight, washed with deionized water and ethanol. Then, the materials were freeze-dried for 48 h to finally obtain the ZrO2-3DG (see Figure S1 for the schematic).

3.3. Preparation of D-ZrO2-3DG

The defective ZrO2-3DG (D-ZrO2-3DG) materials were prepared by plasma etching. During the plasma treatment, the untreated activator samples were removed and tiled on a quartz boat prior to weighing. The quartz ship was placed in a capsule of an RF plasma device (TS-VPM02, Tonson Tech., Shenzhen, China). Each side of the mask dices was plasma activated in an O2 atmosphere with an airflow rate of 60 mL min−1 for 60, 180 and 300 s.

3.4. Characterization

The morphologies, microstructures and elemental distribution of the catalysts were determined by field emission scanning electron microscopy (SEM, ZEISS Gemini 500, ZEISS, Macquarie Park, Australia) and energy dispersive spectroscopy (EDS, Bruker Dual QUANTAX 200 with XFlash6, Bruker, Karlsruhe, Germany). The electronic state and valance position of the catalysts were detected by X-ray photoelectron spectroscopy (XPS, Thermo Scientific K-Alpha Nexsa, Thermo Fisher Scientific, Waltham, MA, USA).

3.5. The Degradation Experiments

The TC degradation experiments with the ZrO2-3DG/PMS system were performed under light (Xe lamp, 350 W) in a catalytic beaker with a water-cooled device. The light source in this study is a Xe lamp (350 W) with a UV cut-off filter. The activator material (10 mg) was added into a 100 mL solution with a TC concentration of 20 mg/L with stirring. Then, a certain amount of PMS was added to the above solution, and 1.5 mL of the solution was extracted from the beaker every 10 min. Subsequently, the extracted sample was filtered and centrifuged twice. The supernatant was collected to determine the TC concentration using a G1315D 12600 DAD detector (detection wavelength at 350 nm) on an HPLC system (Agilent 1200 infinity series, Agilent, Santa Clara, CA, USA). The TC removal rate was calculated using Equation (1).
Removal efficiency (%) = (C0 − Ct)/C0 × 100%
where C0 is the concentration of TC at the beginning, and Ct is the concentration of the TC solution at time t (min).

4. Conclusions

The ZrO2-3DG material was successfully fabricated by a hydrothermal process and the ZrO2-3DG/PMS system was used for TC degradation. It is found that the ZrO2-3DG/PMS system can achieve THE efficient degradation of TC. The introduction of defects can induce an inhibiting effect on the degradation. However, the inhibiting effect can be relieved by tunning the plasma time. Compared with the ZrO2-3DG/PMS system, the D-ZrO2-3DG/PMS system exhibits an excellent resistance to the accumulation of sulfate, which is an important property for practical applications. Moreover, the TC degradation efficiency can be enhanced with the D-ZrO2-3DG/PMS system in the conditions of sulfate accumulation. In contrast to dark environments, light irradiation can induce a higher TC degradation efficiency with the accumulation of sulfate.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal14120846/s1. Table S1. The elemental composition of ZrO2-3DG and defective ZrO2-3DG (plasma treated 60 s). Table S2. Comparison of degradation efficiency under dark conditions. Table S3. Comparison of degradation efficiency under light conditions. Table S4. Degradation of TC in additional SO42− accumulation under dark and light conditions. Figure S1. Schematic diagram of the preparation of materials. Figure S2. The pseudo-first-order kinetic fittings of TC degradation process with ZrO2-3DG/PMS system in dark environment. Figure S3. The pseudo-first-order kinetic fittings of TC degradation process with defective ZrO2-3DG/PMS system in dark environment under plasma-treated conditions (a) 0 s, (b) 60 s, (c) 180 s and (d) 300 s. Figure S4. The pseudo-first-order kinetic fittings of TC degradation process with defective ZrO2-3DG/PMS system under visible light irradiation with the PMS amount of (a) 0.02 mmol, (b) 0.2 mmol, (c) 1.0 mmol and (d) 3.0 mmol. Figure S5. The changes in the apparent rate constant (kapp) for the additional sulfate concentrations of (a) 10 mM, (b) 30 mM and (c) 50 mM in the dark environment. Figure S6. The changes in the apparent rate constant (kapp) for the additional sulfate concentrations of (a) 10 mM, (b) 30 mM and (c) 50 mM with light irradiation.

Author Contributions

Conceptualization, X.W.; methodology, J.D.; formal analysis, J.D.; investigation, J.D. and Z.Y.; writing—original draft preparation, J.D.; writing—review and editing, J.D. and F.C.; supervision, X.W. and F.C.; project administration, X.W.; funding acquisition, X.W. and F.C. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the National Natural Science Foundation of China (Grant No. 42177438, 51909165), Shandong Provincial Natural Science Foundation, China (ZR2024MB135), the Novel Interdisciplinary Cultivation Fund of Southwest Jiaotong University (2682023KJ026), the Start-up Research Funding of Southwest Jiaotong University (YH1100312372222), the Fundamental Research Funds for the Central Universities (2682023CX064), Guangdong Basic and Applied Basic Research Foundation (2023A1515140065, 2024A1515010924). F. Chen acknowledges the Pearl River Talent Program (2019QN01L951).

Data Availability Statement

The data presented in this study are available upon request from the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. SEM and EDS-mapping images for (a–f) ZrO2-3DG and (g–l) defective D-ZrO2-3DG (60 s).
Figure 1. SEM and EDS-mapping images for (a–f) ZrO2-3DG and (g–l) defective D-ZrO2-3DG (60 s).
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Figure 2. (a) XPS survey and high-resolution XPS of; (b) C 1s, (c) O 1s and (d) Zr 3d for pristine ZrO2-3DG and D-ZrO2-3DG (60 s).
Figure 2. (a) XPS survey and high-resolution XPS of; (b) C 1s, (c) O 1s and (d) Zr 3d for pristine ZrO2-3DG and D-ZrO2-3DG (60 s).
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Figure 3. Degradation of TC in dark environment with (a) PMS; (b) ZrO2-3DG/PMS system.
Figure 3. Degradation of TC in dark environment with (a) PMS; (b) ZrO2-3DG/PMS system.
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Figure 4. Degradation of TC with defective D-ZrO2-3DG/PMS system in dark environment under plasma-treated conditions (a) 60 s, (b) 180 s and (c) 300 s.
Figure 4. Degradation of TC with defective D-ZrO2-3DG/PMS system in dark environment under plasma-treated conditions (a) 60 s, (b) 180 s and (c) 300 s.
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Figure 5. Degradation of TC with non-defective and D-ZrO2-3DG/PMS system under visible light irradiation with PMS addition of (a) 0.02 mmol, (b) 0.2 mmol, (c) 1.0 mmol and (d) 3.0 mmol.
Figure 5. Degradation of TC with non-defective and D-ZrO2-3DG/PMS system under visible light irradiation with PMS addition of (a) 0.02 mmol, (b) 0.2 mmol, (c) 1.0 mmol and (d) 3.0 mmol.
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Figure 6. The changes in the apparent rate constant (kapp) of TC degradation with non-defective and D-ZrO2-3DG/PMS system under visible light irradiation, PMS of (a) 0.02 mmol; (b) 0.2 mmol; (c) 1.0 mmol; (d) 3.0 mmol.
Figure 6. The changes in the apparent rate constant (kapp) of TC degradation with non-defective and D-ZrO2-3DG/PMS system under visible light irradiation, PMS of (a) 0.02 mmol; (b) 0.2 mmol; (c) 1.0 mmol; (d) 3.0 mmol.
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Figure 7. Degradation of TC and the corresponding changes in the apparent rate constant (kapp) with non-defective and D-ZrO2-3DG/PMS system in the additional SO42− accumulation of (a,b) 10 mM, (c,d) 30 mM and (e,f) 50 mM in a dark environment.
Figure 7. Degradation of TC and the corresponding changes in the apparent rate constant (kapp) with non-defective and D-ZrO2-3DG/PMS system in the additional SO42− accumulation of (a,b) 10 mM, (c,d) 30 mM and (e,f) 50 mM in a dark environment.
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Figure 8. Degradation of TC with non-defective and defective ZrO2-3DG/PMS system in the additional SO42− accumulation of (a) 10 mM, (c) 30 mM and (e) 50 mM under visible light irradiation. (b,d,f) The changes in the apparent rate constant (kapp) for the above processes.
Figure 8. Degradation of TC with non-defective and defective ZrO2-3DG/PMS system in the additional SO42− accumulation of (a) 10 mM, (c) 30 mM and (e) 50 mM under visible light irradiation. (b,d,f) The changes in the apparent rate constant (kapp) for the above processes.
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MDPI and ACS Style

Duan, J.; Wang, X.; Ye, Z.; Chen, F. Degradation of Tetracycline (TC) by ZrO2-3DG/PMS System: Revealing the Role of Defects in the Conditions of Light Irradiation and Sulfate Accumulation. Catalysts 2024, 14, 846. https://doi.org/10.3390/catal14120846

AMA Style

Duan J, Wang X, Ye Z, Chen F. Degradation of Tetracycline (TC) by ZrO2-3DG/PMS System: Revealing the Role of Defects in the Conditions of Light Irradiation and Sulfate Accumulation. Catalysts. 2024; 14(12):846. https://doi.org/10.3390/catal14120846

Chicago/Turabian Style

Duan, Jixiang, Xin Wang, Zhihong Ye, and Fuming Chen. 2024. "Degradation of Tetracycline (TC) by ZrO2-3DG/PMS System: Revealing the Role of Defects in the Conditions of Light Irradiation and Sulfate Accumulation" Catalysts 14, no. 12: 846. https://doi.org/10.3390/catal14120846

APA Style

Duan, J., Wang, X., Ye, Z., & Chen, F. (2024). Degradation of Tetracycline (TC) by ZrO2-3DG/PMS System: Revealing the Role of Defects in the Conditions of Light Irradiation and Sulfate Accumulation. Catalysts, 14(12), 846. https://doi.org/10.3390/catal14120846

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