Efficient Atrazine Degradation through ZnFe2O4-Catalyzed Peroxymonosulphate Activation

doi:10.21203/rs.3.rs-4312875/v1

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Efficient Atrazine Degradation through ZnFe₂O₄-Catalyzed Peroxymonosulphate Activation

https://doi.org/10.21203/rs.3.rs-4312875/v1

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Atrazine (ATZ) is widely used as an herbicide in agricultural production. However, its extensive application results in contaminated residues that can adversely affect ecosystems because rainwater washes them into and contaminates water bodies. Therefore, there is a pressing need to remove ATZ from the aquatic environment. Using transition metals as catalysts for the persulfate degradation of organic pollutants has received much attention because of their strong ability to oxidize pollutants, including ATZs, and their selectivity for these pollutants. A novel technique for ATZ removal using a catalyst (ZnFe₂O₄) to activate peroxymonosulfate (PMS) was developed in this study . The ZnFe₂O₄ catalyst was prepared through co-precipitation, which involves the doping of zinc in iron-based materials. And this process accelerated the redox cycle, which energized the PMS and promoted the generation of free radicals. Electron paramagnetic resonance analysis revealed that ZnFe₂O₄ activates PMS and generates SO₄•^-, HO•, O₂•^-, and ¹O₂ to eliminate ATZ. In this study, a new approach is proposed for the development of efficient heterogeneous catalysts capable of activating PMS and eliminating the ATZ. Moreover, The ATZ degradation pathway was proposed based on the products identified by UPLC-MS. The results highlighted the efficiency of the as-prepared ZnFe₂O₄ catalyst in ATZ removal and its excellent performance. Given its environmentally friendly and efficient performance, The ZnFe₂O₄ catalyst has significant potential implications for agricultural environmental remediation.

Earth and environmental sciences/Environmental sciences

Physical sciences/Nanoscience and technology

Peroxymonosulfate

Atrazine

ZnFe2O4

catalytic oxidation

free radicals

Modern agriculture is increasingly dependent on the application of pesticides and fertilizers to increase crop yields in order to meet the nutritional needs of a growing population(Rani et al., 2021). Atrazine (ATZ) has become one of the most commonly used triazine herbicides worldwide due to its high weed control efficiency and low cost. The chemical name of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), which is a synthetic selective triazine herbicide widely used in the cultivation of maize, sugarcane, cereals, oilseed rape and other crops to prevent and control annual grass weeds and broadleaf weeds, and inhibit the growth of certain perennial weeds (Giannini-Kurina et al., 2022). However, despite the economic benefits of ATZ, its prolonged use has increased environmental and health risks worldwide. The characteristics of ATZ, including its long half-life, high mobility, limited volatility, and resistance to abiotic hydrolysis and aerobic degradation, enhance its ability to accumulate in soil, contaminate ground and surface water, and persist in the ecosystem.

As it can be transferred through the food chain, transmission to other animals and humans occurs after ingesting contaminated water and crops, posing a threat to human health and the environment (Barchanska et al., 2012). Therefore, exploring methods to remedy the aquatic environments contaminated by ATZ is essential.

In recent years, organic pollutants in water have been removed using various methods such as adsorption, biodegradation (Yang et al., 2021), photodegradation (Dang et al., 2020; Ji et al., 2020), and advanced oxidation processes (AOPs) (Wacławek et al., 2017). Among these, the AOPs, which allow the conversion of large organic molecules to small organic molecules and even H₂O and CO₂, are an effective method for removing organic pollutants (Hao et al., 2016; Zhu et al., 2020).

The SO₄•⁻ radical has higher oxidation potentials, longer lifetimes, and wider pH ranges than HO•, which is usually produced by Fenton reactions (Chen et al., 2020). Typically, persulfates such as peroxymonosulfate (PMS) or peroxydisulfate (PDS) are used to produce SO₄•⁻ (Chen et al., 2019; Jia et al., 2021; Zhang et al., 2021). PMS has an asymmetric structure, which provides higher oxidizing performance compared to PDS with a solid-state symmetric framework (Wang et al., 2022). Therefore, PMS is widely used in radical-sulfate-based AOPs with metal-containing catalysts (Co, Fe, Cu, and Mn) (Abdul Nasir Khan et al., 2019; Asif et al., 2022; Chen et al., 2022; Li et al., 2020; Sun et al., 2022; Zhao et al., 2021b). However, there is still a great need for efficient, reliable and recoverable heterogeneous catalysts for practical applications.

Iron-based catalysts are now commonly utilized to trigger PMS due to their high efficiency, safety, nont-oxicity, and cost-effectiveness among all the transition-metal-based catalysts. And iron-based catalysts, such as magnetic Fe₃O₄, α-Fe₂O₃, γ-Fe₂O₃, and δ-FeOOH could activate PMS to degrade organic pollutants (Zhao et al., 2021a). Although Fe²⁺ and Fe⁰ have low valences and are quickly oxidized, their PMS activation efficiency is low because of the slow redox cycle of Fe²⁺/Fe³⁺ (Liu et al., 2018). And Fe-based bimetallic oxide catalysts have been widely investigated in recent years (Miao et al., 2018; Li et al.,2020; Xu et al., 2022)., and proposed as alternatives because of their excellent activity and stability and ability to mitigate the abovementioned adverse effects (Zhao et al,2023)

In this study, a co-precipitation reaction was conducted to prepare ZnFe₂O₄ and its performance in ATZ degradation was first analyzed. The objectives were: (1) to investigate the physicochemical properties of the prepared catalysts and to evaluate their catalytic efficiency in the PMS system; (2) to study and characterize the effect of external environmental conditions on ATZ degradation; and (3) to examine the mechanism of the reactive oxygen species (ROS) generated in the ZnFe₂O₄/PMS system and elucidate the ATZ degradation mechanism. This study could offer a new perspective for investigating improved, cost-effective, and eco-friendly catalysts.

2.1. Materials

Peroxymonosulfate (KHSO₅·0.5KHSO₄·0.5K₂SO₄), iron hexahydrate chloride (FeCl₃·6H₂O), zinc chloride (ZnCl₂), ATZ, sodium carbonate (Na₂CO₃), sodium dihydrogen phosphate (NaH₂PO₄), Hydrochloric acid (HCl), ethanol (C₂H₅OH ) and sodium hydroxide (NaOH) were all used in the experiment, which were of analytical grade or better without further purification.

2.2. Synthesis of ZnFe₂O₄

ZnFe₂O₄ was synthesized through co-precipitation. FeCl₃·6H₂O and ZnCl₂ were dispersed in 50 mL of ultrapure water and ultrasonically dispersed for 30 min. The resulting mixture was then poured into a water bath at 50 °C and magnetically stirred. NaOH was added to the solution until the pH reached 9, and the suspension was stirred continuously and kept at 50 °C for 1 h. The obtained ZnFe₂O₄ composites were centrifuged, separated, and then washed with ethanol and ultrapure water to maintain pH 7. The obtained composites were dried at 60 °C in a drying oven for at least 24 h, pulverized, passed through an 80-mesh sieve, and finally calcined at 600 °C for 2 h under N₂ flow condition in tube furnace.

2.3. Characterization of the catalyst

X-ray diffraction (XRD) patterns of the ZnFe₂O₄ composites were recorded at a working voltage of 40 kV and current of 250 mA between 5° and 80°. The morphology and particle size distribution of the composites was obtained through scanning electron microscopy (SEM, TESCAN MIRA LMS, Brno, Czech Republic) coupled with energy-dispersive X-ray spectroscopy (EDS). Additionally, X-ray photoelectron (XP) spectroscopy (XPS) was performed to analyze the chemical valences of Zn and Fe in the ZnFe₂O₄ catalysts in order to explore their role in PMS activation; a Thermo Scientific K-Alpha photoelectron spectroscope was used.

2.4. Catalytic activity test

A total of 100 mL of 20 µmol/L ATZ solution was prepared, the ZnFe₂O₄ catalyst was added at 25°C, the initial pH was adjusted, and the conical flask was subsequently shaken (300 r/min) in a thermostatic oscillator for 30 min to reach adsorption–desorption equilibrium. After 30 min of shaking, 1 mL of the sample was taken, and the remaining sample was continued to be shaken with the addition of PMS; the 1 mL sample was taken at regular intervals (1, 5, 10, 15, 20, 25, and 30 min), filtered through a 0.22 µm membrane into a 2 mL of the injection vial. Subsequently, 100 µL of anhydrous ethanol was added to stop the reaction. The residual ATZ concentration in the solution was determined through ultra-performance liquid chromatography (UPLC). A liquid chromatography-tandem mass spectrometry (LC-MS/MS) system was utilized to identify the ATZ oxidation intermediates. Electron paramagnetic resonance (EPR) spectroscopy was conducted to identify the ROS. When the reaction was complete, the catalyst was collected, then washed with ethanol and ultrapure water, and recycled to determine its reusability.

3.1. Characterization

In the XRD patterns of the prepared catalysts (Fig. 1), the peaks matched well with those of cubic spinel ZnFe₂O₄ (JCPDS file No. 22-1012), confirming the presence of the ZnFe₂O₄ crystals. In Fig. 1, six distinct diffraction peaks were observed at 2θ = 18.19°, 29.92°, 35.26°, 42.84°, 45.45°, and 62.21°, which were attributed to the (111), (220), (311), (400), (511), and (440) planes of ZnFe₂O₄, suggesting that the ZnFe₂O₄ crystals exhibit excellent crystallinity and very high surface purity (Zhao et al., 2023).

Figure 2 shows the SEM image of the ZnFe₂O₄ catalyst at various magnifications. The results reveal that ZnFe₂O₄ nanoparticles were uniformly dispersed in hexagonal and spherical structures. The homogeneous characteristics and uniform distribution of the ZnFe₂O₄ particles might facilitate contact between the oxidant and catalyst, promoting PMS activation (Guo et al., 2021). Moreover, the presence of numerous pores on the ZnFe₂O₄ surface is beneficial for the adsorption of ATZ on the catalyst.

Figure 3 shows the peaks at 284.8, 530.8, 711.5, and 1021.6 eV that correspond to C1s, O1s, Fe2p, and Zn2p, respectively. These results indicate the high stability of the ZnFe₂O₄ catalyst. The relative elemental composition of the catalyst is summarized in Table 1. The C1s orbital is characterized by peaks at 286.3, 284.8, 288.9, and 287.2 eV, which can be attributed to C-O, C-C, O = C-O, and C = O, respectively (Table 2). As shown in Fig. 3b, the energy difference between the orbital spin-splitting peaks (2p1/2 and2p3/2) is ∼23 eV, the ratio of the spectral peak areas (2p1/2:2p3/2) is ∼1:2. The Zn2p spectral peaks at 1021.9 eV, as indicated by the database, correspond to ZnO. The Fe2p spectrum in Fig. 3c shows a low-intensity peak at 708.9 eV, verifying the presence of Fe³⁺ species in the catalyst. Meanwhile, those peaks at 710.0, 711.0, 712.0, and 713.0 eV represent the four typical multiple cleavages of Fe³⁺ with their relative contents, as shown in Table 3.

According to the above results, there were no significant changes in the valence states of Fe and Zn in the catalyst. but the carbon content increased after the reaction, while the Fe and Zn concentrations simultaneously decreased. Although Fe in the catalyst is predominantly in the form of Fe³⁺, which increases at low binding energies after the reaction.

3.2. Catalytic activity and reaction parameters

The ATZ removal rates of different systems were studied to evaluate the catalytic efficiency of ATZ degradation by ZnFe₂O₄-activated PMS. The effects of catalyst dosage, PMS addition, starting pH and anions on ATZ degradation were studied to confirm the oxidation efficiency of ZnFe₂O₄ catalyst.

The effect of the ZnFe₂O₄ catalyst amount on ATZ degradation efficiency was studied by adding different amounts of the ZnFe₂O₄ catalyst (0, 0.1, 0.2, 0.5 g/L) at room temperature (25°C), an initial pH of 7, an ATZ concentration of 20 µmol/L, and a PMS concentration of 100 mg/L. As shown in Fig. 4, the ATZ degradation rate reached only 10% within 1 min when only PMS was added without the ZnFe₂O₄ catalyst. However, as the catalyst concentration increased, the ATZ degradation efficiency also increased. Specifically, at catalyst concentrations of 0.1 and 0.2 g/L, the ATZ degradation efficiency was 15% and 22%, respectively. When the catalyst concentration was 0.5 g/L, the degradation efficiency was 30%. This trend could be attributed to the increase in the catalyst amount, which generates more PMS-activated active sites and more ROS (She et al., 2021). Meanwhile, the increased catalyst content might enhance the ATZ adsorption, promoting ATZ oxidation. However, the ATZ degradation efficiency is not very high, either without the catalyst or with 0.5 g/L Catalyst. This limitation could be primarily attributed to the PMS content. The optimization of reaction conditions necessitates the change in the PMS amount; thus, the subsequent experiments were carried out using 0.5 g/L of the catalyst.

Furthermore, the effect of the PMS concentration on ATZ degradation efficiency was studied by adding different concentrations of PMS (0, 100, 200, and 500 mg/L) at room temperature (25°C), an initial pH of 7, an ATZ concentration of 20 µmol/L, and a catalyst concentration of 0.5 g/L. The results are shown in Fig. 5. As shown in Fig. 5, in the absence of PMS, the ZnFe₂O₄/PMS system caused minimal ATZ degradation after 30 min of adsorption, and the ATZ degradation rate increased with the PMS concentration. Specifically, at PMS concentrations of 200 and 500 mg/L, the ATZ degradation rates were 62% and 74%, respectively. The ATZ degradation rate was notably high within the first minute, and decreased with time. When the PMS concentration was 100 and 200 mg/L, the ATZ degradation efficiency increased more than twice. However, no significant decrease in the ATZ degradation efficiency was observed, when the PMS concentration was 500 mg/L. This finding could be attributed to the presence of excess PMS that serves as a free radical scavenger and its competition with ATZ for the formation of reactive substances (Xu et al., 2022). Conversely, the small number of active sites on the catalyst surface hinders effective PMS activation, reducing ATZ degradation efficiency (Miao et al., 2018).

Initial pH of the reaction solution is a crucial parameter that affects the oxidative ATZ degradation by PMS. The effects of initial pH values of ATZ (3, 5, 7, 9, 11) on the ATZ degradation efficiency were investigated at room temperature (25°C), an ATZ concentration of 20 µmol/L, a catalyst concentration of 0.5 g/L, and a PMS concentration of 500 mg/L; the results are shown in Fig. 6. According to these findings, ATZ could undergo degradation by ZnFe₂O₄-activated PMS in a broad pH range. However, the ATZ removal efficiency decreased as the initial pH increased. Generally, the primary active substances are abundant under acidic conditions and are highly effective toward ATZ degradation (Hussain et al., 2017; Liu et al., 2019). However, these active species tend to react with OH⁻ to form HO• under alkaline conditions (Xie et al., 2019). Higher concentrations of OH⁻ may also lead to HO• and OH⁻ interactions, resulting in radical annihilation and thus reducing the degradation efficiency of ATZ.

Two typical inorganic anions, H₂PO₄⁻ and CO₃²⁻, were selected to assess the practical applicability of the ZnFe₂O₄ catalysts. The effects of these two anions on the ATZ degradation efficiency in the ZnFe₂O₄/PMS system were observed by adding 10 mM of H₂PO₄⁻ and CO₃²⁻ at room temperature of 25°C, an initial pH of 7, an ATZ concentration of 20 µmol/L, and a catalyst concentration of 0.5 g/L; the results are shown in Fig. 7.

As shown in Fig. 7, the addition of H₂PO₄⁻ and CO₃²⁻ to the ZnFe₂O₄/PMS system results in the partial degradation of ATZ. When 10 mM H₂PO₄⁻ was added, the ATZ removal rate decreased rapidly to 67%. This decrease could be attributed to the reaction of H₂PO₄⁻ with HO•, generating the less-reactive phosphate (Peng et al., 2018). In addition, H₂PO₄⁻ formed a complex with the catalyst on the surface, inhibiting ATZ degradation. Similarly, in the presence of 10 mM of CO₃²⁻, the ATZ removal rate was only 50% within 30 min. The results showed that CO₃²⁻ induced a scavenging effect on the ROS (Ji et al., 2015). In addition, CO₃²⁻ increased the alkalinity of the solution, which negatively affected ATZ degradation efficiency.

3.3. Reusability of ZnFe₂O₄ in catalytic reaction

One of the most crucial factors for the practical application of a catalyst is its reusability. Four catalysis cycles were conducted under the experimental conditions to assess the reusability of ZnFe₂O₄. As shown in Fig. 8, the ATZ degradation efficiency decreased from 86–81% in 30 min after four cycles, indicating excellent reusability of the ZnFe₂O₄ catalyst. However, slight metal ion overflow was observed on the catalyst, which was believed to have caused the decrease in activity. Moreover, ATZ degradation might be hindered by the absorption of certain intermediate products by the catalyst (Liu et al., 2021).

3.4. Catalytic mechanism

An EPR spectroscopy study of the ROS involved in the ZnFe2O4/PMS system was carried out to understand the catalytic mechanism. In this study, DMPO was utilized to capture SO₄•⁻, HO•, and O₂•⁻, and TEMP was used to detect ¹O₂ using spin trapping. The DMPO-HO• adduct exhibits characteristic peaks as the reaction time increases from 0 to 10 min, as shown in Fig. 9a. The DMPO-O₂•⁻ adduct signals indicate that O₂•⁻ may also participate in ATZ degradation, as shown in Fig. 9b. Moreover, TEMP-¹O₂ adduct signals were observed after 10 min, indicating the participation of ¹O₂ in the reaction. These results demonstrate that the PMS might be activated by the ZnFe₂O₄ catalyst to produce active substances that remove ATZ. And SO₄•⁻ was not detected in the EPR spectra, possibly because SO₄•⁻ was consumed rapidly within 5 min of the reaction.

3.4. ATZ degradation pathways

To elucidate the pathway of ATZ degradation over the ZnFe₂O₄/PMS system, the degradation intermediates were determined through the LC-MS/MS. Electrospray quadrupole time-of-flight mass spectrometry (ESI Q-TOF) was conducted to qualitatively analyze the model compound (ATZ) and its degradation products in a positive ion mode. After analyzing the structure and type of the resulting product, the possible degradation pathway was inferred, primarily involving the reaction channels shown in Fig. 10. The first possible reaction channel of the initial substrate (the proton ion peak [m+H]⁺ obtained through ionization in ESI-MS is at m/z 216; the subsequent ion peaks correspond to proton adducts [m+H]⁺ formed through the ionization of the corresponding product in mass spectrometry appear at m/z 188) involves the cleavage of the C_Sp3-N bond in ATZ to deisopropyl, and 6-chloro-2 is obtained through further cleavage of the C_Sp3-N bond to form deethyl 4-diamino-1,3,5-triazine at m/z 146. The second possible reaction channel involves the cleavage of the C_Sp3-N bond in ATZ to form the deethylated product at m/z 174 and the further cleavage of the C_Sp3-N bond to form the depropyl product [6-chloro-2,4-diamino-1,3] at m/z 188 and 174. This product further reacted with chlorine to yield amino chlorides at m/z 222 and 208. The chlorination of the product at m/z 222 resulted in the further chlorination of the amino group to yield the amino dichlorination product at m/z 256.The subsequent degradation of products m/z 222 and 208 involves the cleavage of C-Sp3-N bonds, leading to the formation of m/z 180 products through the elimination of deprropyl or ethyl groups. The third possible reaction channel involves the oxidation of the methyl group on the N-ethyl group of ATZ to yield a product at m/z 232. The hydrolysis of the chlorine atom leads to the C–Cl bond cleavage at m/z 214, yielding the product at m/z 170. 4,6-Diamino-2-hydroxytriazine (m/z 128) is obtained upon further deethylation. The product at m/z 232 is also formed via the oxidative dehydrogenation of the alcohol hydroxyl group, which yields another product at m/z 230. The fourth possible reaction channel involves the hydrolysis of the chlorine atom of ATZ, yielding the product at m/z 198. Additionally, products at m/z 156 or 170 were obtained through the cleavage of the C_Sp3-N bond to form the propyl or ethyl group, respectively. The reoccurring C_Sp3-N bond was broken to form the deethyl or propyl group, and the 4,6-diamino-2-hydroxytriazine product was obtained at m/z 128. ATZ degradation was also characterized by the monochlorination and dichlorination of ethyl to yield products at m/z 174 and 284. 4,6-Diamino-2-hydroxy-triazine or N²,6-dichloro-2,4-diamino-triazine was further characterized by the cracking and oxidation of the triazine ring to obtain small molecules, such as acids and amines, and finally to obtain H₂O, CO₂, Cl⁻, NO₃⁻, and NH₄⁺.

High-activity ZnFe₂O₄ catalysts were synthesized via co-precipitation and their applicability as PMS activators for ATZ degradation was verified. Under the optimized reaction conditions, the ATZ degradation efficiency reached 86%. Notably, the inorganic anions (H₂PO₄⁻, CO₃²⁻) partially inhibited the degradation of ATZ. In the cycling experiments, ZnFe₂O₄ was found to be catalytic activity and stability. Moreover, the EPR and XPS results suggested that various active substances, including HO•, O₂•⁻, and ¹O₂, were involved in ATZ mineralization. The ATZ degradation mechanism of the ZnFe₂O₄/PMS system was hypothesized to be dependent on the product identified through the UPLC-MS. The study highlighted the effective ATZ removal by the prepared ZnFe₂O₄ catalyst and its excellent catalytic performance.ZnFe₂O₄ catalyst is an environmentally friendly catalyst, and iron and zinc elements avoid secondary pollution to water, which is of great significance for the efficient removal of pollutants in water.

Acknowledgements

This work was funded by Agricultural Science and Technology Innovation Program of China (ASTIP-TRIC06), the Science and Technology Project of Bijie Tobacco Branch Company (2020520500240072, 2023520500240162) and the Science and Technology Project of Hengyang Tobacco Company of Hunan Province (2020430400240090)

Declaration of competing interest

The authors declare no competing interests

Author Contributions

J Y. Gao and X Y, Zhao. design, experiment, analysis, original drafting; C B. Li and Z B Luo, data curation, formal analysis and original drafting; L Zhang. investigation; methodology; Z P, Xiao and T T, Mu, review & editing; F L Liu and R K Gao, date analysis and curation; J G. Zhang and X W Sun. conception, funding acquisition, revising.

Data Statement

Data is available under reasonable request to the corresponding author.

Additional information

Correspondence and requests for materials should be addressed to J G. Zhang or. .X W. Sun.

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Table 1. Relative content of the elements in the samples /at.%.

sample	C	O	Zn	Fe
ZnFe2O4	42.96	35.44	13.97	7.63

Table 1. Relative content of the elements in the samples /at.%.

sample	C	O	Zn	Fe
ZnFe2O4	42.96	35.44	13.97	7.63

Table 3. Relative content of each chemical bond of Fe³⁺/at.%.

sample	1-Fe³⁺	2-Fe³⁺	3-Fe³⁺	4-Fe³⁺
ZnFe2O4	18.96	38.70	23.33	19.01

No competing interests reported.

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Efficient Atrazine Degradation through ZnFe₂O₄-Catalyzed Peroxymonosulphate Activation

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Abstract

Figures

1. Introduction

2. Materials and methods

2.1. Materials

2.2. Synthesis of ZnFe₂O₄

2.3. Characterization of the catalyst

2.4. Catalytic activity test

3. Results and discussion

3.1. Characterization

3.2. Catalytic activity and reaction parameters

3.3. Reusability of ZnFe₂O₄ in catalytic reaction

3.4. Catalytic mechanism

3.4. ATZ degradation pathways

4. Conclusion

Declarations

References

Tables

Additional Declarations

Supplementary Files

Status:

Version 1

Efficient Atrazine Degradation through ZnFe2O4-Catalyzed Peroxymonosulphate Activation

Status:

Version 1

Abstract

Figures

1. Introduction

2. Materials and methods

2.1. Materials

2.2. Synthesis of ZnFe2O4

2.3. Characterization of the catalyst

2.4. Catalytic activity test

3. Results and discussion

3.1. Characterization

3.2. Catalytic activity and reaction parameters

3.3. Reusability of ZnFe2O4 in catalytic reaction

3.4. Catalytic mechanism

3.4. ATZ degradation pathways

4. Conclusion

Declarations

References

Tables

Additional Declarations

Supplementary Files

Status:

Version 1

Efficient Atrazine Degradation through ZnFe₂O₄-Catalyzed Peroxymonosulphate Activation

2.2. Synthesis of ZnFe₂O₄

3.3. Reusability of ZnFe₂O₄ in catalytic reaction