Study on catalytic mechanisms of Fe3O4-rGOx in three typical advanced oxidation processes for tetracycline hydrochloride degradation

Study on catalytic mechanisms of Fe₃O₄-rGO_x in three typical advanced oxidation processes for tetracycline hydrochloride degradation

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Heshan Zheng^a, Yunying Hou^a, Shuo Li^a^,^b^,^c^,^**, Jun Ma^a^,^b, Jun Nan^b^,^c, Nannan Wang^d^,^*

Chinese Chemical Letters | 2023, 34(1) : 107253

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Chinese Chemical Letters | 2023, 34(1): 107253

• Communication •

Study on catalytic mechanisms of Fe₃O₄-rGO_x in three typical advanced oxidation processes for tetracycline hydrochloride degradation

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Heshan Zheng^a, Yunying Hou^a, Shuo Li^a^,^b^,^c^,^**, Jun Ma^a^,^b, Jun Nan^b^,^c, Nannan Wang^d^,^*

Affiliations

^aCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China

^bUrban Water Resources Development and Northern National Engineering Research Center, Harbin 150090, China

^cSchool of Environment, Harbin Institute of Technology, Harbin 150090, China

^dDepartment of Environmental Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Published: 2023-01-15 doi: 10.1016/j.cclet.2022.02.058

Outline

Abstract

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This study explored the catalytic mechanism and performance impacted by the materials ratio of Fe₃O₄-GO_x composites in three typical advanced oxidation processes (AOPs) of O₃, peroxodisulfate (PDS) and photo-Fenton processes for tetracycline hydrochloride (TCH) degradation. The ratio of GO in the Fe₃O₄-GO_x composites exhibited different trends of degradation capacity in each AOPs based on different mechanisms. Fe₃O₄-rGO_20wt% exhibited the optimum catalytic performance which enhanced the ozone decomposition efficiency from 33.48% (ozone alone) to 51.83% with the major reactive oxygen species (ROS) of O₂^•−. In PDS and photo-Fenton processes, Fe₃O₄-rGO_5wt% had the highest catalytic performance in PDS and H₂O₂ decomposition for SO₄^•‒, and ^•OH generation, respectively. Compared with using PDS alone, PDS decomposition rate and TCH degradation rate could be increased by 5.97 and 1.73 times under Fe₃O₄-rGO_5wt% catalysis. In the photo-Fenton system, Fe₃O₄-rGO_5wt% with the best catalyst performance in H₂O₂ decomposition, and TCH degradation rate increased by 2.02 times compared with blank group. Meantime, the catalytic mechanisms in those systems of that the ROS produced by conversion between Fe²⁺/Fe³⁺ were also analyzed.

Key words

Advanced oxidation progresses / Fe₃O₄ / Graphene oxide / Mechanism / Reactive oxygen species

Cite this Article

Heshan Zheng, Yunying Hou, Shuo Li, Jun Ma, Jun Nan, Nannan Wang. Study on catalytic mechanisms of Fe₃O₄-rGO_x in three typical advanced oxidation processes for tetracycline hydrochloride degradation[J]. Chinese Chemical Letters, 2023 , 34 (1) : 107253 - . DOI: 10.1016/j.cclet.2022.02.058

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Advanced oxidation processes (AOPs) could produce reactive oxygen species (ROS) of hydroxyl radicals (^•OH), superoxide radicals (O₂^•−), and sulfate radicals (SO₄^•‒) that with strong oxidation capacity [1]. ^•OH has great oxidation power to degrade recalcitrant organic contaminants, which has wide range of sources and can be produced by Fenton, Fenton-like, ozone, photocatalysis and sulfate radical-based AOPs (SR-AOPs) [2]. O₂^•− is generated by ozone system, and SO₄^•‒ usually appears in persulfate (including peroxodisulfate (PDS) or peroxomonosulfate (PMS)) system [3]. Various AOPs have been widely studied and applied in wastewater treatment for high effective degradation of toxic and biorefractory organic compounds [4].

To improve their efficiency and solve the drawbacks in practical application of low utilization rate of O₃, high energy consumption for activation of SR-AOPs, and narrow pH limitation of Fenton, etc., it is an urgent need to develop new catalysts. As the advantages of high abundance, non-toxicity, and good interface electron transfer ability of iron, iron-based materials have become commonly used heterogeneous catalyst in AOPs. Jin et al. synthesized Cu substituted magnetic Fe₃O₄@FeOOH to degrade ofloxacin in Fenton-like process [5]. Fe₃O₄@hollow@mSiO₂ was used as catalyst to degrade sulfadiazine in ultrasound-assisted Fenton-persulfate system [6]. Fe₃O₄@CuO_x hollow ball activated PS can remove 95% of sulfadiazine [7]. Composite materials such as Fe₃O₄ nanoparticles are used in various advanced oxidations, which can quickly remove organic substances in wastewater. However, some catalysts have complex synthesis processes and large ion leaching concentrations, which are prone to metal agglomeration. Graphene oxide (GO) is highly oxidized structure of grapheme, comprises high density of oxygenated functional groups, which can effectively prevent the agglomeration and corrosion of metal oxides, making it commonly used as a support material in composite materials [8, 9]. Therefore, loading Fe₃O₄ on GO to form a metal composite as a catalyst for AOPs can effectively degrade pollutants. rGO/Fe nanoparticles were used as adsorbents and Fenton-like catalysts to remove 93.6% of mitoxantrone from the wastewater [10]. NGO/Fe₃O₄ was used as a catalyst to activate potassium persulfate to degrade norfloxacin under the assistance of ultraviolet light [11]. GO-Fe₃O₄ nanocomposites was used as catalyst for degradation of ofloxacin by pulsed discharge plasma [12].

Although it is reported that Fe₃O₄-GO_x as a catalyst enhances the degradation of certain organic pollutants in AOPs, the mechanism of its catalytic degradation of pollutants is lack of in-depth analysis. Tetracycline hydrochloride (TCH) as a broad-spectrum antibiotic is widely used as an antibacterial agent and feed additive, thereby we chose it as the target pollutant. Therefore, we studied the catalytic mechanisms of Fe₃O₄-GO_x synergistically catalyzed oxidants decomposition and pollutant degradation in AOPs (including ozonation, persulfate catalysis and photo-Fenton progress) that based on different free radicals. In this paper, (ⅰ) the effect of GO loading ratio on the morphology of the composites was analyzed by characterization; (ⅱ) the effects of different proportions of Fe₃O₄ and GO on the degradation efficiency of TCH in three AOPs were systematically analyzed; (ⅲ) the potential mechanism of TCH degradation of the composites were clarified by detecting the oxidant concentration in the solution, and utilizing X-ray photoelectron spectroscopy (XPS), quenching experiment and electron spin resonance (ESR).

According to the published paper, using solvothermal process synthesized Fe₃O₄ and Fe₃O₄-rGO_x (Text S1 in Supporting information) [12]. The morphology of Fe₃O₄ and Fe₃O₄-rGO_x were observed by SEM, which were shown in Fig. 1a. Fe₃O₄ exhibited irregular rob shape, after loading Fe₃O₄ on the GO layer, the particle size of Fe₃O₄ gradually decreased as the amount of GO increased. This may be that the GO surfaces contain negatively charged oxygen-containing groups which could be adsorbed on the broadside of Fe₃O₄ crystals, and imposed a certain strain on them, thus limiting the growth of Fe₃O₄ [13]. Meantime, with the increase of GO content, the main crystal surface of Fe nanoparticles was affected, which made the larger crystal surface was replaced by the smaller crystal surface [12]. Fig. S1a (Supporting information) was the X-ray diffraction (XRD) patterns of GO, Fe₃O₄ and Fe₃O₄-rGO_x. In the GO spectrum, an evident peak at 2θ = 11.2° was consistent with previous research [12, 14]. The peaks of Fe₃O₄ and Fe₃O₄-rGO_x located at 30.1°, 35.5°, 43.3°, 53.6°, 57.2° and 62.7° were accordance with the (220), (311), (400), (422), (511) and (440) crystal faces of Fe₃O₄ [15]. Moreover, the characteristic peaks of rGO were observed at 21.2° and 26° in Fe₃O₄-rGO_x composites, indicating that GO had been reduced to rGO, which also demonstrated the successful synthesis of composites [16]. Fig. S1b (Supporting information) displayed the FT-IR patterns of Fe₃O₄ and Fe₃O₄-rGO_x. The absorbed H₂O molecule or surface hydroxyl were detected the range of 3000–3500 cm⁻¹ [17]. The −CH₂− was observed at 2800–2900 cm⁻¹ in Fe₃O₄-rGO_x, and the peak shifted from 1633 to 1600 cm⁻¹ because of GO doping to form −COO− [3]. Besides, all samples had an obvious absorption peak at 570 cm⁻¹, which was the Fe−O−Fe stretching vibration [18].

Figs. 1b–e depicted degradation rate of TCH with different ratio of Fe₃O₄ to GO_x in AOPs. All catalysts did not significantly adsorb TCH during 30 min, indicating that catalytic oxidation dominated the removal of TCH. The adsorption efficiency also increased with the increase of GO loading. However, when the GO loading increased to 30 wt%, the adsorption efficiency was only 3.6%. The reason was that GO folding each other lead to a reduction in the size and number of pores. The salient features and trends in TCH degradation in AOPs, as evident from the results were presented in Fig. 1. In Fig. 1b, the degradation rate was limited by the ozone dissolution in catalytic ozonation stages. After 5 min of treatment, the efficiency of O₃ to remove TCH alone was 9.31%, and it reached 57.93% after 15 min. After adding Fe₃O₄, the removal efficiency of TCH increased to 80.55%. Compared with Fe₃O₄, Fe₃O₄-rGO_x enhanced the removal efficiency of TCH clearly. Because strong interaction between Fe₃O₄ and GO could decompose O₃ to produce O₂^•− and H₂O₂, and then H₂O₂ reacted with O₃ to produce ^•OH [19, 20]. Meantime, GO acted as a carrier to disperse the active sites on its surface and expanded the contact area between oxidants and contaminants. Fig. S2a (Supporting information) showed the transient photocurrent response of pure Fe₃O₄ and Fe₃O₄-rGO_x. Compared with Fe₃O₄, Fe₃O₄-rGO_x composites exhibited a significantly enhanced photocurrent density, which indicated that the electron transfer was promoted between Fe₃O₄ and rGO. Meantime, the higher photocurrent response of the sample was, the more effective separation of the photoelectron-hole pairs will be obtained, which evidenced that Fe₃O₄-rGO_20wt% composite that with the most efficient separation were due to the strongest photocurrent response. Therefore, with the increased of GO content, the removal rate of TCH also increased. The degradation efficiency of TCH by the Fe₃O₄-rGO_20wt% was 100% and the reaction rate constant (k₂) was 0.017 g mg⁻¹ min⁻¹ and higher than that derived from other catalysts (the k₂ of other catalysts were 0.004, 0.005, 0.005, 0.006 and 0.002 g mg⁻¹ min⁻¹) (Text S2, Fig. S1c and Table S1 in Supporting information).

As illustrated in Fig. 1c, the removal of TCH was observed about 52.17% in the blank group during 30 min reaction time, which may be attributed that PDS under the heating condition produced ROS to degrade TCH. Fe₃O₄ and GO activating PDS systems had only 76.51% and 26.13% removal ratio of TCH, respectively. Under the support of GO, the catalytic performance of Fe₃O₄-rGO_x was remarkably improved. From Fig. S1d and Table S1 (Supporting information), TCH had a highest rate constant of 0.0052 g mg⁻¹ min⁻¹ (R² = 0.954) in Fe₃O₄-rGO_5wt%/PDS system, approximately 1.3 times than that of Fe₃O₄/PDS system. The raised degradation efficiency was obviously ascribed to the increase of available active sites for PDS decomposition. When GO loading was 2.5 wt%, 10 wt%, 20 wt% and 30 wt%, TCH removal rate and k₂ were both reduced. This was mainly attributable to the enhancement of free radicals scavenging effect of reactive sites on Fe₃O₄-rGO_x surface, meantime, acidic conditions will limite the produce of ^•OH [21].

In photo-Fenton system, as was displayed in Fig. 1d, TCH degradation efficiency was less than 50% after 90 min without catalyst. However, the degradation rate of pure Fe₃O₄ to TCH was 90.60%, which was close to that of Fe₃O₄-rGO_5wt% to TCH (98.11%). Therefore, a pseudo-first-order model was used to compare the catalytic activity of the two catalysts. In Fig. S1e and Table S1 (Supporting information), the rate constant of Fe₃O₄-rGO_5wt% was 1.5 times that of Fe₃O₄, so the catalytic activity of Fe₃O₄-rGO_5wt% was better than Fe₃O₄. From the UV-vis diffuse reflectance spectrum of pure Fe₃O₄ and GO, Fe₃O₄-rGO_x composites, which can be seen that the optical properties of materials. Fig. 1e showed that the Fe₃O₄-rGO_x composites exhibited stronger absorption throughout visible light range than Fe₃O₄ and GO. This may be attributed to the specific structure: GO sheets and Fe₃O₄ particles allowed multiple reflections of light. According to the study of Moztahida et al. [15], and the results of UV-vis diffuse reflectance spectrum and photocurrent (Fig. 1e and Fig. S2a in Supporting information) also showed that the addition of rGO increased the light adsorption capacity of Fe₃O₄-rGO_x composites and provided more electrons and holes (h⁺) for the production of ROS. However, by GO loading ratio from 5 wt% to 30 wt% increasing, its removal efficiency was diminished from 98.11% to 60.37%. Because the increase of GO loading affected the turbidity of solution, which lead the increase of the resistance of UV to penetrate it and shielded light adsorption [22], even affected charge separation [15]. Hence, the Fe₃O₄-rGO_5wt% had the optimum catalytic performance.

To investigate the potential for recycling of catalysts, the tetracycline oxidation testing was performed in 5 cycles in three AOPs, respectively. As could be seen from Fig. S2b (Supporting information), the removal efficiency of the TCH gradually decreased with the increase of the number of times of use. The removal rate of about 80% indicated that materials were stable and had a certain reusability. Compared with the 1^st run, TCH degradation rate decreased slightly in the 5^th, which might be due to the surface oxidation of the catalyst and leaching of metal ions during the catalytic process [20]. The leaching rate of metal ions was shown in Table S2 (Supporting information). And the leaching amount of total iron and Fe²⁺ was less than 0.1% with respect to the catalyst dose of 500 mg/L. However, the temperature condition of PDS system was 60 ℃ (O₃ and photo-Fenton systems were carried out at room temperature), which lead the increase of ion leaching rate of catalysts. In addition, the leached Fe concentration at the end of each round almost kept the same level, which satisfied the water environment discharge standards (2 mg/L) imposed by the European Union [23].

The proportion of GO in Fe₃O₄-rGO_x affected TCH degradation in the three AOPs. Therefore, we conducted a series of experiments to explore the effect of GO loading ratio on TCH degradation and the mechanism of catalysts in AOPs. Fig. 1a showed that GO_x affected the morphology of catalyst, and further effected TCH degradation (Fig. 1b). To verify that catalysts enhanced O₃ decomposition, this experiment measured the ozone concentration in liquid phase of each system, and the test results were shown in Fig. 2a. The ozone concentration in the solution gradually rose within 5 min, because ozone undergo a mass transfer process from the gas phase to the liquid phase [24, 25], and TCH degradation hardly changed within 5 min. The concentration of liquid phase ozone reached 3.76 mg in 5 min in blank group, and then remained stable; after adding Fe₃O₄, the ozone concentration reached 3.58 mg/L in 5 min, and Fe₃O₄-rGO_20wt%/O₃ system reached 1.48 mg/L in 5 min (other catalysts system reached about 3.5 mg/L), and the solution ozone concentration finally reached 2.4, 1.33, 2.31, 1.73, 1.71, 1.54, 0.46 and 2.09 mg/L, respectively. It indicated that the catalyst can accelerate ozone decomposition, reduce solution ozone concentration, and thereby improve the utilization mass of ozone. Eq. S3 (Text S3 in Supporting information) was used to calculate the ozone utilization mass to better show the mechanism of Fe₃O₄-GO_x/O₃ system [26].

The ozone utilization mass was shown in Fig. 2b. According to Eq. S3, it under those systems was 19.19, 25.31, 19.70, 27.2, 27.92, 28.46, 31.45 and 21.47 mg, respectively. Compared with control groups, Fe₃O₄-rGO_x enhanced TCH degradation and O₃ utilization mass clearly. The reason was that strong interaction between Fe₃O₄ and GO_x could decompose O₃ to produce O₂^•− and H₂O₂, and then H₂O₂ reacted with O₃ to produce ^•OH (Text S4 and Eqs. S4-S13 in Supporting information) [19, 20]. Fig. 2c was XPS spectra of Fe 2p before and after Fe₃O₄-rGO_20wt%, which corroborated the Fe²⁺/Fe³⁺ species participated in the electron-transfer processes and contributed to the utilization of ozone (Fe²⁺ changed from 51.87% to 42.90%). The fitting peaks at the binding energies of 710.7 and 724.3 eV belong to Fe²⁺, while the fitting peaks at the binding energies of 712.7 and 726.3 eV were Fe³⁺ [27, 28]. To explore ROS in O₃ system, tert‑butanol (TBA), benzoquinone (BQ), furfuryl alcohol (FFA) and phosphate (KDP) were added in solution to quench ^•OH, O₂^•−, ¹O₂ and surface of ^•OH, respectively Fig. 2d displayed the major ROS in ozone system. After BQ injected, all the O₂^•− generated in Fe₃O₄-rGO_20wt%/O₃ system was nearly quenched and resulting in a decrease in TCH removal from 100% (without quencher) to 23.35%. The addition of TBA, FFA and KDP reduced the TCH removal rate to 78.46%., 90.52%. and 97.31%. Therefore, it was deduced that O₂^•− was the main reactive oxygen species generated in the Fe₃O₄-rGO_20wt%/O₃ system, ^•OH and ¹O₂ had no significant effects in the catalytic ozone system. However, ¹O₂ and O₂^•− were the major ROS in GO and Fe₃O₄ system. ESR measurements were carried out to further accurately elucidate the existence of ROS in Fe₃O₄-rGO_20wt%/O₃ system (Fig. 2e). The O₂^•− and ^•OH signals can be observed in the Fe₃O₄-rGO_20wt%/O₃ process in Fig. 2e indicated that Fe₃O₄-rGO_20wt% can decompose ozone to generate O₂^•− and ^•OH.

As shown in Fig. 1c, PDS as the main oxidant participating of Fe₃O₄-rGO_x/PDS process played an important role. In order to explore catalytic mechanism in system, PDS concentration and decomposition rate were measured and concluded in solution. It can be seen in Figs. 3a and b, PDS decomposition increased with the decreased concentration of that in solution. Comparing with other catalysts, Fe₃O₄-rGO_5wt% had the lowest PDS concentration (45.63 mg/L) and the highest PDS decomposition rate (54.37%). Therefore, Fe₃O₄-rGO_5wt% had the highest TCH degradation in PDS system. As exhibited in Fig. 3c, compared with fresh Fe₃O₄-rGO_5wt%, it was found that the peak area of Fe²⁺ decreases and Fe³⁺ increased after reaction, which indicated that the transition between Fe²⁺ and Fe³⁺ during the reaction activated the decomposition of PDS to produce ROS. Therefore, to further explore the mechanism for Fe₃O₄-rGO_5wt%, we analyzed the type of ROS in this system. It was reported that SO₄^•‒ and ^•OH could be produced by the metal-based catalysts activated PDS [29, 30]. As given in Fig. 3d, the TCH degradation efficiency decreased from 90.4% to 24.38% and 57.3% with addition of methanol (MeOH) and TBA, respectively. And adding BQ, the removal rate of TCH decreased to 64.16%. This result clearly indicated that the degradation process was a pure radical-based oxidation process. Moreover, both SO₄^•‒ and ^•OH occurred in the Fe₃O₄-rGO_5wt%/PDS system and the latter one played a much more important role. Similarly, Chen et al. [30] claimed that the sulfate radical was the dominating radical species responsible for the degradation of norfloxacin by CoFe₂O₄-GO/PMS system. However, Fig. 3d results revealed that ¹O₂, O₂^•− and SO₄^•‒ were generated in PDS, GO/PDS and Fe₃O₄/PDS system, in which ¹O₂ and O₂^•− were the dominant ROS [15]. Therefore, PDS itself will produce a small amount of ROS to degrade TCH at 60 ℃. Meantime, in a review about the treatment of wastewater by the sulfate-based AOPs, Fang et al. [31] have analyzed that SO₄^•‒ dominate the acidic pH conditions. According to study of Wang et al. [32] and Jing et al. [3], a possible mechanism for PDS activation by Fe₃O₄-rGO_5wt% was proposed (Eqs. S14-S26 shown in Supporting information Text S5). ESR signals of ^•OH, SO₄^•‒ and O₂^•− were observed in the system (Fig. 3e), the results confirmed the previous inference that SO₄^•‒, O₂^•− and ^•OH existed in Fe₃O₄-rGO_5wt%/PDS system. The increase of GO loading ratio expanded the reaction site and produced a large amount of ROS. However, excessive SO₄^•‒ will quench each other. Therefore, Fe₃O₄-rGO_5wt% had the best catalytic performance compared with others.

About the difference of TCH degradation in photo-Fenton progress, it was speculated that increase of GO loading lead the turbidity of solution increased, which made high resistance for light to penetrate solution, decreased H₂O₂ decomposition and further affected TCH degradation. To verify this hypothesis, the influences of those catalysts were tested on the concentration of H₂O₂. In Fig. 4a, the H₂O₂ concentration of blank, Fe₃O₄, GO and Fe₃O₄-rGO_x were 155.62, 104.53, 150.24, 100.77, 80.42, 129.41, 141.07 and 143.85 mg/L, which suggested that GO loading ratio affected H₂O₂ decomposition and TCH degradation. Compared with other systems, Fe₃O₄-rGO_5wt%/UV-H₂O₂ system had the lowest H₂O₂ concentration. Moreover, using Fig. 4b analyzed the interfacial charge transfer capabilities of Fe₃O₄ and Fe₃O₄-rGO_5wt%. The arc radius of the Nyquist curve for Fe₃O₄-rGO_5wt% was significantly smaller than that of Fe₃O₄, which implied that the charge of the Fe₃O₄-rGO_5wt% at the interface migration resistance decreased and the e⁻ mobility of the composite was enhanced. As shown in Fig. 4c, supported by the fitting parameters, that of Fe²⁺ and Fe³⁺ for the pristine Fe₃O₄-rGO_5wt% were 48.55% and 18.12%, respectively. After the degradation reactions, the peak area of Fe²⁺ slumped to 43.87%, while the peak area ratio of Fe³⁺ went up to 22.80%, which suggested that Fe²⁺/Fe³⁺ were involved in electron transfer processes. And Fig. 4d illustrated ^•OH and h⁺ were the main ROS in Fe₃O₄-rGO_5wt%/UV/H₂O₂ system (ethylenediamine tetraacetic acid disodium (EDTA-2Na) quenched h⁺), O₂^•−, ^•OH and h⁺ existed in GO and Fe₃O₄ system, and the major ROS of blank group were O₂^•− and ^•OH (corresponding degradation mechanism was shown in Eqs. S27-S34 and Text S6 in Supporting information) [15, 33]. As shown in Fig. 4e, characteristic ESR signals of ^•OH, O₂^•− and ¹O₂ can be observed in the catalytic system of Fe₃O₄-rGO_5wt%/UV/H₂O₂, thus ^•OH, O₂^•− and ¹O₂ were existed in this system. Meantime, researchers also observed the similar conclusion in the removal of sulfamethoxazole in the Fe₃S₄ derived from MIL-100(Fe)/Vis/H₂O₂ system.

In order to understand the source of O₂^•− in three AOPs, nitrogen bubble was blown into the solution to further verify and revealed degradation mechanism. In Fig. S3 (Supporting information), the degradation rate of TCH in PDS system was 72.96%. Compared with no N₂, that of TCH decreased by 17.44%. However, in Fig. 3d, the inhibition rate of TCH after adding BQ was 26.24%, which indicated that the formation of O₂^•− in PDS system was attributed in dissolved oxygen in solution and the decomposition of water molecules. However, none of the other systems were affected, which indicated that O₂^•− all came from the reaction between catalyst and substances in systems. And among these three AOPs, O₃ system completely removed TCH within 15 min, which is far superior to the PDS and photo-Fenton systems. Therefore, O₃ system is an effective technology to treat TCH wastewater.

In conclusion, the content of GO in Fe₃O₄-rGO_x composites greatly affected the performance and mechanism of TCH degradation in three typical AOPs. In O₃ system, Fe₃O₄-rGO_20wt% exhibited the best catalytic efficiency which could increase the degradation rate of TCH from 57.93% (only O₃) to 100%. The results showed that the strong force between Fe₃O₄ and rGO also improved the decomposition rate of O₃ by Fe₃O₄-rGO_20wt%, and the conversion between Fe²⁺ and Fe³⁺ decomposed oxidant and produced O₂^•− and ^•OH to degrade TCH that detected by ESR spectra. For PDS oxidation system, Fe₃O₄-rGO_5wt% showed higher catalytic activity compared with others By detecting the concentration of PDS in the solution, quenching experiment and ESR analysis found that Fe₃O₄-rGO_5wt% can effectively decompose PDS and produce SO₄^•‒ and O₂^•−, and PDS decomposition rate and TCH degradation rate were 5.97 and 1.73 times higher than those of the blank group. In the photo-Fenton system, the rate of H₂O₂ decomposition by Fe₃O₄-rGO_5wt% was higher than that of others. Meantime, the addition of rGO enhanced the corresponding light region of the composite and separation of photogenerated electron-holes. However, increased GO ratio also enhanced the turbidity of the solution and shielded UV. Therefore, though Fe₃O₄-rGO_10wt%-Fe₃O₄-rGO_30wt% with higher photocurrent density, Fe₃O₄-rGO_5wt% exhibited a higher rate of TCH degradation in UV-H₂O₂ system. In this system, multiple reactive species including ^•OH, O₂^•− and ¹O₂ were detected that responsible for the TCH degradation.

Declaration of competing interest

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All authors declared that they do not have any commercial and associative interests that represent a conflict of interest in connection with the other work submitted.

Acknowledgments

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The work was supported by the National Natural Science Foundation of China (Nos. 21906088, 51902169, 52170039), the National Science Foundation for Post-doctoral Scientists of China (No. 2021T140165), the Natural Science Foundation of Heilongjiang Province, China (No. LH2020B023), Department of Education Heilongjiang Province (No. 135309338), University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (Nos. UNPYSCT-2020068, UNPYSCT-2020067), the authors also gratefully acknowledge the financial support by the Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary (No. BMHXJKF009).

Supplementary materials

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Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2022.02.058.

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Year 2023 volume 34 Issue 1

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doi: 10.1016/j.cclet.2022.02.058

Receive Date：2021-12-02
Online Date：2025-11-20
Published：2023-01-15

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Received：2021-12-02
Revised：2022-01-19
Accepted：2022-02-20

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^aCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China

^bUrban Water Resources Development and Northern National Engineering Research Center, Harbin 150090, China

^cSchool of Environment, Harbin Institute of Technology, Harbin 150090, China

^dDepartment of Environmental Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China

Corresponding:

^**College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China E-mail addresses: shuo_105@163.com (S. Li),

^*wnn_flying@163.com (N. Wang).

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表12种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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Fig. 1. (a) SEM images of pure Fe₃O₄ and Fe₃O₄-rGO_x samples. Catalytic degradation of TCH in (b) O₃ system, (c) PDS system; (d) photo-Fenton progress. (e) UV-vis diffuse reflectance spectrum of pure Fe₃O₄ and Fe₃O₄-rGO_x samples (Reaction conditions: [TCH] = 60 mg/L, [O₃] = 4.0 mg/min, [PDS] = 0.1 g, the temperature of PDS system = 60 ℃, [H₂O₂] = 0.2 mol/L, [UV] = 200–400 nm, [catalysts] = 0.5 g/L, pH 4.6).

Fig. 2. (a) Ozone concentration and (b) ozone utilization mass in solution. (c) XPS spectra for Fe 2p regions of fresh and used Fe₃O₄-rGO_20wt% in O₃ system. (d) Effects degradation efficiency of TCH with the presence of quenchers. (e) ESR spectra detected in Fe₃O₄-rGO_20wt%/O₃ systems for DMPO-^•OH and DMPO-O₂^•− (Reaction conditions: [TCH] = 60 mg/L, [O₃] = 4.0 mg/min, [catalysts] = 0.5 g/L, pH 4.6).

Fig. 3. (a) PDS concentration in solution and (b) PDS decomposition rate. (c) XPS spectra for Fe 2p regions of fresh and used Fe₃O₄-rGO_5wt% in PDS system. (d) Effects degradation efficiency of TCH with the presence of quenchers. (e) ESR spectra detected in Fe₃O₄-rGO_5wt%/PDS system for DMPO-^•OH, DMPO-SO₄^•‒ and DMPO-O₂^•− (Reaction conditions: [TCH] = 60 mg/L, [PDS] = 0.1 g, the temperature of PDS system = 60 ℃, [catalysts] = 0.5 g/L, pH 4.6).

Fig. 4. (a) H₂O₂ concentration in photo-Fenton system. (b) EIS Nyquist plots of Fe₃O₄ and Fe₃O₄-rGO_5wt%. (c) XPS spectra for Fe 2p regions of fresh and used Fe₃O₄-rGO_5wt% in PDS system. (d) Effects degradation efficiency of TCH with the presence of quenchers. (e) ESR spectra detected in Fe₃O₄-rGO_5wt%/UV/H₂O₂ system for DMPO-^•OH, DMPO-O₂^•− and DMPO-¹O₂ (Reaction conditions: [TCH] = 60 mg/L, [H₂O₂] = 0.2 mol/L, [UV] = 200–400 nm, [catalysts] = 0.5 g/L, pH 4.6).

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