Synthesis and application of iron sulfide−based materials to activate persulfates for wastewater remediation: a review

Abstract

Rapid industrial development has led to excessive levels of various contaminants in natural water, which poses a challenge to the innovation of environmental remediation technology. In recent years, iron sulfide and its modified materials have attracted extensive attention in environmental remediation due to their high activity in advanced oxidation processes and widespread existence in anoxic environment. This paper reviewed the latest advances of the synthesis methods for iron sulfide and modified FeS. In addition, the application of persulfate activation by iron sulfide materials (FeS, FeS_x, S−ZVI, FeS@Carbon materials and MFe_xS_y) for contaminants remediation is also reviewed, and the enhancement of this system by photo irradiation, ultrasound, and microwave have also been concluded. Additionally, the interaction mechanism of iron sulfide and persulfate with contaminants was reviewed. Based on the above contents, we concluded that the long−term stability of iron sulfide, the toxicity to organisms of iron sulfide materials in the treated water, and the combination of FeS/PS with other assisted technologies should be focused in future.

1 Introduction

As one of the global environmental problems, water pollution caused by various organic pollutants (such as drugs and metabolites, endocrine disrupting chemicals (EDCs), dyes, plastic additives, pesticides, antibiotics, etc.) is increasingly serious (Petrie, et al., 2015; Pan, et al., 2018; Li, et al., 2019a; Liu, et al., 2019; Bhatt, et al., 2021; Wang, et al., 2021). Advanced oxidation processes based on persulfates (PS−AOPs) can degrade refractory contaminants effectively via radical or non−radical routes, the related reactive oxidation species (ROSs) include SO₄^•−, •OH, O₂^•−, ¹O₂, high valent metals, and electron−transfer process.

Various methods such as ultrasonic (Hao, et al., 2014), thermal (Qi, et al., 2014; Wang and Wang, 2018), electric (Silveira, et al., 2017), photo irradiation (Lin and Wu, 2014) and transition metal (Anipsitakis and Dionysiou, 2004; Wu, et al., 2022) activation have been developed to activate persulfates for pollutant degradation, among which Fe−based catalysts have wider application due to their high reactivity, stability, low cost, environmentally friendly, and simple synthesis (Li, et al., 2021a; Hou, et al., 2021; Liu, et al., 2022a).

As a rate−limiting step in Fe−mediated PS−AOPs, the low regeneration rate from Fe (III) to Fe (II) (0.002–0.01 M⁻¹ s⁻¹) decrease the efficiency of the catalytic reaction (Wang, et al., 2014). Therefore, many strategies have been proposed to accelerate Fe (III)/Fe (II) cycling, such as combining bimetals or adding some reductants (Hou, et al., 2016; Luo, et al., 2020; Xiang, et al., 2020; Zhang, et al., 2022). However, the synthesis of those composite materials is complex and expensive. Therefore, catalyst with auto−enhanced effect may be more promising (Cai, et al., 2022a).

Iron sulfide (FeS), also known as mackinawite, is a kind of tetragonal system common non−toxic mineral (Gong, et al., 2016). With unique molecular structure and surface chemistry, FeS is very effective in fixing divalent metals such as Fe²⁺, Mn²⁺, Ca²⁺, Mg²⁺, Ni²⁺, Cd²⁺ and Hg²⁺ (Wharton et al., 2000; Mariëtte, et al., 2003). Due to the reducibility of FeS, both Fe (II) and S (−II) can act as electron donors. Therefore, both surface−bound Fe (II) and self−released dissolved Fe²⁺ in FeS can serve as continuous iron sources, which can be used to activate persulfate to generate free radicals (Eqs.1, 2) (Fan, et al., 2018a). In addition, the lattice S (−II) on FeS surface can also provide electrons to Fe (III), which can effectively alleviate the excessive consumption of Fe²⁺ and accumulation of Fe³⁺ to maintain the Fe (III)/Fe (II) cycle on the catalyst surface (Eq. 3) (Hou, et al., 2022). Therefore, FeS have been used in recent years to activate PS for the degradation of organic pollutants (Sühnholz, et al., 2021; Xiang, et al., 2022).

The purpose of this paper is to focus on the synthesis, modification, and application of iron sulfide to activate PS for pollutants degradation in recent years. Specifically, this review aims to: 1) review the synthesis methods of iron sulfide particles; 2) Clarify the activation mechanism of iron sulfides for PMS to degrade organic pollutants; and 3) Put forward the existing knowledge gap in exist research and the prospect of future research.

2 Synthesis methods of iron sulfide

2.1 The synthesis of FeS and other FeS_x

FeS particles are usually synthesized by physicochemical and biochemical methods. Physicochemical method is the co−precipitation of different types of iron salts and sulfide salts in the aqueous solution under the condition of hypoxia (Eq. 4). Common source of Fe²⁺ include ferrous chloride (FeCl₂), ferric sulfate heptahydrate (FeSO₄·7H₂O), and ammonium ferrous sulfate (Fe (NH₄)₂·(SO₄)₂·6H₂O). Sodium sulfide (Na₂S) is usually used as the source of S²⁻ (Chen, et al., 2019).

Biosynthetic FeS has much attracted attention due to its environmental friendliness. In general, ferroreductive bacteria (FRBS) and sulfate−reducing bacteria (SRBS) reduce Fe³⁺ and sulfur substances (including sulfate, thiosulfate and elemental sulfur) to S²⁻ and Fe²⁺ respectively, and subsequently to produce FeS nanoparticles (Xie, et al., 2013; Zhou, et al., 2017).

However, FeS particles prepared by traditional methods, especially co−precipitation, tend to rapidly aggregate, which greatly reduces their specific surface area and leads to significant reduction in pollutant removal efficiency (Gong, et al., 2012). Therefore, the preparation of dispersible FeS nanoparticles with small particle size, large specific surface area and high reactivity has attracted extensive attention. Previous studies have explored various techniques to prepare FeS nanoparticles with controllable particle morphology and size distribution, such as reverse micelles (Ajay, et al., 1996), SRB−assisted production (Watson, et al., 2001), high−energy mechanical grinding (Soori, et al., 2016), wet chemical synthesis (Paknikar, et al., 2005), etc.

Recent studies have shown that the presence of polymer stabilizers and surfactants during the synthesis of FeS particles can effectively control the nucleation and growth of nanoparticles through simultaneous electrostatic repulsion and steric hindrance, thus effectively promoting the size control of FeS in aqueous solution. This can not only reduce the aggregation of nanostructured materials, but provide a large number of functional groups to degrade pollutants (Shao, et al., 2016). For example, polyelectrolyte stabilizer carboxymethyl cellulose (CMC) is widely used to modify nanoparticles to enhance the stability of nano FeS due to a large number of carboxylic and hydroxyl groups in its macromolecular chains (Xiong, et al., 2009; Gong, et al., 2012; Gong, et al., 2014; Van Koetsem, 2016). Additionally, other macromolecular biomaterials with similar physical and chemical properties, such as starch, cyclodextrin (CD), chitosan, polysaccharide sodium alginate (SA), etc., have also been used as stabilizers to synthesize nano FeS particles (Shao, et al., 2016; Wu, et al., 2017; Sun, et al., 2018a; Sun, et al., 2018b). The mechanism and processes of synthesis of iron sulfide are exhibited in Figures 1A, B.

FIGURE 1

In aqueous solution, the reducibility of ferrous ions will decrease with the pH value decreasing, which means acidic environment can inhibit the oxidation of ferrous ions to ferric ions (Liu, et al., 2022b). Therefore, the elemental valence state of the synthesized iron sulfide catalysts can also be adjusted. Liu et al. (Liu, et al., 2022a) obtained three kinds of iron sulfides by controlling the pH of the co−precipitation system of iron and sulfide salt to synthesize FeS₂, Fe₇S₈, Fe₃S₄ at , 5, 7, respectively. Hydrothermal method is also a common method for the synthesis of FeS_x. To mix dissolved ferrous salts (FeSO₄·7H₂O, FeCl₂·4H₂O, etc.) with sulfide (thiourea, Na₂S₂O₃, etc.) in a reaction vessel, and keep the vessel at 200°C for 24 h to obtain FeS₂ (Wang, et al., 2020a; Mohamed, et al., 2023). Magnetic Fe₃S₄ was obtained by dissolving FeCl₃·6H₂O and thiourea in ethylene glycol, and then heating in a hydrothermal kettle at 180°C for 12 h (Shi, et al., 2020; Li, et al., 2022b). The mechanism and processes of synthesis of FeSx are exhibited in Figure 1C

Because of the synergistic effect between zero−valent iron (ZVI) and Fe_xS_y (FeS and FeS₂), S−ZVI has high reactivity and selectivity for PS activation to degrade refractory contaminants (Li, et al., 2017a; Wei, et al., 2022). S−ZVI can be synthesized by the “one−pot” process, where ferrous ions react with borohydrides and sulfides. While in the two−step process, sulfur compounds (sodium sulfide and thiosulfate) are added to the synthesized nZVI to form S−ZVI (Li, et al., 2017b). For S−ZVI prepared by one−pot process, FeS_x are distributed both inside and on the surface of ZVI particles, while prepared by two−step method, FeS_x are only formed on the surface of ZVI to form a core−shell structure (Su, et al., 2018; Xu, et al., 2019). In addition, vulcanized micro−scale S−ZVI can be prepared by ball−milling S and ZVI powders under dry conditions (Gu, et al., 2017; He, et al., 2022). The structure, physicochemical properties and performance in PS based Fenton−like reactions of S−ZVI produced by various synthesis methods are mainly affected by the molar ratio of S/Fe (Fan, et al., 2017; Zhang, et al., 2020). Kim et al. (Kim, et al., 2011) reported that the degradation rate of TCE by S−nZVI increased linearly with increasing molar ratio of S/Fe, but decreased with increasing molar ratio of S/Fe when the concentration of Na₂S₂O₄ increased to 2.0 g/L (S/Fe molar ratio was 0.33). However, Han et al. (Han and Yan, 2016) reported that when S/Fe ratio is smaller than 0.025, the degradation rate of TCE becomes faster with the increase of S/Fe molar ratio, and then becomes stable when the molar ratio of S/Fe molar ratio exceeds 0.025. Rajajayavel et al. (Rajajayavel and Ghoshal, 2015) showed that the reducing ability of S−nZVI on TCE was strongly dependent on the S/Fe molar ratio, which provided the highest TCE dechlorination rate in the range of 0.04–0.083. Since the reaction conditions (including synthesis methods, reaction conditions and the properties of the target stain, etc.) used by different researchers to obtain the optimal S/Fe molar ratio are very different, the optimal S/Fe molar ratio values in different studies are not comparable. Based on the above examples, higher S/Fe molar ratio results in more production of FeSx and a larger surface area of the synthesized S−ZVI, thus facilitates the pollutants degradation (Gu, et al., 2017; Huang, et al., 2017). However, excess S content blocks the active Fe site on the surface, which will decrease their activity for PS activation. In addition, the conversion of Fe⁰ to ferric/ferrous (hydrogen) oxides may be intensified at high S/Fe ratio, leading to waste of ZVI with strong reducing capacity (Li, et al., 2017a). Therefore, it is essential to find the optimal S/Fe molar ratio in different reaction systems. The mechanism and processes of synthesis of S−ZVI are exhibited in Figure 2A.

FIGURE 2

2.2 The synthesis of carbon modified FeS

The large surface area of carbon material can greatly reduce the agglomeration of iron−based nanoparticles, thus improving the activity of catalyst. Additionally, strong electron transfer capacity of carbon material can greatly enhance the electron transfer rate of iron−based catalyst (Li, et al., 2018; Ma, et al., 2021). Due to environmentally friendly, good surface physical and chemical properties, and rich oxygen−containing functional groups. Biochar (BC), graphene/graphene oxide (GO)/reductive graphene oxide (rGO), carbon nanotubes (CNTs), graphite carbon nitride (g−C₃N₄), etc., are commonly selected as supports to load FeS. They have been proven to significantly reduce the aggregation of FeS, resulting in better catalytic activity (Ma, et al., 2015; Sun, et al., 2020; Lyu, et al., 2018a; Zhang, et al., 2019a; Bin, et al., 2020; Zhuang, et al., 2020; Han, et al., 2022; Xu, et al., 2022). Generally, the composite of FeS and carbon materials can be obtained by loading iron salt on carbon materials firstly followed with sulfidation process, and freeze−drying, ultrasound or mechanical stirring are widely used loading methods (Sun, et al., 2020; Han, et al., 2022; Xu, et al., 2022). Specifically, these hybrids can be synthesized by mixing carbon materials with ferrous salt and sulfide and then reacted at high temperature under hypoxia condition (Ma, et al., 2015; Lyu, et al., 2018b; Hong, et al., 2021), or carbon materials mixed with pre−synthesized iron sulfide and then treated by hydrothermal method (Li, et al., 2022a). In addition, ball−milling can also achieve the combination of FeS with some carbon materials (Lyu, et al., 2018b; He, et al., 2021; Xia, et al., 2022). The mechanism and processes of synthesis of FeS@Carbon materials are exhibited in Figure 2B.

2.3 The synthesis of multicomponent iron sulfide

Multicomponent iron sulfides exhibit better electrochemical and catalytic properties due to the synergistic effect between metal ions and redox reactions. It can be synthesized by improved hydrothermal methods. Li et al. (Li, et al., 2020) mixed FeCl₂, Co (NO₃)₂, NH₄F and g−C₃N₄ powders at 25°C for 30 min, then heated the mixture in hydrothermal reactor at 140°C for 9 h. Put the Fe−Co precursor and thionoacetamide solution in hydrothermal reactor at 160°C for 6 h, FeCo₂S₄−CN composite can then be obtained. Nie et al. (Nie, et al., 2019) mixed CuCl, FeCl₃·6H₂O and (NH₄)₂S for 30 min, and heated at 200°C for 10 h in hydrothermal reactor to obtain CuFeS₂ NPs. Yan et al. (Yan, et al., 2020) loaded ferric nitrate, cobalt nitrate hexahydrate, ammonium fluoride, urea solution, and reduced graphene oxide film (RGOF) in a hydrothermal kettle at 120°C for 8 h, and then placed the obtained Fe−Co precursor and sodium sulfide solution in the hydrothermal reactor at 160°C for 8 h to obtain FeCo₂S₄/RGOF composite material. The mechanism and processes of synthesis of multicomponent iron sulfide are exhibited in Figure 1C.

3 Applications and mechanism of iron sulfides in AOPs

3.1 Bare FeS

Among various iron sulfides, FeS and FeS₂ are the most commonly used materials for persulfate activation. Since FeS is widely distributed in anoxic environment, and has strong reducibility and high reactivity to organic pollutants, it has been widely used as PS activators for water remediation. As shown in Figure 3, Xu et al. (Xu and Sheng, 2021) used FeS/PMS system to degrade chloramphenicol (CAP), sulfoxamycin (TAP), ciprofloxacin (CIP) and norfloxacin (NOR), and 100% NOR, 100% CIP, 93.5% CAP and 98.5% TAP was degraded within 2 h. Fan et al. (Fan, et al., 2018b) used FeS/PDS system to degrade PCA, and PCA degradation reached nearly 100% in acidic conditions within 240 min. And Sarah et al. used FeS as PDS activator and reached nearly complete removal of TCE within 20 min. These results showed that the FeS/PS system can effectively remediate the organic pollutants containing wastewater. In addition, the catalytic performance of iron−based catalysts in PS based Fenton−like reactions is summarized in Table 1.

FIGURE 3

So far, the mechanism of PS activation through FeS has been considered to be homogeneous and heterogeneous activation. Homogeneous activation refers to the continuous release of dissolved Fe²⁺ by FeS for persulfate activation, and the slow release of Fe²⁺ by FeS can effectively inhibit the self−quenching effect on SO₄^•− to promote the degradation of pollutants (Eqs. 5, 6). Heterogeneous activation refers to the surface of FeS combines Fe (II) or structural ≡Fe (II) for persulfate activation (Yuan, et al., 2015; Chen, et al., 2017; Fan, et al., 2018a; Sühnholz, et al., 2022). Fan et al. (Fan, et al., 2018b) found the presence of binding free radicals (≡SO₄^•−) on the surface of the catalyst through radical quenching experiments, indicating the activation of persulfate by structural Fe (Ⅱ). In addition, it was found that S_aq²⁻ ion itself could not activate PS to produce oxidation radicals (Eq. 7) (Oh, et al., 2011), but SO₄²⁻, S⁰, polysulfide (S_n²⁻) and S⁻ were detected on the surface of FeS after PS activation by X−ray photoelectron spectroscopy (XPS) and FT−IR analysis (Eq. 3 and Eqs. 8, 9), indicating that S (−Ⅱ) in FeS can indirectly provide electrons to PS by facilitating the reduction of Fe (III) to Fe (II). Once S²⁻ is exhausted, Fe (II) regeneration via PS reduction will dominate, since S²⁻ is non−renewable in FeS/PS systems (Eq. 10). In addition, Xu et al. (Xu and Sheng, 2021) also demonstrated that Fe (Ⅳ) was generated in the FeS/PS system, but its contribution to pollutant degradation as reactive species is not significant.

Therefore, the mechanism of FeS for persulfate activation can be proposed in Figures 4A, B, which is also explained as follows:

FIGURE 4

Homogeneous activation process: Firstly, FeS release Fe²⁺ ions (Eqs. 11, 12), which can activate PS to form SO₄^•− (Eqs. 1, 2). The Fe³⁺ can be reduced to Fe²⁺ by reacting with FeS or S²⁻ (Eq. 3, 13). Finally, the regenerated Fe²⁺ continue to maintain PS activation for pollutant degradation.

Heterogeneous activation process: ≡Fe (II) in FeS activates PS as electron donor to produce SO₄^•−(Eqs. 1, 2), then ≡S²⁻ and HS⁻ adsorbed on the surface of FeS can also give electrons to ≡Fe (III) and reduce it to ≡Fe (II), ensuring that the heterogeneous activation process can be continued (Eqs. 14, 15) (Yang, et al., 2022).

In addition, it is worth mentioning that solution pH is one of the most significant influencing factors in the remediation of contaminants by nano−sized FeS, which not only plays an important role in the decomposition of oxidants, but affects the surface charge of FeS−based catalysts and the speciation of substrates to be transformed (Chen, et al., 2019; Li, et al., 2021b). In general, when the solution pH is greater than the pH value at point of zero charge (pH_pzc), the surface of the catalyst is negatively charged, otherwise positively charged (Li, et al., 2020). Under strongly alkaline or strongly acidic conditions, the adsorption capacity is significantly reduced, which not only destroys the active sites on surface and accelerates the corrosion of FeS nanoparticles, but promotes the hydrolysis of bio−modifiers, thus decrease the stability and dispersion of modified nano−FeS. In addition, under strongly alkaline conditions, Fe (II) species will be reduced due to the precipitation of ferric hydroxide in reaction system and produce passivation layer on the surface of FeS. Additionally, negatively charged hydroxide ions compete for absorption with other negatively charged contaminants, which will influence the degradation of contaminants by FeS. Therefore, neutral conditions can provide optimal degradation of pollutants with FeS materials as catalysts for PS.

3.2 FeS_x

FeS₂ can also effectively activate persulfate to degrade pollutants, and the good persulfate activation performance is attributed to the low−valent Fe and S (Fe²⁺ and S⁻¹) (Hou, et al., 2021). By being fully oxidized to SO₄²⁻ and Fe³⁺, FeS₂ can provide 15 electrons. Therefore, FeS₂ can slowly and sustainably releases dissolved Fe²⁺, which activates persulfates to produce reactive free radicals to degrade pollutants (Eqs. 1, 2). Fe²⁺ comes from the water corrosion process of FeS₂ (Oh, et al., 2011), and Fe²⁺ will activate persulfate to be consumed, which will accelerate the water corrosion reaction of FeS₂ (Eq. 10 and Eqs. 16–18). ≡S⁻¹ could also give electrons to persulfate or Fe (III), which would cause Fe²⁺ to continue to form (Liang, et al., 2010). In addition, surface−bound ≡Fe (Ⅱ) can activate molecular oxygen to produce O₂^•− through single electron transfer pathway (Liu, et al., 2015), while surface−bound ≡Fe (Ⅱ) is also reduced, allowing the degradation to continue. The mechanism of FeS₂ for persulfate activation can be proposed in Figures 4C, D.

S−ZVI has been widely used in activating persulfate to degrade refractory organic pollutants, such as tetracycline (Dong, et al., 2019a), bisphenol S (Cai and Zhang, 2022), tetrabromobisphenol A (Quoc, et al., 2021), trichloroethylene (Zhou, et al., 2021a), sulfadiazine (SDZ) (Guo, et al., 2020), etc., indicating that S−ZVI/PS system can effectively treat organic wastewater.

S−ZVI has high electron utilization efficiency, 10–50 times larger than that of unsulfide ZVI. Its sulfide layer can significantly enhance the activity of ZVI and promote to release ferrous ions into the environment (Fan, et al., 2016; Fan, et al., 2018b). This is because there are delocalized electrons in the FeS layer, which has good electrical conductivity and facilitates the transfer of electrons from Fe⁰, thus accelerating the ferrous ions formation (Kim, et al., 2011; Song, et al., 2017). According to electrochemical test, the results of Tafel curve and electrochemical impedance spectroscopy (EIS) also confirm that S−ZVI supports better electron transfer (Turcio−Ortega, et al., 2012; Wang, et al., 2019). Hence, the sulfide layer mainly acts as conductor of electrons to promote the release of Fe²⁺ during the reaction process, rather than source of Fe²⁺ production, which can be used to activate persulfate.

In addition to promoting the release of ferrous ions, the sulfur compounds in the sulfide layer have strong reducing capacity, which can reduce Fe³⁺ to Fe²⁺ (Eq. 3), and these ferrous species will be subsequently used to activate persulfate based on the electron transfer capacity of the sulfide layer (Fan, et al., 2018a; Li, et al., 2019a). Fe⁰ in S−ZVI can also reduce Fe (III) to Fe (Ⅱ) (Eq. 19), and a small amount of FeS₂ in S−ZVI can react with water to produce Fe²⁺ to further enhancing the iron cycle (Eq. 20). The cycle of iron species enables the degradation reaction to be carried out contumely and efficiently (Liu, et al., 2015). The mechanism of S−ZVI for persulfate activation can be proposed in Figure 5.

FIGURE 5

3.3 Carbon modified FeS

FeS@Caobon materials has been widely used to activate persulfate for degradation of organic pollutants, such as petroleum hydrocarbons (Xia, et al., 2022), 2, 4−dichlorophenoxyacetic acid (Hong, et al., 2021), tetracycline (He, et al., 2021), sulfamethazine (Jin, et al., 2022), etc., indicating the potential of FeS@Caobon/PMS system in wastewater remediation.

It has been reported that in heterogeneous activation systems, radicals are first produced near the surface of the activator and then diffused into the solution to degrade pollutants (Liu, et al., 2014), but it has also been reported that both activation and degradation processes may occur near the surface of the carbon−based activator (He, et al., 2019). By measuring the levels of dissolved ion (dissolved Fe²⁺ and total Fe) in the reaction system, and using hydrophobic phenol and 1, 10−phenanthroline to chelate with surface−bound Fe (II) and dissolved Fe²⁺ as quenchers, confirming that the active radicals were mainly generated on the Fe@Carbon surface (He, et al., 2021; Han, et al., 2022). According to the XPS results of catalysts before and after the reaction, the ratio of Fe²⁺ to S²⁻ decreased significantly after the reaction, while that of other sulfur species such as S_n²⁻ and SO₄²⁻ increased, indicating that Fe (II) and S (−II) species were involved in the reaction process, and S (−II) contribute to the conversion of Fe (III) and Fe (II), which will further enhance the activation of PS (Xia, et al., 2022; Yu, et al., 2022). All of these results suggest that surface−bound Fe (II) plays an important role in the PS activation process and generates ROSs on the FeS@Carbon surface. In addition, a small amount of Fe²⁺ dissolved in solution can also directly activate persulfate to produce free radicals (He, et al., 2021).

During the process of contaminants degradation in FeS@Carbon/PS system, carbon materials can prevent the agglomeration of FeS particles to make FeS particles evenly dispersed, which increase the chance of catalyst contact with solution and further increase the concentration of sustainably released Fe²⁺ (Wang, et al., 2017). Besides, the adsorption capacity of carbon materials can make contaminants adsorbed on the surface or inside of composite materials, which make the free radicals produced easier to contact with contaminants (Qu, et al., 2022). Additionally, carbon material itself can act as intermediary of electron transport to accelerate the electron transfer process and improve the degradation efficiency (Qiu, et al., 2021), CNTs and BC has strong electron donor groups on surface, such as hydrogen peroxide (−OOH) and hydroxyl (−OH), which can also activate persulfate to produce more radicals (Eqs. 21−24) (Zhou, et al., 2020; Qiu, et al., 2022). In the composite of FeS and graphene, the bond length between FeS and graphene layer is relatively long, which indicates the weaker bonding, resulting in the higher activity of S to react with SO₅²⁻ during PMS activation. With long bond length, greater electron localization could be facilitated on the S sites to reduce the barrier of pollutant bonding and accelerate the regeneration of metal species (Zhuang, et al., 2020).

Therefore, there are three possible mechanisms of FeS@Carbon to activate persulfate: 1) the adsorption of contaminants by FeS@Carbon; 2) The active sites on catalyst surface, such as oxygen−containing functional groups, Fe²⁺, S²⁻, etc. act as electron donors in reaction process to activate PS and then produce ROSs for pollutants degradation (Eqs. 21−30). In addition, S²⁻ also participates in the reduction of Fe³⁺, enabling the continuous generation of Fe²⁺, which can be further used for the activation of PS (Eqs. 1−3); 3) Carbon materials can accelerate the electron transfer process, which promote the electron transfer from pollutants to PS and further improve the generation rate of radicals on catalyst surface. The mechanism of FeS@Carbon for persulfate activation can be proposed in Figure 6.

FIGURE 6

3.4 Multicomponent iron sulfide

Compared with single−component sulfide, multi−component metal sulfide exhibits better catalytic performance due to its richer redox reactions and synergistic effects between metals (Li, et al., 2019c). Moreover, as an electron donor, the low electronegativity of S²⁻ can promote the redox cycle of metal ions, making multi−component metal sulfide an effective catalyst for the activation of PMS. CuFeS₂ (Nie, et al., 2019), NiFe₂S₄ (Fan, et al., 2022), Cu₂FeSnS₄ (CFTS) (Li, et al., 2022a), CoFe₂S₄ (Li, et al., 2022b) etc., have been widely used in the field of persulfate activation to degrade organic pollutants, showing good pollutant removal effect.

During the process of persulfate activation by polymetallic sulfide, Cu⁺, Co²⁺, Fe²⁺, Ni²⁺ act as active sites to accelerate the generation of radicals such as SO₄^•−, •OH, O₂^•− by destroying the O−O bond of PS, and they are themselves oxidized into Ni³⁺, Fe²⁺, Ni³⁺, Co³⁺. (Eqs. 31, 32). Due to the strong reducibility of sulfur species such as S²⁻ and S₂²⁻, the high valent metal ions formed can be reduced to low valent states (Eqs. 33−35). The reduction of Fe³⁺ by Cu⁺ and Ni²⁺ is easy to achieve, which is thermodynamically advantageous (Eqs. 36, 37) (Nie, et al., 2019; Fan, et al., 2022). Therefore, the synergistic interaction between these metals on the catalyst surface facilitates interfacial electron transfer. In addition, ROSs produced by hydrolysis of persulfate can also oxidize high−valent metals to low−valent metals (Eq. 10), and the regenerated active sites such as Cu⁺, Ni²⁺ and Fe²⁺ on the surface can again participate in the continuous generation of ROSs induced by persulfate activation. In the CFTS/PMS system, there is S→M σ bond ((M = Cu, Fe, and Sn) which is favorable for electron transfer and contribute to form ≡Fe (II)*. It has been reported that Sn(Ⅱ) can also activate persulfate to produce active free radicals due to the synergy between ≡Fe (II)* and Sn (Eqs. 38−40) (Kong, et al., 2019). The mechanism of multicomponent iron sulfide for persulfate activation can be proposed in Figures 7A−C.

FIGURE 7

Considering the poor dispersion of metal sulfides and large amount of metal ions leaching, the researchers further modified these catalysts. For example, Li. et al. (Li, et al., 2020) used FeCo₂S₄ modified g−C₃N₄ (FeCo₂S₄−CN) composite for PMS activation to degrade sulfamethoxazole (SMX). As shown in Figure 7D, in this system, there is a synergistic effect between FeCo₂S₄ and g−C₃N₄, thus the removal rate of SMX is higher than that of FeCo₂S₄/PMS, g−C₃N₄/PMS and PMS alone. Moreover, due to the synergistic effect between metal ions and g−C₃N₄, iron and cobalt ions, excessive leaching of metal ions is avoided. Li. et al. (Li, et al., 2022a) synthesized CoFe₂S₄/BC catalyst by a two−step hydrothermal method and combined it with PMS for the degradation of sodium sulfadimethacil (SMT). As shown in Figure 7E, in this system, in addition to the free radical pathway induced by the metal active site, there is also a non−free radical pathway. On the one hand, electrons can be transferred directly from the contaminants to the PMS through the active center of BC, leading to the direct decomposition of the pollutant. On the other hand, BC can activate the O−O bond in the PMS and directly oxidize the target compound.

4 Hybrid activation systems

4.1 Photoassisted systems

FeS and its derivatives are considered promising candidates for photocatalytic water treatment due to their ability to absorb visible and/or ultraviolet light, narrow optical band gap, and charge transport properties (Ayodhya and Veerabhadram, 2018; Li, et al., 2021a). Bibhutibhushan et al. (Show, et al., 2017) synthesized FeS nanospheres by a simple electrochemical route, which act as photocatalysts to successfully degrade alizarin red S (ARS), methylene blue (MB), rose red (RB) and phenol, and no degradation of these dyes was observed in the dark and very slow degradation was observed in the absence of FeS but the presence of light, which indicates that FeS has a strong synergistic effect when working together with photoassisted technologies.

During the reaction process, when FeS are exposed to visible light, illumination causes the excitation of valence band electrons in the conduction band, and this charge separation leads to the formation of electron−hole pairs (Suroshe, et al., 2018). Photogenerated electron (e⁻)−hole pairs (h⁺) can react with adsorbed surface species such as O₂, H₂O, and OH⁻ to form ROSs such as O²⁻ and •OH, for pollutants degradation (Eqs. 41−45) (Nair, et al., 2011; Chabri, et al., 2016). In addition, the Fe²⁺ and S²⁻ in FeS can react as persulfate activator for pollutants degradation. Additionally, visible light will accelerate the cyclic conversion between Fe³⁺ and Fe²⁺ (Eq. 46) (Chen, et al., 2021), further improving the continuous degradation. Hence, possible light−induced reactions can be proposed as Eqs. 1−3 and Eqs. 41–46:

4.2 Electro−assisted systems

Electrochemical advanced oxidation processes (EAOPs) have attracted increasing attention due to their environmental compatibility, ease of scaling up and high efficiency in degrading refractory contaminants compared to conventional advanced oxidation processes (Luo, et al., 2020). Iron sulfide shows good electrocatalytic performance due to its excellent electrical conductivity, hybrid d orbital, and general redox properties (Li, et al., 2021b), which has great potential in the field of wastewater treatment when combined with EAOPs.

Ammar. et al. (Ammar, et al., 2015) used pyrite as a heterogeneous source of Fe²⁺ catalyst to degrade tyrosol (TY) in an electro−assisted process, which possesses superior performance due to the self−regulation of Fe²⁺ content in the medium. As shown in Figure 8A, (Labiadh, et al., 2015),used pyrite/EF system to generate H₂O₂in situ and regenerate Fe²⁺ to completely remove azo dye (4−amino−3−hydroxy−2−p−toluene −naphthalene−1−sulfonic acid) (AHPS) from water, the mineralization rate of pyrite/EF system was superior to that of EF system alone under the same conditions, specifically, more than 90% TOC was removed in pyrite/EF within 300 min, whereas in the same reaction time only 70% TOC was removed with the conventional EF process. This is due to the self−regulation effect of pyrite on pH and soluble Fe²⁺ without additional acidification. As shown in Figure 8C, Ye et al. (Ye, et al., 2020) used FeS₂/C nanocomposites as highly active, stable and recyclable catalysts to treat fluoxetine in polyphase EF system, which achieved an impressive 90% TOC removal, while conventional EF processes produce a maximum TOC removal of 60%. The good performance of pyrite/EF system was attributed to the large amount of •OH produced by the pyrite induced Fenton reaction, which mainly attributed to the following aspects: (1) The mass transfer restriction of FeS₂ is very small, and it can act as the transfer intermediate of Fe²⁺ to participate in the homogeneous reaction to produce •OH. Meanwhile, pyrite can provide rich active sites, and ≡Fe (II) can activate H₂O₂ to produce •OH by Fe−S bond. (2) the ≡Fe (II) on the surface of FeS₂ can promote the activation of molecule O₂, thus accelerating the formation of O₂^•− (Liu, et al., 2015). In addition, the boron−doped diamond (BDD) anode used in the electro−assisted system also contributes to the generation of physical adsorption •OH in pyrite/EF system. The heterogeneous mechanism of the system is dominant because the concentration of dissolved iron is relatively low. The mechanism of electro−assisted pyrite/persulfate system for contaminants degradation can be proposed in Figures 8B, D.

FIGURE 8

4.3 Ultrasonic−assisted technology

Increasing attention has been paid to the application of ultrasonic (US) combined with advanced oxidation technology in water treatment. On the one hand, US has strong mechanical effect, which can enhance the mass transfer between interfaces, remove the passivation film on the metal surface and make the surface regenerate continuously. These properties can overcome the heterogeneous mass transfer barrier in the process of degrading organic matter, and achieve good contaminants removal effect (Xiang, et al., 2022). On the other hand, US lead to form cavitation effect, and its local high temperature and high pressure can produce •OH, O₂^•− and other ROSs (Chi, et al., 2022; Savun−Hekimoğlu, 2020; Wei, et al., 2017).

Chi et al. (Chi, et al., 2022) used US to enhance ferrous sulfide (FeS) to activate persulfate (PDS) for 2’−deoxycoformycin (DCF) degradation. US/FeS/PDS system with excellent activity presented an optimal DCF degradation efficiency (98.9%), which was 56.7, 5.81, 1.48 times than that of US, US/PDS and FeS/PDS systems (Figure 9B). Wei. et al. (Xiang, et al., 2022) demonstrated good degradation effect of carbamazepine (CBZ) by using ultrasonic−enhanced FeS/PDS system, which can remove 94.2% CBZ in 60 min, while FeS/PDS system can only remove 71.2% CBZ under same conditions (Figure 9A), confirming the synergistic enhancement effect of US and FeS contributed to the degradation of contaminants.

FIGURE 9

In ultrasonic enhanced FeS/persulfate system, US can promote the interfacial sulfur−iron electron transfer and the disintegration of passivation layer, which avoid the passivation and deactivation of FeS, and provide redox energy between S²⁻/S_x²⁻ and Fe²⁺/Fe³⁺ to promote continuous production of Fe²⁺. Additionally, US can directly activate PDS, H₂O and dissolved oxygen to form SO₄^•− and •OH. In a word, US greatly promotes both heterogeneous and homogeneous iron cycles in the system. Hence, possible US−assisted reactions can be summarized as Eqs.1−3, Eqs. 47, 48, and the mechanism of US−assisted FeS/persulfate system for contaminants degradation can be proposed in Figure 9C

4.4 Microwave assisted technology

Microwave (MW) activation of persulfate has been widely studied. It has been proved to be superior to conventional thermal activation in terms of accelerating reaction rate, increasing yield and selectively activating or inhibiting reaction pathways, thus leading to higher degradation rate and significant savings in energy consumption and treatment time (Qi, et al., 2014). Wang et al. (Wang, et al., 2020a) used microwave radiation combined with FeS to activate persulfate to treat dinitrodiazophenol in explosive production wastewater. The Chemical Oxygen Demand (COD) removal efficiency of the MW–FeS/PS process reached 76.16%, which was 2.62, 2.57, and 1.42 times than that of MW/FeS, FeS/PS and MW/PS systems, indicating the strong synergistic effect between FeS and MW.

In MW–FeS/PS system, in addition to the persulfate activation performance of FeS, MW radiation can not only activate PS to produce SO₄^•− by its thermal effect, but make some functional groups and structures on organic pollutants vulnerable. Furthermore, the MW and FeS have strong synergic effect. Therefore, microwave−assisted FeS activation of persulfate can show higher treatment efficiency and higher PS utilization efficiency (Wang, et al., 2020b).

5 Reusability and stability

The reusability and stability of FeS−based catalysts are very important for their practical application. In general, FeS−based catalysts can maintain satisfactory catalytic performance in multiple continuous cycles due to the internal Fe (Ⅲ)/Fe (Ⅱ) cycle, which is shown in Eqs 49, 50:

As shown in Figure 10, the Cu₂FeSnS₄/PS system degraded more than 80% of BPA within 45 min after three reuse cycles (Yangju et al., 2019). In S−Fe@C/PDS system, no evident decline on Rh B degradation suggested the catalyst could be at least reused for five times (Yu, et al., 2022). In FeS₂/C−EF system, a slight but progressive performance decrease was observed after five cycles, with only 61% fluoxetine removal achieved at 60 min (Ye, et al., 2020). Fortunately, the activity of FeS−based catalysts can be restored by various treatments, such as washing with organic solvents (Ye, et al., 2020), ultrasonic treatment (Zhao, et al., 2020), and pickling (Peng, et al., 2020).

FIGURE 10

6 Reactive oxidation species

In the PS based Fenton−like reactions activated by FeS−based materials, organics were normally degraded through two oxidation pathways involving free radical (e.g., •OH, SO₄^•− and O₂^•−) and non−radical (e.g., ¹O₂ and Fe (IV) = O) reactive oxidation species (Li, et al., 2021b).

In general, SO₄^•− and •OH are most frequently detected radicals during PS activation. Fe (II) in the FeS−based catalysts reacts with PS and split O−O bond to form SO₄^•− (Eqs 1, 2). Fan et al. (Fan, et al., 2018a) proposed that surface−bound radicals (e.g., •OH_ads and SO₄^•−_ads) produced by the combination of surface Fe (II) and PS can diffuse from the catalyst surface and convert into free radicals (e.g., •OH_free and SO₄^•−_free) to degrade contaminants. In PS activation process, •OH may be generated by two main pathways, one is produced by the reaction of SO₄^•− with H₂O (Eq. 25), and the other is formed by radical conversion reaction of SO₄^•− with OH⁻ under neutral or alkaline conditions (Eq. 26) (Zhao, et al., 2016). It was found that the main ROSs in the activation process of PS is severely pH−dependent, with SO₄^•− under acidic and •OH at alkaline conditions, respectively (Feng, et al., 2015). Usually, •OH always transform into O₂^•− under alkaline conditions through a complex series of radical chain steps (Li, et al., 2016; Ma, et al., 2019). Additionally, some FeS−based materials can also react directly with PS to produce O₂^•− (Jin, et al., 2022).

Non−radical reactive oxidation species such as ¹O₂ and Fe (IV) = O can also be produced in the PS activation process by FeS−based materials. ¹O₂ can be formed by the self−decomposition of PMS at alkaline condition (Eq. 53) (Zhou, et al., 2021a). Carbon modified FeS materials, such as FeS@GO and FeS@BC, can also form ¹O₂ in PS activation, in which carbonaceous materials play a key role in the generation of ¹O₂ (Wang, et al., 2023b). Furthermore, ¹O₂ can result from the conversion of O₂^•− and H₂O (Eqs. 54, 55) (Zhou, et al., 2021b; Cai, et al., 2022b; Li, et al., 2022b). High−valent iron−oxo species (e.g., ≡Fe (Ⅳ) = O and ≡FeV = O) is a burgeoning ROS produced in PS activation (Li, et al., 2021a). In the activation of PS by FeS−based catalysts, the aqueous Fe (II) released from the FeS surface reacts with the PS and contribute to the formation of Fe (IV) (Eqs. 56, 57), which then effectively degrades the contaminants through non− radical pathways (Xu and Sheng, 2021).

7 Toxicity assessment

To ensure safe environmental applications of FeS−based catalysts, it is necessary to conduct toxicity assessments of the catalysts and their degradation intermediates to understand the potential environmental risks to ecosystems and human health. Bare Iron sulfide (FeS) nanoparticles were reported to bind with DNA, limiting the ability of DNA to interact with other nucleic acids and amino acids (Hatton and Rickard, 2008). Rickard, D. et al. (Rickard, et al., 2011) proposed that when the concentration of FeS nanoparticles is lower than its solubility limit, it will cause incision in DNA molecules, and pose genotoxicity by reacting with polynucleic acids when above solubility limit. Furthermore, FeS particles will inhibit the growth of microorganisms and plants. For instance, in the presence of FeS nanoparticles of 2 × 10⁻⁵ M to 5 × 10⁻³ M, the growth rate of E. coli is reduced under anaerobic conditions. FeS particles may impede nutrients uptake and will decrease seed yield and viability when deposited on the roots of wild rice plants (Pastor, et al., 2017). Zheng et al. (Zheng, et al., 2018) illustrated that exposure to CMC−FeS nanoparticles significantly damaged DNA and proteins due to nanoparticle induced oxidative stress. At present, although the biotoxicity of FeS−based catalysts in advanced oxidation processes have been gradually carried out, the evaluation of catalyst toxicity to water environment and the targeted regulation of highly toxic intermediates to harmless transformation are still insufficient.

8 Conclusion and future research expected

References

• 1

  AjayC., RameshK. S.CharterD. S. A., DadyB. D. (1996). Iron sulfide catalysts for coal liquefaction prepared using a micellar technique. Ind. Eng. Chem. Res., 35, 2916, 2919. 10.1021/ie950694y9)

  • CrossRef
  • Google Scholar

• 2

  AmmarS.OturanM. A.LabiadhL.GuersalliA.AbdelhediR.OturanN.et al (2015). Degradation of tyrosol by a novel electro−Fenton process using pyrite as heterogeneous source of iron catalyst. Water Res.74, 77–87. 10.1016/j.watres.2015.02.006

  • CrossRef
  • Google Scholar

• 3

  AnipsitakisG. P.DionysiouD. D. (2004). Radical generation by the interaction of transition metals with common oxidants. Environ. Sci. Technol.38 (13), 3705–3712. 10.1021/es035121o

  • CrossRef
  • Google Scholar

• 4

  AyodhyaD.VeerabhadramG. (2018). A review on recent advances in photodegradation of dyes using doped and heterojunction based semiconductor metal sulfide nanostructures for environmental protection. Mater Today Energy9, 83–113. 10.1016/j.mtener.2018.05.007

  • CrossRef
  • Google Scholar

• 5

  BhattP.GangolaS.BhandariG.ZhangW.MaithaniD.MishraS.et al (2021). New insights into the degradation of synthetic pollutants in contaminated environments. Chemosphere268, 128827. 10.1016/j.chemosphere.2020.128827

  • CrossRef
  • Google Scholar

• 6

  BinQ.LinB.ZhuK.ShenY.ManY.WangB.et al (2020). Superior trichloroethylene removal from water by sulfide−modified nanoscale zero−valent iron/graphene aerogel composite. J. Environ. Sci.88, 90–102. 10.1016/j.jes.2019.08.011

  • CrossRef
  • Google Scholar

• 7

  CaiH.ZouJ.LinJ.LiJ.HuangY.ZhangS.et al (2022a). Sodium hydroxide−enhanced acetaminophen elimination in heat/peroxymonosulfate system: Production of singlet oxygen and hydroxyl radical. Chem. Eng. J.429 (2), 132438. 10.1016/j.cej.2021.132438

  • CrossRef
  • Google Scholar

• 8

  CaiJ.ZhangY. (2022). Enhanced degradation of bisphenol S by persulfate activated with sulfide−modified nanoscale zero−valent iron. Environ. Sci. Pollut. R.29 (6), 8281–8293. 10.1007/s11356-021-16156-8

  • CrossRef
  • Google Scholar

• 9

  CaiY.FanJ.LiuZ. (2022b). Enhanced degradation of tetracycline over FeS−based Fenton−like process: Autocatalytic decomposition of H₂O₂ and reduction of Fe(III). J. Hazard Mater436, 129092. 10.1016/j.jhazmat.2022.129092

  • CrossRef
  • Google Scholar

• 10

  ChabriS.DharaA.ShowB.AdakD.SinhaA.MukherjeeN. (2016). Mesoporous CuO–ZnO p–n heterojunction based nanocomposites with high specific surface area for enhanced photocatalysis and electrochemical sensing. Catal. Sci. Technol.6 (9), 3238–3252. 10.1039/c5cy01573a

  • CrossRef
  • Google Scholar

• 11

  ChenG.YuY.LiangL.DuanX.LiR.LuX.et al (2021). Remediation of antibiotic wastewater by coupled photocatalytic and persulfate oxidation system: A critical review. J. Hazard Mater408, 124461. 10.1016/j.jhazmat.2020.124461

  • CrossRef
  • Google Scholar

• 12

  ChenH.ZhangZ.FengM.LiuW.WangW.YangQ.et al (2017). Degradation of 2,4−dichlorophenoxyacetic acid in water by persulfate activated with FeS (mackinawite). Chem. Eng. J.313, 498–507. 10.1016/j.cej.2016.12.075

  • CrossRef
  • Google Scholar

• 13

  ChenY.LiangW.LiY.WuY.ChenY.XiaoW.et al (2019). Modification, application and reaction mechanisms of nano−sized iron sulfide particles for pollutant removal from soil and water: A review. Chem. Eng. J.362, 144–159. 10.1016/j.cej.2018.12.175

  • CrossRef
  • Google Scholar

• 14

  ChiN.LiuJ.FengL.GuoZ.ChenY.PanT.et al (2022). FeS redox power motor for PDS continuous generation of active radicals on efficient degradation and removal of diclofenac: Role of ultrasonic. Chemosphere300, 134574. 10.1016/j.chemosphere.2022.134574

  • CrossRef
  • Google Scholar

• 15

  DongH.HouK.QiaoW.ChengY.ZhangL.WangB.et al (2019a). Insights into enhanced removal of TCE utilizing sulfide−modified nanoscale zero−valent iron activated persulfate. Chem. Eng. J.359, 1046–1055. 10.1016/j.cej.2018.11.080

  • CrossRef
  • Google Scholar

• 16

  DongH.WangB.LiL.WangY.NingQ.TianR.et al (2019b). Activation of persulfate and hydrogen peroxide by using sulfide−modified nanoscale zero−valent iron for oxidative degradation of sulfamethazine: A comparative study. Sep. Purif. Technol.218, 113–119. 10.1016/j.seppur.2019.02.052

  • CrossRef
  • Google Scholar

• 17

  El AsmarR.BaalbakiA.Abou KhalilZ.NaimS.BejjaniA.GhauchA. (2021). Iron−based metal organic framework MIL−88−A for the degradation of naproxen in water through persulfate activation. Chem. Eng. J.405, 126701. 10.1016/j.cej.2020.126701

  • CrossRef
  • Google Scholar

• 18

  FanD.LanY.TratnyekP. G.JohnsonR. L.FilipJ.O CarrollD. M.et al (2017). Sulfidation of Iron−Based materials: A review of processes and implications for water treatment and remediation. Environ. Sci. Technol.51 (22), 13070–13085. 10.1021/acs.est.7b04177

  • CrossRef
  • Google Scholar

• 19

  FanD.O'BrienJ. G.TratnyekP. G.JohnsonR. L. (2016). Sulfidation of nano zerovalent iron (nZVI) for improved selectivity during In−Situ chemical reduction (ISCR). Environ. Sci. Technol.50 (17), 9558–9565. 10.1021/acs.est.6b02170

  • CrossRef
  • Google Scholar

• 20

  FanJ.GuL.WuD.LiuZ. (2018a). Mackinawite (FeS) activation of persulfate for the degradation of p−chloroaniline: Surface reaction mechanism and sulfur−mediated cycling of iron species. Chem. Eng. J.333, 657–664. 10.1016/j.cej.2017.09.175

  • CrossRef
  • Google Scholar

• 21

  FanJ.ZhaoZ.DingZ.LiuJ. (2018b). Synthesis of different crystallographic FeOOH catalysts for peroxymonosulfate activation towards organic matter degradation. Rsc Adv.8 (13), 7269–7279. 10.1039/c7ra12615h

  • CrossRef
  • Google Scholar

• 22

  FanS.ShangJ.KulanS.HeX.WangX.NasenB.et al (2022). Enhanced degradation of carbamazepine in water over SC−modified NiFe2S4 nanocomposites by peroxymonosulfate activation. Chem. Eng. J.450, 138190. 10.1016/j.cej.2022.138190

  • CrossRef
  • Google Scholar

• 23

  FengM.QuR.ZhangX.SunP.SuiY.WangL.et al (2015). Degradation of flumequine in aqueous solution by persulfate activated with common methods and polyhydroquinone−coated magnetite/multi−walled carbon nanotubes catalysts. Water Res.85, 1–10. 10.1016/j.watres.2015.08.011

  • CrossRef
  • Google Scholar

• 24

  FuX.ZhangJ.ZhaoH.ZhangS.NieT.ZhangY.et al (2020). Enhanced peroxymonosulfate activation by coupling zeolite−supported nano−zero−valent iron with weak magnetic field. Sep. Purif. Technol.230, 115886. 10.1016/j.seppur.2019.115886

  • CrossRef
  • Google Scholar

• 25

  GongY.LiuY.XiongZ.KabackD.ZhaoD. (2012). Immobilization of mercury in field soil and sediment using carboxymethyl cellulose stabilized iron sulfide nanoparticles. Nanotechnology23 (29), 294007. 10.1088/0957-4484/23/29/294007

  • CrossRef
  • Google Scholar

• 26

  GongY.LiuY.XiongZ.ZhaoD. (2014). Immobilization of mercury by carboxymethyl cellulose stabilized iron sulfide nanoparticles: Reaction mechanisms and effects of stabilizer and water chemistry. Environ. Sci. Technol.48 (7), 3986–3994. 10.1021/es404418a

  • CrossRef
  • Google Scholar

• 27

  GongY.TangJ.ZhaoD. (2016). Application of iron sulfide particles for groundwater and soil remediation: A review. Water Res.89, 309–320. 10.1016/j.watres.2015.11.063

  • CrossRef
  • Google Scholar

• 28

  GuX.LuS.GuoX.SimaJ.QiuZ.SuiQ. (2015). Oxidation and reduction performance of 1,1,1−trichloroethane in aqueous solution by means of a combination of persulfate and zero−valent iron. Rsc Adv.5 (75), 60849–60856. 10.1039/c5ra07655b

  • CrossRef
  • Google Scholar

• 29

  GuY.WangB.HeF.BradleyM. J.TratnyekP. G. (2017). Mechanochemically sulfidated microscale zero valent iron: Pathways, kinetics, mechanism, and efficiency of trichloroethylene dechlorination. Environ. Sci. Technol.51 (21), 12653–12662. 10.1021/acs.est.7b03604

  • CrossRef
  • Google Scholar

• 30

  GuoW.ZhaoQ.DuJ.WangH.LiX.RenN. (2020). Enhanced removal of sulfadiazine by sulfidated ZVI activated persulfate process: Performance, mechanisms and degradation pathways. Chem. Eng. J.388, 124303. 10.1016/j.cej.2020.124303

  • CrossRef
  • Google Scholar

• 31

  HanM.LiangL.WangY.DengY.ZhangQ.YeY.et al (2022). Peroxymonosulfate activation by sponge−based FeS material for efficient degradation of tetracycline: The critical role of sponge. J. Water Process Eng.46, 102605. 10.1016/j.jwpe.2022.102605

  • CrossRef
  • Google Scholar

• 32

  HanY.YanW. (2016). Reductive dechlorination of trichloroethene by Zero−valent iron nanoparticles: Reactivity enhancement through sulfidation treatment. Environ. Sci. Technol.50 (23), 12992–13001. 10.1021/acs.est.6b03997

  • CrossRef
  • Google Scholar

• 33

  HaoF.GuoW.WangA.LengY.LiH. (2014). Intensification of sonochemical degradation of ammonium perfluorooctanoate by persulfate oxidant. Ultrason. Sonochem21 (2), 554–558. 10.1016/j.ultsonch.2013.09.016

  • CrossRef
  • Google Scholar

• 34

  HattonB.RickardD. (2008). Nucleic acids bind to nanoparticulate iron (II) monosulphide in aqueous solutions. Orig. Life Evol. Biosphere38 (3), 257–270. 10.1007/s11084-008-9132-7

  • CrossRef
  • Google Scholar

• 35

  HeJ.TangJ.ZhangZ.WangL.LiuQ.LiuX. (2021). Magnetic ball−milled FeS@biochar as persulfate activator for degradation of tetracycline. Chem. Eng. J.404, 126997. 10.1016/j.cej.2020.126997

  • CrossRef
  • Google Scholar

• 36

  HeJ.XiaoY.TangJ.ChenH.SunH. (2019). Persulfate activation with sawdust biochar in aqueous solution by enhanced electron donor−transfer effect. Sci. Total Environ.690, 768–777. 10.1016/j.scitotenv.2019.07.043

  • CrossRef
  • Google Scholar

• 37

  HeM.LiW.XieZ.YangS.HeC.XiongZ.et al (2022). Peracetic acid activation by mechanochemically sulfidated zero valent iron for micropollutants degradation: Enhancement mechanism and strategy for extending applicability. Water Res.222, 118887. 10.1016/j.watres.2022.118887

  • CrossRef
  • Google Scholar

• 38

  HongQ.LiuC.WangZ.LiR.LiangX.WangY.et al (2021). Electron transfer enhancing Fe(II)/Fe(III) cycle by sulfur and biochar in magnetic FeS@biochar to active peroxymonosulfate for 2,4−dichlorophenoxyacetic acid degradation. Chem. Eng. J.417, 129238. 10.1016/j.cej.2021.129238

  • CrossRef
  • Google Scholar

• 39

  HouK.PiZ.ChenF.HeL.YaoF.ChenS.et al (2022). Peroxymonosulfate (PMS) activation by mackinawite for the degradation of organic pollutants: Underappreciated role of dissolved sulfur derivatives. Sci. Total Environ.811, 151421. 10.1016/j.scitotenv.2021.151421

  • CrossRef
  • Google Scholar

• 40

  HouK.PiZ.YaoF.WuB.HeL.LiX.et al (2021). A critical review on the mechanisms of persulfate activation by iron−based materials: Clarifying some ambiguity and controversies. Chem. Eng. J.407, 127078. 10.1016/j.cej.2020.127078

  • CrossRef
  • Google Scholar

• 41

  HouX.HuangX.AiZ.ZhaoJ.ZhangL. (2016). Ascorbic acid/Fe@Fe₂O₃: A highly efficient combined fenton reagent to remove organic contaminants. J. Hazard Mater310, 170–178. 10.1016/j.jhazmat.2016.01.020

  • CrossRef
  • Google Scholar

• 42

  HuangD.HeJ.GuY.HeF. (2017). Mechanochemically sulfidated zero valent iron as an efficient Fenton−like catalyst for degradation of organic contaminants. Acta Chim. Sin.75 (9), 866. 10.6023/a17020060

  • CrossRef
  • Google Scholar

• 43

  HussainI.LiM.ZhangY.LiY.HuangS.DuX.et al (2017). Insights into the mechanism of persulfate activation with nZVI/BC nanocomposite for the degradation of nonylphenol. Chem. Eng. J.311, 163–172. 10.1016/j.cej.2016.11.085

  • CrossRef
  • Google Scholar

• 44

  JinZ.LiY.DongH.XiaoS.XiaoJ.ChuD.et al (2022). A comparative study on the activation of persulfate by mackinawite@biochar and pyrite@biochar for sulfamethazine degradation: The role of different natural iron−sulfur minerals doping. Chem. Eng. J.448, 137620. 10.1016/j.cej.2022.137620

  • CrossRef
  • Google Scholar

• 45

  KimE.KimJ.AzadA.ChangY. (2011). Facile synthesis and characterization of Fe/FeS nanoparticles for environmental applications. Acs Appl. Mater Inter3 (5), 1457–1462. 10.1021/am200016v

  • CrossRef
  • Google Scholar

• 46

  KongL.FangG.ChenY.XieM.ZhuF.MaL.et al (2019). Efficient activation of persulfate decomposition by Cu₂FeSnS₄ nanomaterial for bisphenol A degradation: Kinetics, performance and mechanism studies. Appl. Catal. B Environ.253, 278–285. 10.1016/j.apcatb.2019.04.069

  • CrossRef
  • Google Scholar

• 47

  LabiadhL.OturanM. A.PanizzaM.HamadiN. B.AmmarS. (2015). Complete removal of AHPS synthetic dye from water using new electro−fenton oxidation catalyzed by natural pyrite as heterogeneous catalyst. J. Hazard Mater297, 34–41. 10.1016/j.jhazmat.2015.04.062

  • CrossRef
  • Google Scholar

• 48

  LiH.WanJ.MaY.WangY. (2016). Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero−valent iron. Sci. Total Environ.562, 889–897. 10.1016/j.scitotenv.2016.04.093

  • CrossRef
  • Google Scholar

• 49

  LiJ.LiuQ.GouG.KangS.TanX.TanB.et al (2022c). New insight into the mechanism of peroxymonosulfate activation by Fe₃S₄: Radical and non−radical oxidation. Sep. Purif. Technol.286, 120471. 10.1016/j.seppur.2022.120471

  • CrossRef
  • Google Scholar

• 50

  LiJ.RenY.JiF.LaiB. (2017a). Heterogeneous catalytic oxidation for the degradation of p−nitrophenol in aqueous solution by persulfate activated with CuFe₂O₄ magnetic nano−particles. Chem. Eng. J.324, 63–73. 10.1016/j.cej.2017.04.104

  • CrossRef
  • Google Scholar

• 51

  LiJ.WanY.LiY.YaoG.LaiB. (2019a). Surface Fe(III)/Fe(II) cycle promoted the degradation of atrazine by peroxymonosulfate activation in the presence of hydroxylamine. Appl. Catal. B Environ.256, 117782. 10.1016/j.apcatb.2019.117782

  • CrossRef
  • Google Scholar

• 52

  LiJ.YangL.LaiB.LiuC.HeY.YaoG.et al (2021a). Recent progress on heterogeneous Fe−based materials induced persulfate activation for organics removal. Chem. Eng. J.414, 128674. 10.1016/j.cej.2021.128674

  • CrossRef
  • Google Scholar

• 53

  LiJ.ZhangX.SunY.LiangL.PanB.ZhangW.et al (2017b). Advances in sulfidation of zerovalent iron for water decontamination. Environ. Sci. Technol.51 (23), 13533–13544. 10.1021/acs.est.7b02695

  • CrossRef
  • Google Scholar

• 54

  LiJ.ZouJ.ZhangS.CaiH.HuangY.LinJ.et al (2022b). Sodium tetraborate simultaneously enhances the degradation of acetaminophen and reduces the formation potential of chlorinated by−products with heat−activated peroxymonosulfate oxidation. Water Res.224, 119095. 10.1016/j.watres.2022.119095

  • CrossRef
  • Google Scholar

• 55

  LiX.LiuX.LinC.ZhangH.ZhouZ.FanG.et al (2019b). Activation of peroxymonosulfate by magnetic catalysts derived from drinking water treatment residuals for the degradation of atrazine. J. Hazard Mater366, 402–412. 10.1016/j.jhazmat.2018.12.016

  • CrossRef
  • Google Scholar

• 56

  LiX.ZhouM.PanY. (2018). Enhanced degradation of 2,4−dichlorophenoxyacetic acid by pre−magnetization Fe−C activated persulfate: Influential factors, mechanism and degradation pathway. J. Hazard Mater353, 454–465. 10.1016/j.jhazmat.2018.04.035

  • CrossRef
  • Google Scholar

• 57

  LiY.DongH.LiL.TangL.TianR.LiR.et al (2021b). Recent advances in waste water treatment through transition metal sulfides−based advanced oxidation processes. Water Res.192, 116850. 10.1016/j.watres.2021.116850

  • CrossRef
  • Google Scholar

• 58

  LiY.LiJ.PanY.XiongZ.YaoG.XieR.et al (2020). Peroxymonosulfate activation on FeCo₂S₄ modified g−C₃N₄ (FeCo₂S₄−CN): Mechanism of singlet oxygen evolution for nonradical efficient degradation of sulfamethoxazole. Chem. Eng. J.384, 123361. 10.1016/j.cej.2019.123361

  • CrossRef
  • Google Scholar

• 59

  LiY.ZhaoX.YanY.YanJ.PanY.ZhangY.et al (2019c). Enhanced sulfamethoxazole degradation by peroxymonosulfate activation with sulfide−modified microscale zero−valent iron (S−mFe⁰): Performance, mechanisms, and the role of sulfur species. Chem. Eng. J.376, 121302. 10.1016/j.cej.2019.03.178

  • CrossRef
  • Google Scholar

• 60

  LiY.ZhouY.NiR.ShangJ.ChengX. (2022a). Degradation of sulfamethazine sodium salt by peroxymonosulfate activated by biochar supported CoFe₂S₄: Performance, mechanism and response surface method optimization. J. Environ. Chem. Eng.10 (5), 108059. 10.1016/j.jece.2022.108059

  • CrossRef
  • Google Scholar

• 61

  LiangC.GuoY.ChienY.WuY. (2010). Oxidative degradation of MTBE by Pyrite−Activated persulfate: Proposed reaction pathways. Ind. Eng. Chem. Res.49 (18), 8858–8864. 10.1021/ie100740d

  • CrossRef
  • Google Scholar

• 62

  LinC.WuM. (2014). UV/S₂O₈²⁻ process for degrading polyvinyl alcohol in aqueous solutions. Chem. Eng. Process. Process Intensif.85, 209–215. 10.1016/j.cep.2014.08.012

  • CrossRef
  • Google Scholar

• 63

  LiuH.YaoJ.WangL.WangX.QuR.WangZ. (2019). Effective degradation of fenitrothion by zero−valent iron powder (Fe⁰) activated persulfate in aqueous solution: Kinetic study and product identification. Chem. Eng. J.358, 1479–1488. 10.1016/j.cej.2018.10.153

  • CrossRef
  • Google Scholar

• 64

  LiuJ.PengC.ShiX. (2022a). Preparation, characterization, and applications of Fe−based catalysts in advanced oxidation processes for organics removal: A review. Environ. Pollut.293, 118565. 10.1016/j.envpol.2021.118565

  • CrossRef
  • Google Scholar

• 65

  LiuW.AiZ.CaoM.ZhangL. (2014). Ferrous ions promoted aerobic simazine degradation with Fe@Fe₂O₃ core–shell nanowires. Appl. Catal. B Environ.150−151, 1–11. 10.1016/j.apcatb.2013.11.034

  • CrossRef
  • Google Scholar

• 66

  LiuW.WangY.AiZ.ZhangL. (2015). Hydrothermal synthesis of FeS₂ as a High−Efficiency fenton reagent to degrade alachlor via Superoxide−Mediated Fe(II)/Fe(III) cycle. Acs Appl. Mater Inter7 (51), 28534–28544. 10.1021/acsami.5b09919

  • CrossRef
  • Google Scholar

• 67

  LiuX.LiH.GaoS.BaiZ.TianJ. (2022b). Peroxymonosulfate activation by different iron sulfides for bisphenol−A degradation: Performance and mechanism. Sep. Purif. Technol.289, 120751. 10.1016/j.seppur.2022.120751

  • CrossRef
  • Google Scholar

• 68

  LuoT.FengH.TangL.LuY.TangW.ChenS.et al (2020). Efficient degradation of tetracycline by heterogeneous electro−Fenton process using Cu−doped Fe@Fe₂O₃: Mechanism and degradation pathway. Chem. Eng. J.382, 122970. 10.1016/j.cej.2019.122970

  • CrossRef
  • Google Scholar

• 69

  LyuH.GaoB.HeF.ZimmermanA. R.DingC.TangJ.et al (2018a). Experimental and modeling investigations of ball−milled biochar for the removal of aqueous methylene blue. Chem. Eng. J.335, 110–119. 10.1016/j.cej.2017.10.130

  • CrossRef
  • Google Scholar

• 70

  LyuH.TangJ.ShenB.SiddiqueT. (2018b). Development of a novel chem−bio hybrid process using biochar supported nanoscale iron sulfide composite and Corynebacterium variabile HRJ4 for enhanced trichloroethylene dechlorination. Water Res.147, 132–141. 10.1016/j.watres.2018.09.038

  • CrossRef
  • Google Scholar

• 71

  MaJ.YangM.YuF.ChenJ. (2015). Easy solid−phase synthesis of pH−insensitive heterogeneous CNTs/FeS Fenton−like catalyst for the removal of antibiotics from aqueous solution. J. Colloid Interf. Sci.444, 24–32. 10.1016/j.jcis.2014.12.027

  • CrossRef
  • Google Scholar

• 72

  MaW.WangN.DuY.TongT.ZhangL.Andrew LinK.et al (2019). One−step synthesis of novel Fe₃C@nitrogen−doped carbon nanotubes/graphene nanosheets for catalytic degradation of Bisphenol A in the presence of peroxymonosulfate. Chem. Eng. J.356, 1022–1031. 10.1016/j.cej.2018.09.093

  • CrossRef
  • Google Scholar

• 73

  MaY.GuY.JiangD.MaoX.WangD. (2021). Degradation of 2,4−DCP using persulfate and iron/E−carbon micro−electrolysis coupling system. J. Hazard Mater413, 125381. 10.1016/j.jhazmat.2021.125381

  • CrossRef
  • Google Scholar

• 74

  MaZ.YangY.JiangY.XiB.YangT.PengX.et al (2017). Enhanced degradation of 2,4−dinitrotoluene in groundwater by persulfate activated using iron–carbon micro−electrolysis. Chem. Eng. J.311, 183–190. 10.1016/j.cej.2016.11.083

  • CrossRef
  • Google Scholar

• 75

  MariëtteW.SjierkJ. V. D. G.DavidR. (2003). The structure of disordered mackinawite. Am. Mineral.88 (11−12), 2007–2015. 10.2138/am-2003-11-1245

  • CrossRef
  • Google Scholar

• 76

  MengF.SongM.SongB.WeiY.CaoQ.CaoY. (2020). Enhanced degradation of Rhodamine B via α−Fe₂O₃ microspheres induced persulfate to generate reactive oxidizing species. Chemosphere243, 125322. 10.1016/j.chemosphere.2019.125322

  • CrossRef
  • Google Scholar

• 77

  MohamedM. M.AbdelmonemE. E.El−SayedG. O. (2023). Graphene foam mediated FeS₂/α−Fe₂O₃ composites for chloramphenicol photodegradation using persulfate activation under visible light irradiation. J. Water Process Eng.53, 103633. 10.1016/j.jwpe.2023.103633

  • CrossRef
  • Google Scholar

• 78

  NairM. G.NirmalaM.RekhaK.AnukalianiA. (2011). Structural, optical, photo catalytic and antibacterial activity of ZnO and Co doped ZnO nanoparticles. Mater Lett.65 (12), 1797–1800. 10.1016/j.matlet.2011.03.079

  • CrossRef
  • Google Scholar

• 79

  NieW.MaoQ.DingY.HuY.TangH. (2019). Highly efficient catalysis of chalcopyrite with surface bonded ferrous species for activation of peroxymonosulfate toward degradation of bisphenol A: A mechanism study. J. Hazard Mater364, 59–68. 10.1016/j.jhazmat.2018.09.078

  • CrossRef
  • Google Scholar

• 80

  OhS.KangS.KimD.ChiuP. C. (2011). Degradation of 2,4−dinitrotoluene by persulfate activated with iron sulfides. Chem. Eng. J.172 (2−3), 641–646. 10.1016/j.cej.2011.06.023

  • CrossRef
  • Google Scholar

• 81

  PaknikarK. M.NagpalV.PethkarA. V.RajwadeJ. M. (2005). Degradation of lindane from aqueous solutions using iron sulfide nanoparticles stabilized by biopolymers. Sci. Technol. Adv. Mat.6 (3−4), 370–374. 10.1016/j.stam.2005.02.016

  • CrossRef
  • Google Scholar

• 82

  PanY.ZhouM.ZhangY.CaiJ.LiB.ShengX. (2018). Enhanced degradation of Rhodamine B by pre−magnetized Fe⁰/PS process: Parameters optimization, mechanism and interferences of ions. Sep. Purif. Technol.203, 66–74. 10.1016/j.seppur.2018.03.039

  • CrossRef
  • Google Scholar

• 83

  PastorJ.DeweyB.JohnsonN. W.SwainE. B.MonsonP.PetersE. B.et al (2017). Effects of sulfate and sulfide on the life cycle ofZizania palustris in hydroponic and mesocosm experiments. Ecol. Appl.27 (1), 321–336. 10.1002/eap.1452

  • CrossRef
  • Google Scholar

• 84

  PengJ.ZhouH.LiuW.AoZ.JiH.LiuY.et al (2020). Insights into heterogeneous catalytic activation of peroxymonosulfate by natural chalcopyrite: pH−dependent radical generation, degradation pathway and mechanism. Chem. Eng. J.397, 125387. 10.1016/j.cej.2020.125387

  • CrossRef
  • Google Scholar

• 85

  PetrieB.BardenR.Kasprzyk−HordernB. (2015). A review on emerging contaminants in wastewaters and the environment: Current knowledge, understudied areas and recommendations for future monitoring. Water Res.72, 3–27. 10.1016/j.watres.2014.08.053

  • CrossRef
  • Google Scholar

• 86

  QiC.LiuX.LinC.ZhangX.MaJ.TanH.et al (2014). Degradation of sulfamethoxazole by microwave−activated persulfate: Kinetics, mechanism and acute toxicity. Chem. Eng. J.249, 6–14. 10.1016/j.cej.2014.03.086

  • CrossRef
  • Google Scholar

• 87

  QiuM.HuB.ChenZ.YangH.ZhuangL.WangX. (2021). Challenges of organic pollutant photocatalysis by biochar−based catalysts. Biochar3 (2), 117–123. 10.1007/s42773-021-00098-y

  • CrossRef
  • Google Scholar

• 88

  QiuM.LiuL.LingQ.CaiY.YuS.WangS.et al (2022). Biochar for the removal of contaminants from soil and water: A review. Biochar4 (1), 19. 10.1007/s42773-022-00146-1

  • CrossRef
  • Google Scholar

• 89

  QuJ.XuY.ZhangX.SunM.TaoY.ZhangX.et al (2022). Ball milling−assisted preparation of N−doped biochar loaded with ferrous sulfide as persulfate activator for phenol degradation: Multiple active sites−triggered radical/non−radical mechanism. Appl. Catal. B Environ.316, 121639. 10.1016/j.apcatb.2022.121639

  • CrossRef
  • Google Scholar

• 90

  QuocT. N.NguyenK. H.ThuyH. N. T.TienN. T. H.MinhC. T. T.DaoV.et al (2021). Feasibility of using sequential sulfurized nanoscale zerovalent Iron−Persulfate process to degrade tetrabromobisphenol A. J. Nanomater, 2021: 1–8. 10.1155/2021/8053120

  • CrossRef
  • Google Scholar

• 91

  RajajayavelS. R. C.GhoshalS. (2015). Enhanced reductive dechlorination of trichloroethylene by sulfidated nanoscale zerovalent iron. Water Res.78, 144–153. 10.1016/j.watres.2015.04.009

  • CrossRef
  • Google Scholar

• 92

  RenY.LinL.MaJ.YangJ.FengJ.FanZ. (2015). Sulfate radicals induced from peroxymonosulfate by magnetic ferrospinel MFe₂O₄ (M = Co, Cu, Mn, and Zn) as heterogeneous catalysts in the water. Appl. Catal. B Environ.165, 572–578. 10.1016/j.apcatb.2014.10.051

  • CrossRef
  • Google Scholar

• 93

  RickardD.HattonB.MurphyD. M.ButlerI. B.OldroydA.HannA. (2011). FeS−Induced radical formation and its effect on plasmid DNA. Aquat. Geochem17 (4−5), 545–566. 10.1007/s10498-010-9116-x

  • CrossRef
  • Google Scholar

• 94

  Savun−HekimoğluB. (2020). A review on sonochemistry and its environmental applications. Acoustics−Basel2 (4), 766–775. 10.3390/acoustics2040042

  • CrossRef
  • Google Scholar

• 95

  ShangW.DongZ.LiM.SongX.ZhangM.JiangC.et al (2019). Degradation of diatrizoate in water by Fe(II)−activated persulfate oxidation. Chem. Eng. J.361, 1333–1344. 10.1016/j.cej.2018.12.139

  • CrossRef
  • Google Scholar

• 96

  ShaoD.RenX.WenJ.HuS.XiongJ.JiangT.et al (2016). Immobilization of uranium by biomaterial stabilized FeS nanoparticles: Effects of stabilizer and enrichment mechanism. J. Hazard Mater302, 1–9. 10.1016/j.jhazmat.2015.09.043

  • CrossRef
  • Google Scholar

• 97

  ShiY.WangX.LiuX.LingC.ShenW.ZhangL. (2020). Visible light promoted Fe₃S₄ Fenton oxidation of atrazine. Appl. Catal. B Environ.277, 119229. 10.1016/j.apcatb.2020.119229

  • CrossRef
  • Google Scholar

• 98

  ShowB.MukherjeeN.MondalA. (2017). Reusable iron sulfide nanospheres towards promoted photocatalytic and electrocatalytic activities. New J. Chem.41 (18), 10083–10095. 10.1039/c7nj02018j

  • CrossRef
  • Google Scholar

• 99

  SilveiraJ. E.Garcia−CostaA. L.CardosoT. O.ZazoJ. A.CasasJ. A. (2017). Indirect decolorization of azo dye Disperse Blue 3 by electro−activated persulfate. Electrochim Acta258, 927–932. 10.1016/j.electacta.2017.11.143

  • CrossRef
  • Google Scholar

• 100

  SongQ.FengY.WangZ.LiuG.LvW. (2019). Degradation of triphenyl phosphate (TPhP) by CoFe₂O₄−activated peroxymonosulfate oxidation process: Kinetics, pathways, and mechanisms. Sci. Total Environ.681, 331–338. 10.1016/j.scitotenv.2019.05.105

  • CrossRef
  • Google Scholar

• 101

  SongS.SuY.AdeleyeA. S.ZhangY.ZhouX. (2017). Optimal design and characterization of sulfide−modified nanoscale zerovalent iron for diclofenac removal. Appl. Catal. B Environ.201, 211–220. 10.1016/j.apcatb.2016.07.055

  • CrossRef
  • Google Scholar

• 102

  SooriM.ZarezadehK.SheibaniS.RashchiF. (2016). Mechano−chemical processing and characterization of nano−structured FeS powder. Adv. Powder Technol.27 (2), 557–563. 10.1016/j.apt.2016.02.004

  • CrossRef
  • Google Scholar

• 103

  SuY.JassbyD.SongS.ZhouX.ZhaoH.FilipJ.et al (2018). Enhanced oxidative and adsorptive removal of diclofenac in heterogeneous Fenton−like reaction with sulfide modified nanoscale zerovalent iron. Environ. Sci. Technol.52 (11), 6466–6475. 10.1021/acs.est.8b00231

  • CrossRef
  • Google Scholar

• 104

  SühnholzS.GawelA.KopinkeF.MackenzieK. (2021). Evidence of heterogeneous degradation of PFOA by activated persulfate – FeS as adsorber and activator. Chem. Eng. J.423, 130102. 10.1016/j.cej.2021.130102

  • CrossRef
  • Google Scholar

• 105

  SühnholzS.KopinkeF.MackenzieK. (2022). Heterogeneous activation of persulfate by FeS – surface influence on selectivity. Chem. Eng. J.450, 138192. 10.1016/j.cej.2022.138192

  • CrossRef
  • Google Scholar

• 106

  SühnholzS.KopinkeF.MackenzieK. (2020). Reagent or catalyst? – FeS as activator for persulfate in water. Chem. Eng. J.387, 123804. 10.1016/j.cej.2019.123804

  • CrossRef
  • Google Scholar

• 107

  SunM.ChengG.GeX.ChenM.WangC.LouL.et al (2018a). Aqueous Hg(II) immobilization by chitosan stabilized magnetic iron sulfide nanoparticles. Sci. Total Environ.621, 1074–1083. 10.1016/j.scitotenv.2017.10.119

  • CrossRef
  • Google Scholar

• 108

  SunY.GuM.LyuS.BrusseauM. L.LiM.LyuY.et al (2020). Efficient removal of trichloroethene in oxidative environment by anchoring nano FeS on reduced graphene oxide supported nZVI catalyst: The role of FeS on oxidant decomposition and iron leakage. J. Hazard Mater392, 122328. 10.1016/j.jhazmat.2020.122328

  • CrossRef
  • Google Scholar

• 109

  SunY.LiuY.LouZ.YangK.LvD.ZhouJ.et al (2018b). Enhanced performance for Hg(II) removal using biomaterial (CMC/gelatin/starch) stabilized FeS nanoparticles: Stabilization effects and removal mechanism. Chem. Eng. J.344, 616–624. 10.1016/j.cej.2018.03.126

  • CrossRef
  • Google Scholar

• 110

  SurosheJ. S.MloweS.GarjeS. S.RevaprasaduN. (2018). Preparation of iron sulfide nanomaterials from iron(II) thiosemicarbazone complexes and their application in photodegradation of methylene blue. J. Inorg. Organomet. P28 (3), 603–611. 10.1007/s10904-018-0816-9

  • CrossRef
  • Google Scholar

• 111

  TanC.DongY.FuD.GaoN.MaJ.LiuX. (2018). Chloramphenicol removal by zero valent iron activated peroxymonosulfate system: Kinetics and mechanism of radical generation. Chem. Eng. J.334, 1006–1015. 10.1016/j.cej.2017.10.020

  • CrossRef
  • Google Scholar

• 112

  TanC.GaoN.DengY.DengJ.ZhouS.LiJ.et al (2014). Radical induced degradation of acetaminophen with Fe3O4 magnetic nanoparticles as heterogeneous activator of peroxymonosulfate. J. Hazard Mater276, 452–460. 10.1016/j.jhazmat.2014.05.068

  • CrossRef
  • Google Scholar

• 113

  Turcio−OrtegaD.FanD.TratnyekP. G.KimE.ChangY. (2012). Reactivity of Fe/FeS nanoparticles: Electrolyte composition effects on corrosion electrochemistry. Environ. Sci. Technol.46 (22), 12484–12492. 10.1021/es303422w

  • CrossRef
  • Google Scholar

• 114

  Van KoetsemF.Van HavereL.Du LaingG. (2016). Impact of carboxymethyl cellulose coating on iron sulphide nanoparticles stability, transport, and mobilization potential of trace metals present in soils and sediment. J. Environ. Manage168, 210–218. 10.1016/j.jenvman.2015.10.047

  • CrossRef
  • Google Scholar

• 115

  WangG.YangY.XuX.ZhangS.YangZ.ChengZ.et al (2023b). Rape straw supported FeS nanoparticles with encapsulated structure as peroxymonosulfate and hydrogen peroxide activators for enhanced oxytetracycline degradation. Molecules28 (6), 2771. 10.3390/molecules28062771

  • CrossRef
  • Google Scholar

• 116

  WangJ.LiaoZ.IfthikarJ.ShiL.ChenZ.ChenZ. (2017). One−step preparation and application of magnetic sludge−derived biochar on acid orange 7 removal via both adsorption and persulfate based oxidation. Rsc Adv.7 (30), 18696–18706. 10.1039/c7ra01425b

  • CrossRef
  • Google Scholar

• 117

  WangJ.WangS. (2018). Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants. Chem. Eng. J.334, 1502–1517. 10.1016/j.cej.2017.11.059

  • CrossRef
  • Google Scholar

• 118

  WangJ.XiongB.MiaoL.WangS.XieP.WangZ.et al (2021). Applying a novel advanced oxidation process of activated peracetic acid by CoFe₂O₄ to efficiently degrade sulfamethoxazole. Appl. Catal. B Environ.280, 119422. 10.1016/j.apcatb.2020.119422

  • CrossRef
  • Google Scholar

• 119

  WangL.HuangX.HanM.LyuL.LiT.GaoY.et al (2019). Efficient inhibition of photogenerated electron−hole recombination through persulfate activation and dual−pathway degradation of micropollutants over iron molybdate. Appl. Catal. B Environ.257, 117904. 10.1016/j.apcatb.2019.117904

  • CrossRef
  • Google Scholar

• 120

  WangQ.TianS.NingP. (2014). Degradation mechanism of methylene blue in a heterogeneous Fenton−like reaction catalyzed by ferrocene. Ind. Eng. Chem. Res.53 (2), 643–649. 10.1021/ie403402q

  • CrossRef
  • Google Scholar

• 121

  WangX.WangY.ChenN.ShiY.ZhangL. (2020c). Pyrite enables persulfate activation for efficient atrazine degradation. Chemosphere244, 125568. 10.1016/j.chemosphere.2019.125568

  • CrossRef
  • Google Scholar

• 122

  WangY.GuZ.YangS.ZhangA. (2020a). Activation of persulfate by microwave radiation combined with FeS for treatment of wastewater from explosives production. Environ. Sci. Water Res. Technol.6 (3), 581–592. 10.1039/c9ew00803a

  • CrossRef
  • Google Scholar

• 123

  WangY.GuZ.YangS.ZhangA. (2020b). Performance of a microwave radiation induced persulfate−hydrogen peroxide binary−oxidant process in treating dinitrodiazophenol wastewater. Sep. Purif. Technol.236, 116253. 10.1016/j.seppur.2019.116253

  • CrossRef
  • Google Scholar

• 124

  WangY.LinY.YangC.WuS.FuX.LiX. (2023a). Calcination temperature regulates non−radical pathways of peroxymonosulfate activation via carbon catalysts doped by iron and nitrogen. Chem. Eng. J.451, 138468. 10.1016/j.cej.2022.138468

  • CrossRef
  • Google Scholar

• 125

  WatsonJ. H. P.CroudaceI. W.WarwickP. E.JamesP. A. B.CharnockJ. M.EllwoodD. C. (2001). Adsorption of radioactive metals by strongly magnetic iron sulfide nanoparticles produced by sulfate−reducing bacteria. Sep. Sci. Technol.36 (12), 2571–2607. 10.1081/ss-100107214

  • CrossRef
  • Google Scholar

• 126

  WeiX.YuanH.LiJ.ChenT.YuanY.ChenW.et al (2022). Reactive oxygen species generated in iron sulfide mediated advanced oxidation systems: A critical review of mechanisms and implications for geochemistry and environmental remediation. J. Environ. Chem. Eng.10 (6), 108841. 10.1016/j.jece.2022.108841

  • CrossRef
  • Google Scholar

• 127

  WeiZ.VillamenaF. A.WeaversL. K. (2017). Kinetics and mechanism of ultrasonic activation of persulfate: An in situ EPR spin trapping study. Environ. Sci. Technol.51 (6), 3410–3417. 10.1021/acs.est.6b05392

  • CrossRef
  • Google Scholar

• 128

  WhartonM. J.AtkinsB.CharnockabJ. M.PattrickR. A. D.CollisonD. (2000). An X−ray absorption spectroscopy study of the coprecipitation of Tc and Re with mackinawite (FeS). Appl. Geochem15 (3), 347–354. 10.1016/s0883-2927(99)00045-1

  • CrossRef
  • Google Scholar

• 129

  WuJ.WangB.CagnettaG.HuangJ.WangY.DengS.et al (2020a). Nanoscale zero valent iron−activated persulfate coupled with Fenton oxidation process for typical pharmaceuticals and personal care products degradation. Sep. Purif. Technol.239, 116534. 10.1016/j.seppur.2020.116534

  • CrossRef
  • Google Scholar

• 130

  WuJ.WangX.ZengR. J. (2017). Reactivity enhancement of iron sulfide nanoparticles stabilized by sodium alginate: Taking Cr (VI) removal as an example. J. Hazard Mater333, 275–284. 10.1016/j.jhazmat.2017.03.023

  • CrossRef
  • Google Scholar

• 131

  WuS.LiuH.YangC.LiX.LinY.YinK.et al (2020b). High−performance porous carbon catalysts doped by iron and nitrogen for degradation of bisphenol F via peroxymonosulfate activation. Chem. Eng. J.392, 123683. 10.1016/j.cej.2019.123683

  • CrossRef
  • Google Scholar

• 132

  WuS.YangC.LinY.ChengJ. J. (2022). Efficient degradation of tetracycline by singlet oxygen−dominated peroxymonosulfate activation with magnetic nitrogen−doped porous carbon. J. Environ. Sci.115, 330–340. 10.1016/j.jes.2021.08.002

  • CrossRef
  • Google Scholar

• 133

  WuX.GuX.LuS.QiuZ.SuiQ.ZangX.et al (2015). Strong enhancement of trichloroethylene degradation in ferrous ion activated persulfate system by promoting ferric and ferrous ion cycles with hydroxylamine. Sep. Purif. Technol.147, 186–193. 10.1016/j.seppur.2015.04.031

  • CrossRef
  • Google Scholar

• 134

  XiaC.LiuQ.ZhaoL.WangL.TangJ. (2022). Enhanced degradation of petroleum hydrocarbons in soil by FeS@BC activated persulfate and its mechanism. Sep. Purif. Technol.282, 120060. 10.1016/j.seppur.2021.120060

  • CrossRef
  • Google Scholar

• 135

  XiangW.ChenH.ZhongZ.ZhangC.LuX.HuangM.et al (2022). Efficient degradation of carbamazepine in a neutral sonochemical FeS/persulfate system based on the enhanced heterogeneous−homogeneous sulfur−iron cycle. Sep. Purif. Technol.282, 120041. 10.1016/j.seppur.2021.120041

  • CrossRef
  • Google Scholar

• 136

  XiangW.HuangM.WangY.WuX.ZhangF.LiD.et al (2020). New insight in the O2 activation by nano Fe/Cu bimetals: The synergistic role of Cu(0) and Fe(II). Chin. Chem. Lett.31 (10), 2831–2834. 10.1016/j.cclet.2020.08.006

  • CrossRef
  • Google Scholar

• 137

  XieY. F.LiX. D.LiF. D. (2013). Study on application of biological iron sulfide composites in treating vanadium−extraction wastewater containing chromium (VI) and chromium reclamation. J. Environ. Biol.34 (2), 301–305.

  • Google Scholar

• 138

  XiongZ.HeF.ZhaoD.BarnettM. O. (2009). Immobilization of mercury in sediment using stabilized iron sulfide nanoparticles. Water Res.43 (20), 5171–5179. 10.1016/j.watres.2009.08.018

  • CrossRef
  • Google Scholar

• 139

  XuH.ShengY. (2021). New insights into the degradation of chloramphenicol and fluoroquinolone antibiotics by peroxymonosulfate activated with FeS: Performance and mechanism. Chem. Eng. J.414, 128823. 10.1016/j.cej.2021.128823

  • CrossRef
  • Google Scholar

• 140

  XuJ.WangY.WengC.BaiW.JiaoY.KaegiR.et al (2019). Reactivity, selectivity, and Long−Term performance of sulfidized nanoscale zerovalent iron with different properties. Environ. Sci. Technol.53 (10), 5936–5945. 10.1021/acs.est.9b00511

  • CrossRef
  • Google Scholar

• 141

  XuL.LiL.FangP.ChangK.ChenC.LiaoQ. (2022). Removal of uranium (VI) ions from aqueous solution by graphitic carbon nitride stabilized FeS nanoparticles. J. Mol. Liq.345, 117050. 10.1016/j.molliq.2021.117050

  • CrossRef
  • Google Scholar

• 142

  YanS.LuoS.FengJ.LiP.GuoR.WangQ.et al (2020). Rational design of flower−like FeCo₂S₄/reduced graphene oxide films: Novel binder−free electrodes with ultra−high conductivity flexible substrate for high−performance all−solid−state pseudocapacitor. Chem. Eng. J.381, 122695. 10.1016/j.cej.2019.122695

  • CrossRef
  • Google Scholar

• 143

  YanZ.GuY.WangX.HuY.LiX. (2021). Degradation of aniline by ferrous ions activated persulfate: Impacts, mechanisms, and by−products. Chemosphere268, 129237. 10.1016/j.chemosphere.2020.129237

  • CrossRef
  • Google Scholar

• 144

  YangS.HeC.XieZ.LiL.XiongZ.ZhangH.et al (2022). Efficient activation of PAA by FeS for fast removal of pharmaceuticals: The dual role of sulfur species in regulating the reactive oxidized species. Water Res.217, 118402. 10.1016/j.watres.2022.118402

  • CrossRef
  • Google Scholar

• 145

  YangjuL.XiugeZ.YanY.JianfeiY.YutingP.YunhongZ.et al (2019). Enhanced sulfamethoxazole degradation by peroxymonosulfate activation with sulfide−modified microscale zero−valent iron (S−mFe⁰): Performance, mechanisms, and the role of sulfur species. Chem. Eng. J.376 (C), 121302. 10.1016/j.cej.2019.03.178

  • CrossRef
  • Google Scholar

• 146

  YeZ.PadillaJ. A.XurigueraE.BeltranJ. L.AlcaideF.BrillasE.et al (2020). A highly stable metal–organic Framework−Engineered FeS₂/C nanocatalyst for heterogeneous Electro−Fenton treatment: Validation in wastewater at mild pH. Environ. Sci. Technol.54 (7), 4664–4674. 10.1021/acs.est.9b07604

  • CrossRef
  • Google Scholar

• 147

  YuZ.MaJ.HuangX.LvY.LiuY.LinC.et al (2022). Insights into enhanced peroxydisulfate activation with S doped Fe@C catalyst for the rapid degradation of organic pollutants. J. Colloid Interf. Sci.610, 24–34. 10.1016/j.jcis.2021.12.046

  • CrossRef
  • Google Scholar

• 148

  YuanY.TaoH.FanJ.MaL. (2015). Degradation of p−chloroaniline by persulfate activated with ferrous sulfide ore particles. Chem. Eng. J.268, 38–46. 10.1016/j.cej.2014.12.092

  • CrossRef
  • Google Scholar

• 149

  ZhangJ.QiuS.FengH.HuT.WuY.LuoT.et al (2022). Efficient degradation of tetracycline using core–shell Fe@Fe₂O₃−CeO₂ composite as novel heterogeneous electro−Fenton catalyst. Chem. Eng. J.428, 131403. 10.1016/j.cej.2021.131403

  • CrossRef
  • Google Scholar

• 150

  ZhangP.TanX.LiuS.LiuY.ZengG.YeS.et al (2019a). Catalytic degradation of estrogen by persulfate activated with iron−doped graphitic biochar: Process variables effects and matrix effects. Chem. Eng. J.378 (2), 122141. 10.1016/j.cej.2019.122141

  • CrossRef
  • Google Scholar

• 151

  ZhangS.LyuH.TangJ.SongB.ZhenM.LiuX. (2019b). A novel biochar supported CMC stabilized nano zero−valent iron composite for hexavalent chromium removal from water. Chemosphere217, 686–694. 10.1016/j.chemosphere.2018.11.040

  • CrossRef
  • Google Scholar

• 152

  ZhangW.GaoJ.DuanW.ZhangD.JiaJ.WangY. (2020). Sulfidated nanoscale zero−valent iron is an efficient material for the removal and regrowth inhibition of antibiotic resistance genes. Environ. Pollut.263, 114508. 10.1016/j.envpol.2020.114508

  • CrossRef
  • Google Scholar

• 153

  ZhaoL.JiY.KongD.LuJ.ZhouQ.YinX. (2016). Simultaneous removal of bisphenol A and phosphate in zero−valent iron activated persulfate oxidation process. Chem. Eng. J.303, 458–466. 10.1016/j.cej.2016.06.016

  • CrossRef
  • Google Scholar

• 154

  ZhaoZ.PanS.YeY.ZhangX.PanB. (2020). FeS₂/H₂O₂ mediated water decontamination from p−arsanilic acid via coupling oxidation,adsorption and coagulation: Performance and mechanism. Chem. Eng. J.381 (2), 122667. 10.1016/j.cej.2019.122667

  • CrossRef
  • Google Scholar

• 155

  ZhengM.LuJ.ZhaoD. (2018). Toxicity and transcriptome sequencing (RNA−seq) analyses of adult zebrafish in response to exposure carboxymethyl cellulose stabilized iron sulfide nanoparticles. Sci. Rep−Uk8 (1), 8083. 10.1038/s41598-018-26499-x

  • CrossRef
  • Google Scholar

• 156

  ZhouL.LiuJ.DongF. (2017). Spectroscopic study on biological mackinawite (FeS) synthesized by ferric reducing bacteria (FRB) and sulfate reducing bacteria (SRB): Implications for in−situ remediation of acid mine drainage. Spectrochimica Acta Part A Mol. Biomol. Spectrosc.173, 544–548. 10.1016/j.saa.2016.09.053

  • CrossRef
  • Google Scholar

• 157

  ZhouX.LuoM.XieC.WangH.WangJ.ChenZ.et al (2021a). Tunable S doping from Co₃O₄ to Co₉S₈ for peroxymonosulfate activation: Distinguished Radical/Nonradical species and generation pathways. Appl. Catal. B Environ.282, 119605. 10.1016/j.apcatb.2020.119605

  • CrossRef
  • Google Scholar

• 158

  ZhouX.ZengZ.ZengG.LaiC.XiaoR.LiuS.et al (2020). Insight into the mechanism of persulfate activated by bone char: Unraveling the role of functional structure of biochar. Chem. Eng. J.401, 126127. 10.1016/j.cej.2020.126127

  • CrossRef
  • Google Scholar

• 159

  ZhouY.WangX.ZhuC.DionysiouD. D.ZhaoG.FangG.et al (2018). New insight into the mechanism of peroxymonosulfate activation by sulfur−containing minerals: Role of sulfur conversion in sulfate radical generation. Water Res.142, 208–216. 10.1016/j.watres.2018.06.002

  • CrossRef
  • Google Scholar

• 160

  ZhouZ.HuangJ.XuZ.AliM.ShanA.FuR.et al (2021b). Mechanism of contaminants degradation in aqueous solution by persulfate in different Fe(II)−based synergistic activation environments: Taking chlorinated organic compounds and benzene series as the targets. Sep. Purif. Technol.273, 118990. 10.1016/j.seppur.2021.118990

  • CrossRef
  • Google Scholar

• 161

  ZhuK.XuH.ChenC.RenX.AlsaediA.HayatT. (2019). Encapsulation of Fe⁰−dominated Fe₃O₄/Fe⁰/Fe₃C nanoparticles into carbonized polydopamine nanospheres for catalytic degradation of tetracycline via persulfate activation. Chem. Eng. J.372, 304–311. 10.1016/j.cej.2019.04.157

  • CrossRef
  • Google Scholar

• 162

  ZhuangY.WangX.ZhangL.DionysiouD. D.KouZ.ShiB. (2020). Double−network hydrogel templated FeS/graphene with enhanced PMS activation performance: Considering the effect of the template and iron species. Environ. Sci. Nano7 (3), 817–828. 10.1039/c9en01391a

  • CrossRef
  • Google Scholar