Novel sulfur vacancies featured MIL-88A(Fe)@CuS rods activated peroxymonosulfate for coumarin degradation: Different reactive oxygen species generation routes under acidic and alkaline pH
Graphical Abstract
Introduction
The pleasant fragrance of coumarin (COU) makes it frequently used in perfumes, soaps, and cosmetics products, resulting in the release of the substance into the aquatic environment (Zeng et al., 2021a). COU has been reported to induce estrogenic responses in fish species and exacerbate hepatotoxicity and tumor development in rodents (Montanaro et al., 2017, Blanco et al., 2019). It is also a potential endocrine disruptor for mammals and some of people are much more susceptible to its toxicity (Abraham et al., 2010). As a result, there is a growing demand to seek efficient water treatment technologies to remove COU from water matrix.
Advanced oxidation processes (AOPs), certified as an efficient and promising technique, have been extensively utilized in hazardous organics removal (Zeng et al., 2020). Some AOPs methods have been attempted to remove COU. Görmez et al. investigated the electro-Fenton and subcritical water oxidation processes to degrade COU, achieving 99 % and 88 % COU degradation, respectively (Görmez et al., 2022). Montanaro et al. used boron-doped diamond anodes and UV irradiation to degrade COU via electrochemical oxidation, and 50 mg/L COU was complete removal and mineralized after 3 h (Montanaro et al., 2017). However, UV and electrochemical oxidation are uneconomical and unsustainable due to the additional energy required. Sulfate radical (SO4•−) based AOPs (SR-AOPs) are considered as a preference on account of the wide adaptive pH range, higher redox potential, longer half-life and excellent selectivity of SO4•− (Zeng et al., 2021b). Generally, transition metals like Cu, Fe, Ni, Co, and Mn have been regarded as effective activators for PMS and no energy input is required (Wang and Wang, 2018, Zeng et al., 2022, Zhu et al., 2022, Xia et al., 2022). Yet, metal ions addition in homogeneous reaction system greatly limits its application because of the inevitable secondary pollution and metal sludge (Dong et al., 2019). Thus, it is necessary to construct novel heterogeneous catalysts building on transition metals with high activity and stability (Zhang et al., 2021, Zhu et al., 2021).
Metal organic frameworks (MOFs) have received a surge of interest in the fields of adsorption/separation (Zhou et al., 2014, Yang et al., 2013), photo-catalysis (Tian et al., 2019) and catalysis (Zhou et al., 2021, Zhang et al., 2018), owing to excellent properties of large pore volume, high apparent surface areas, well-defined structure (Liao et al., 2019), and fine dispersion of active metal sites (Duan et al., 2018). Especially, iron-based MOFs have received tremendous attention in environmental remediation due to their environmental friendliness and unique structural characteristics (Liu et al., 2017, Luo et al., 2021). For example, MIL-101 (Fe), MIL-100 (Fe), MIL-53 (Fe), and MIL-88B (Fe) have been developed to remove acid orange 7 (AO7) via adsorption and persulfate activation (Li et al., 2016). Among numerous iron-based MOFs, MIL-88A(Fe) possesses impressive water/chemical stability (Liu et al., 2018, Amaro-Gahete et al., 2019) and excellent swelling properties (Mellot-Draznieks et al., 2005). Wang et al. synthesized a series of MIL-88A(Fe) in diverse preparation conditions to activate persulfate and realized the removal of 96.4 % Orange gelb (Wang et al., 2016). However, as the coordination spheres of metal ions in MOFs are completely connected or obstructed by organic linkers, the intrinsic shortage of free unsaturated metal sites in MOFs limits their ability to degrade organic contaminants (Liu et al., 2014). In view of this, an effective method has been attempted to produce more active metal sites by introducing metal complexes to connect with organic linkers in MOFs (Wu et al., 2013).
Copper sulfide (CuS), a natural mineral, has been served as photo-catalysts due to its fantastic optical property. Recently, copper sulfide (CuS) and its derivatives have been applied as activators for H2O2 (Zhang et al., 2021, Nie et al., 2013), PMS (Wang et al., 2020), and PS (Peng et al., 2018) for organics elimination. It was reported that the unsaturated S atoms distributed on the surface of metal sulfides could facilitate the conversion of Fe(III)/Fe(II) (Xing et al., 2018). Zhang el al. found that the sulfur in Fe3O4@CuS nanoparticles promoted the conversion of Cu(II)/Cu(I) and Fe(III)/Fe(II), and the reaction kinetic rate constant achieved by Fe3O4@CuS was more than 20 times higher than that of Fe3O4 (Zhang et al., 2021). Yan et al. also reported that the ciprofloxacin degradation obtained by CuS/Fe2O3/Mn2O3 nanocomposite (81.6 %) was much higher than Fe2O3/Mn2O3 (~ 30 %) (Huang et al., 2020). In addition, sulfur vacancies (Sv) have been studied to adjust the surface electronic and geometric structure of nanomaterials to improve the catalytic activity and adsorption free energy (Gao et al., 2020). Our previous study demonstrated that Sv in CuS@MIL-101(Fe) could boost the metal reduction and enhance the catalytic activity (Zhou et al., 2021). Kuang et al. also verified that Sv in MoS2 improved the adsorption energy of Fe3+ to accelerate the Fenton reaction process (Kuang et al., 2021). Benefiting from the well-defined structure of MIL-88A(Fe) and Sv in CuS, incorporating CuS onto MIL-88A(Fe) is expected to be a more efficient approach for PMS activation (Chen et al., 2021). Unfortunately, to the best of our knowledge, no attempt has been made to construct MIL-88A(Fe)@CuS as heterogeneous catalyst for activating PMS for organics degradation. Besides, initial acidic and alkaline pH are considered to hold a crucial influence on reactive oxygen species (ROS) production in heterogeneous PMS activation, but the mechanism of the effect remains underdeveloped and needs further clarification.
Herein, a novel MIL-88A(Fe)@CuS rod featured with abundant sulfur vacancies was successfully synthesized by in-situ growing CuS on rod-like MIL-88A(Fe). The morphology, crystal structure, and chemical composition of the as-synthesized catalysts were characterized. The catalytic activity of MIL@CuS toward PMS activation for COU degradation was studied systematically. The generation routes of reactive oxygen species (ROS) in the catalytic system under acidic and alkaline pH were unveiled. The possible activation mechanisms and degradation pathways of COU were proposed.
Section snippets
Materials
FeCl3·6H2O, CuCl2·2H2O, Thiourea (CH4N2S), NaCl, NaNO3, Na2SO4, NaHCO3, H2SO4, NaOH, ethyl alcohol (EtOH), N,N-Dimethylformamide (DMF), methanol (MeOH), nitrobenzene (NB), furfuryl alcohol (FFA) were purchased from Sinopharm Chemical Reagent Co., Ltd. Fumaric acid (FA) and p-hydroxybenzoic acid (HBA) were obtained from Shanghai Macklin Biochemical Co., Ltd. Sigma-Aldrich Chemical Co. Ltd., (China) provided Sulfamethoxazole (SMX), sulfadiazine (SDZ), carbamazepine (CBZ), bisphenol A (BPA),
Catalysts characterization
The surface morphology and microstructure of MIL-88A(Fe), CuS, and 65 %MIL@CuS were examined using SEM as depicted in Fig. 1. MIL-88A(Fe) exhibits a rod-like crystal morphology with a diameter of 4 µm and a length of around 13 µm (Fig. 1a and b). CuS displays a flower-like sphere with a diameter of 2 µm (Fig. 1c and d). In Fig. 1e and f, the as-synthesized 65 %MIL@CuS remains the rod-shape structure just like MIL-88A(Fe), with CuS nanoparticles uniformly attached on the surface of MIL-88A(Fe).
Conclusions
In this work, we synthesized novel sulfur vacancies featured MIL-88A(Fe)@CuS rod and used it as PMS activator for the COU degradation. The loading amount of MIL-88A(Fe) greatly affected on the catalytic performance. 0.2 g/L of the as-synthesized 65 %MIL@CuS and 0.5 mM of PMS could completely remove 30 μM of COU in 7 min, and the reaction rate constant was 0.650 min−1. The initial solution pH greatly influenced activation mechanisms. EPR and radicals scavenging tests identified that •OH and 1O2
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
We were grateful to the financial support from The Science and Technology Innovation Program of Hunan Province (2021RC3039) and Natural Science Foundation of Hunan Province (2021JJ40069).
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Haojie Zhang and Chan Zhou contributed equally to this article.