Research articleA nanoscale “yarn ball”-like heteropoly blue catalyst for extremely efficient elimination of antibiotics and dyes
Graphical abstract
Introduction
Water pollution caused by various refractory antibiotics and dyes has affected millions of people worldwide and aroused great concern and discussion in the field of scientific community and public society (Kanakaraju et al., 2018; Matafonova and Batoev, 2012; Wei et al., 2017). It also has affected plants and organisms living in lakes, rivers and oceans due to unregulated industries and biologic excretion (Hu et al., 2018a, 2018b). Therefore, finding a practical solution and technology for antibiotics and dyes treatment in wastewater has become the challenging task of the day. Several methods have been reported to tackle the problem, and all come with their advantages and disadvantages (Dai et al., 2017; Kuo, 1992; Vikesland et al., 2017). Traditional methods such as adsorption, filtration and coagulation have the advantages of simple process and mature technology (Bolisetty and Mezzenga, 2016). However, the methods just transfer organic pollutants from the liquid phase to the solid or gaseous phase and cause secondary pollution inevitably (Kumar et al., 2010). Biological methods such as aerobiotic and anaerobic just can deal with the biochemical oxygen demand (BOD) in contaminated water and show the dissatisfactory performance in coping with toxic refractory organics. Furthermore, the efficiencies of biochemical methods are largely influenced by environmental factors such as temperature and initial concentrations of contaminants. Compared with the above methods, the advanced oxidation processes (AOPs) are considered as one of the most effective methods to remove organic pollutants in wastewater (Davarnejad and Nasiri, 2017; Fei et al., 2017; Kanakaraju et al., 2018; Xu et al., 2018). Of these technologies, the Fenton methods have widely been used due to its wide treatment range and high efficiency (Leifeld et al., 2018; Lopez-Ramon et al., 2018; Peng et al., 2018). Fenton methods generally can be divided into both homogeneous system and heterogeneous process. However, the homogeneous Fenton process confronts several shortcomings as follows: (1) narrow optimal pH range (2–4) limits its application in water treatment; (2) the chroma of solution and sludge caused by the dissolved ferric species should to be post-treatment; (3) the potential second pollution of acids makes this technology complex and uneconomical. All of these questions result in the application prospect of homogeneous Fenton limited (Li et al., 2018). Considering these disadvantages of homogeneous Fenton, more and more efforts have been made to develop effective heterogeneous Fenton-like catalysts (Dong et al., 2017; Li et al., 2018; Liu et al., 2018; Zhang et al., 2017).
Polyoxometalates (POMs) are one class of compounds consisting of metal (usually transition metal such as molybdenum and tungsten) oxides. They have been extensively explored in environmental remediation and become promising candidates because of their good catalytic performance, the property of mixed-valence and high charge densities, which make them suitable for organic pollutants degradation (Cao et al., 2017; Spielman-Sun et al., 2017). However, the reports about POMs as Fenton-like catalysts are a very few. Heteropoly blue (HPB), a kind of reduced POMs with higher charge density than oxidative POMs, is usually obtained by the reduction of heteropoly acid salt. Considering the catalytic mechanisms of HPBs and the mixed-valence properties of W/Mo containing transition metal oxide, the application of reductive W/Mo contained HPBs in heterogeneous Fenton-like should be more promising and advantageous (Cui et al., 2016).
Researches on HPBs were very flourishing in the last century, but most HPBs were obtained by indirect reductions rather than direct synthesis, and high-dimensional (3D) HPBs especially constructed with Keggin structure units are rarely reported. In all, the main objectives of this work were to (1) synthesize a novel “yarn ball”-like mixed-valence Mo/W–containing HPB catalyst (1) via hydrothermal process; (2) investigate the morphology, structure and physicochemical properties of 1; (3) extremely efficient eliminate the effluents of malachite green (MG), tetracycline (TC) and methyl orange (MO) in pharmaceutical and printing industries; (4) clarify the possible mechanisms of MG, TC and MO degradation; (5) evaluate the stability and recyclability of 1 during the Fenton-like process. The findings of this work try to expanse the heterogeneous Fenton-like catalyst family and its application in the field of water treatment.
Section snippets
Reagents and materials
All experimental details including chemical regents and characterizations used in this study are shown in S1 (see in supplementary information). More the necessary information will be introduced in specific condition.
Synthesis of (1)
A mixture of (NH4)6Mo7O24·4H2O (0.3708 g, 0.3 mmol), H4SiW12O40·7H2O (0.432 g, 0.15 mmol), TiSO4 (0.072 g, 0.3 mmol), Mg(NO3)2·6H2O (0.768 g, 3 mmol), C6H15NO3 (0.0447 g, 0.3 mmol), C2H5NO2 (0.0225 g, 0.3 mmol) and distilled water (30 mL) was put into a 50 mL PFA-lined autoclave
Characterization of 1
Technologies of SEM and TEM were used to characterize the micro-morphology of 1. In detail, Fig. 1a–c depicts the overall morphology and single ball of 1. They show a lot of nanoscale balls with various sizes (600–800 nm), and especially, some of the balls are hollow (Fig. 2a and b). In addition, it's more interesting that the morphology of 1 became thread-like after ultrasound (Fig. 2c and d), liking wires-tangled “yarn balls”. Furthermore, TEM analysis was carried out as shown in Fig. 1d–f.
Conclusion
A nanoscale “yarn ball”-like HPB (1) was successfully synthesized and a series of techniques and methods were used to confirm its physicochemical properties. The 1/H2O2 heterogeneous Fenton-like system displayed excellent catalytic performance in deal with the refractory effluents containing malachite green (MG), tetracycline (TC) and methyl orange (MO). The batches experiments confirmed that the degradation rates of MG and TC were found to be 90.69% and 81.46% in 60 min for the initial
Acknowledgement
This work was supported by the Natural Science Foundation of China (21277146), the Science and Technology Major Projects of Anhui Province (18030801104), the Key Technologies R & D Program Foundation of Anhui Province (1704a0802136) and the Chinese academy of sciences key deployment project (KFZD-SW-309).
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