Ionic liquid covered iron-oxide magnetic nanoparticles decorated zeolite nanocomposite for excellent catalytic reduction and degradation of environmental toxic organic pollutants and dyes
Introduction
Toxic pollutants, namely, organic dyes and pigments are released from various industries such as leather, textile, printing, rubber processing, cosmetics, food processing and pharmaceuticals manufacturers. [1] Humans, plants, animals and most living organisms are affected by these highly toxic and hazardous dye wastes. [1] Furthermore, nitroanilines constitute a major class of toxic chemicals that pollute the environment. They are produced as byproducts in the synthesis of dyes, pesticides, herbicides, fungicides, pharmaceuticals, polymers and can also be produced by petroleum refinery industries. [2] On account of their toxicities and recalcitrant natures, they can pollute the environment; specifically, groundwater and air. Generally, nitroanilines are carcinogenic chemicals that are produced by industries and they can affect the lung tissues of humans to generate cancer. [3] Several research studies have already been undertaken to address this issue. Much ongoing research concerning environmental pollution is aimed at the removal of dyes and other toxic hazardous chemicals from industrial wastewater. A recent alternative approach involves the conversion/degradation of toxic chemicals into harmless or less harmful chemicals. [4], [5]
Due to the carcinogenic nature and toxicities of many dyes, the degradation of organic dyes in wastewater is significant in daily life. However, it is difficult to degrade most of these organic dyes and nitroanilines without the assistance of effective catalysts. Chemical, biological and other methods, such as adsorption by activated carbon, dissolved air flotation, biochemical and microorganisms-mediated reductions have been used for the treatment of wastewater or effluents containing dyes and toxic chemicals. [6], [7] However, the methods which have already been reported have some disadvantages; specifically, high cost, harsh reaction conditions, difficulties in the removal of microorganisms from the reaction mixtures or degraded dye molecules, phase transfer of pollutants, difficulty in maintaining stable conditions for photolysis and an extremely resistive character of dyes in microorganisms. Therefore, there is an urgent need to develop a new and efficient method for the removal of pollutants from the environment. This is one of the important global environmental issues. To date, technologies such as chemical reduction and chemical oxidation [8], ion exchange [9], electrodialysis [10], biological method [11] and adsorption [12] have been developed for wastewater treatment. Of the above methods, adsorption is a widely used method, due to its simplicity of operation, high separation efficiency and low cost. The adsorption method depends predominantly on the materials which possess excellent adsorption capacity, high specific surface area and surface energy as requisite properties for adsorptive materials. It would be very useful to incorporate such adsorbents in designing new materials for the removal of dyes. In this regard, it is noted that numerous nanomaterials have been used for wastewater clean-up. Some of the materials which are used to make nanocomposites for wastewater treatment are: zeolites [13], activated carbon [14], chitosan [15] and kaolinite [16]. Silicates, zeolites, carbon nanotubes (CNTs) and metal–organic frameworks (MOFs) have been used to synthesize many mixed-matrix membranes (MMMs). [17]
Zeolites are a class of microporous crystalline hydrated aluminosilicate minerals of alkaline or alkaline earth metals, which have been used as molecular sieves. Sedimentary rock of volcanic origin is one of the naturally occurring sources for zeolite and it can also be synthetically produced. Zeolite has been employed as a successful adsorbent in industries under the name of ‘mordenite’ (MOR). [18]. Spurred on by their various properties; many zeolites-based porous nanostructures have been prepared. [19] Numerous studies have been reported on the synthesis of novel nanomaterials with hybrid properties and with wide applications. In particular, zeolite has been used as a supporting material to host and stabilize the various metals and oxides of metals to regulate their sizes in their nano states. [20] In addition, the composite of zeolite with activated carbon (Z-AC) plays a vital role in the adsorption of dyes and toxic chemicals from wastewater, arising from their good adsorbent property coupled with cost-effectiveness. [21] On account of appropriate pore size and shape-selective properties, zeolites have been used for gas separation and as an inorganic filler in mixed-matrix membranes (MMMs). [22]
Magnetic nanomaterials are finding favour with researchers because of their attractive properties with a wide range of applications in an eco-friendly manner. A few of their applications are in catalysis, wastewater treatment, anti-electromagnetic interference, electronic devices and biomedicine. [23], [24] Furthermore, magnetic nanoparticles and their nanocomposites can be easily separated from the reaction mixtures or wastewater and they can be reused in further processes by exploiting their magnetic properties. Some magnetic zeolite nanocomposites have been used for the adsorption of heavy metals from wastewater. [25]
Ionic liquid (IL) incorporated nanoparticles have been combined with porous materials, namely, zeolites, to yield nanocomposites, which may be very effective in various applications, including, the removal of dyes from wastewater. The particular reasons for the inclusion of ILs in nanocomposites are their unique properties, such as non-volatility, high thermal stability, good electrolytic nature, non-flammability, solubility, high ionic conductivity, dissolving capacity for CO2 and large liquid ranges. [26] Room temperature ILs have been used to improve membranes in terms of interphase morphologies and enhancement of polymer/inorganic filler compatibility. [27] Recently IL-modified zeolites have been used as highly selective membranes for CO2. [28] In comparison with MOFs, zeolite-IL frameworks proved to be more suitable for wastewater treatment due to their high thermal and chemical stability, low cost as well as porous nature. [29] The present study describes the synthesis and characterisation of IL-modified Fe3O4 magnetic nanoparticles incorporated zeolite nanocomposite and its catalytic application for reduction of several nitroanilines and dyes to their corresponding amines and other less harmful chemicals. Time-dependent UV–vis spectroscopy was used to monitor the reduction reaction at room temperature.
Section snippets
Materials and method
Ferrous sulphate (98%), ferric chloride (96%), liquid ammonia (30%), 2-oxopyrrolidine (99%), epichlorohydrin (96%), acetonitrile (99%), zeolite (98%), sodium hydroxide (98%), sodium borohydride (99%), methylene blue (98%), allura red (96%), 2-nitroaniline (98%), 3-nitroaniline (96%), 4-nitroaniline (98%) and nitrophehylene diamine (NPDA) (98%) were purchased from Sigma Aldrich. In this investigation double deionised water was used in all experiments requiring water.
Synthesis of 2′,3′-epoxy propyl-N-methyl-2-oxopyrrolidinium salicylate [EPMpyr][SAL] IL
The IL (2′,3′-epoxy
Catalytic activity
A series of nitroanilines (NAs) and dyes were reduced by synthesized nanocomposite as a catalyst, to prove its catalytic activity. The reduction reactions used for this investigation as shown in Fig. 2. Typically, the following solutions were placed in 6 separate quartz cuvettes: 2-nitroaniline (2-NA) (0.5 mL, 0.05 M), 3-nitroaniline (3-NA) (0.75 mL, 0.05 M), 4-nitroaniline (4-NA) (0.75 mL, 0.01 M), 4-nitrophehylene diamine (NPDA) (0.75 mL, 0.005 M) as well as methylene blue (MB) (0.75 mL,
Result and discussion
Several spectroscopic techniques were used to characterize the synthesized materials. Initially, FTIR spectra of IL, MNP and IL/MNP/Zeo were recorded in the range of 4000–400 cm−1 as shown in Fig. S1. For comparison study, the FTIR spectra of zeolite and magnetic nanoparticles were recorded and included in the same Fig. S1. The absorption peak at 3427 cm−1 is ascribed to the silanol group in a terminal position on the external surface of the zeolite. [35], [36] The broad and strong peak in the
Comparison studies
Table S1 represents recently reported nanocomposites that have been used as a catalyst for the reduction of series of nitroanilines, nitrophenols and dyes. [42], [43], [44], [45], [46], [47], [48], [49], [50], [51], [52], [53], [54], [55], [56], [57], [58], [59], [60], [61] A search of the literature reveals that the quantity of catalyst and sodium borohydride used, pollutant concentrations and the duration of the reaction all play significant roles in the catalytic reduction of the organics.
Postulated mechanism
From the above results, the postulated mechanism for the catalytic reduction of 4-NA to PDA with NaBH4 over the IL/MNP/Zeo nanocomposite is: NaBH4 interacts with nanocomposite to activate the nanocomposite to provide protons. However, the improved catalytic activity of nanocomposite is attributed to the active MNP (Fe3O4) layers and significant adsorption of 4-NA reactants onto the iron oxide nanoparticles. In this case, both sodium borohydride and the nitrocompound react at the surface of iron
Conclusion
The IL bonded magnetic nanoparticles-doped zeolite nanocomposite was successfully synthesised and characterised with both microscopic and macroscopic techniques. This material was used as a catalyst for the reduction of a series of nitroanilines and dyes to their corresponding amines and relative less toxic derivatives respectively. In this reaction, only a minute quantity of NaBH4 has been used for the initiation of the reaction. The reduced amine derivatives are less toxic than their parent
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.
Acknowledgement
The authors are grateful to the Natural Science Foundation of Hainan Province (2019RC166, 2019RC110) and National Natural Science Foundation of China (21965011) for financial support. The authors also acknowledge Durban University of Technology, South Africa, and Eskom Holdings, South Africa for financial support. This work was funded by Researchers Supporting Project number (RSP-2021/27), King Saud University, Riyadh, Saudi Arabia. Dr Vasanthakumar acknowledges the Postdoctoral Funding of
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