Carbon Nanomaterials for the Removal of Endocrine-Disrupting Chemicals: History
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Subjects: Water Resources
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The large-scale production and frequent use of endocrine-disrupting chemicals (EDCs) have led to the continuous release and wide distribution of these pollutions in the natural environment. At low levels, EDC exposure may cause metabolic disorders, sexual development, and reproductive disorders in aquatic animals and humans. Adsorption treatment, particularly using nanocomposites, may represent a promising and sustainable method for EDC removal from wastewater. EDCs could be effectively removed from wastewater using various carbon-based nanomaterials, such as carbon nanofiber, carbon nanotubes, graphene, magnetic carbon nanomaterials, carbon membranes, carbon dots, carbon sponges, etc.

  • endocrine-disrupting chemicals
  • carbon nanomaterials
  • synthesis

1. Development of Carbon Nanomaterials

In recent years, carbon has become one of the most multilateral elements present in the periodic table due to its strength and ability to form bonds with other elements. Carbon-based nanomaterials and associated modified composites have excellent adsorption properties due to their environmentally friendly, extremely high specific surface area, large pore volume, uniform microporosity, and adjustable surface chemical properties [61,62]. Biomass carbon nanocomposites are a low-cost, readily available, widely distributed, and renewable nanomaterial. Several promising reports have emerged in recent years on the synthesis of carbon nanomaterials from cost-effective, rich, and renewable biomaterial resources such as saw dust, crab shells, bagasse, olive stone waste, and activated carbon cloth [63,64]. Activated carbon is widely used for the control of synthetic and naturally occurring EDCs in drinking water [65]. Carbon nanotubes (CNTs), which were discovered back in the year 1991, have been extensively adapted to study the adsorption capability in water treatment [66]. Graphene, a new material for which the Noble Prize was won, has received increasing attention due to its unique physico-chemical properties for removing EDC pollutants from wastewater [67]. Carbon dots with abundant functional groups (-OH, -COOH, -C=O) on their surface were specially designed to enhance the adsorption capacity [68]. Highly porous carbon sponges always contain some functional groups, which could enhance the surface sensitivity and selectivity of EDC pollutants [69]. Many carbon nanocomposites have been synthesized and used as adsorbents for the removal of EDC pollutants from wastewater. There are many industries such as mining, battery manufacturers, the pharmaceutical industry, the cultivation industry, galvanization, and metal finishing which generate wastewater containing EDCs and emit it directly or indirectly into the nearest water resources [5]. Carbon nanomaterials play an important role in nanoadsorbents.

1.1. Carbon Nanofiber

Carbon nanofiber (CN), also known as nano-activated carbon, is widely used for the treatment of organic wastewater and removal of EDC substances. In addition to the high adsorption capability, the regeneration of ACF could be carried out under a lower temperature than granular activated carbon [90]. The adsorption efficiency of ACF is significantly higher than that of granular or powdered activated carbon. Murayama et al. used ACF to recover organic chlorine pesticides (OCPs) from rainwater, river water, and seawater samples and confirmed that ACF adsorbed sub-ng/L level OCPs from environmental water samples [70].

1.2. Carbon Nanotubes (CNTs)

CNTs are a kind of carbon allotrope with an aromatic surface rolled up to form a cylindrical structure; the length of CNTs varies from 10 s of nm to 10 s of mm [76]. They can be divided into single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs), both of which have high a mechanical strength and elasticity as well as chemical and structural stability. SWCNTs and MWCNTs are widely used in removing EDCs from wastewater after being modified by different functional groups (polydopamine, magnetic particles, and molecular imprinting polymers e.g.,) [91]. Mashkoor et al. [92] summarized the adsorption capacities of the original and modified CNTs for different dyes; the adsorption capacity of glycine-β-cyclodextrin MWCNTs for methylene blue was up to 90.90 mg/g, while the adsorption capacities of modified MWCNTs for Hg2+, Cr4+, and As3+ were 123.45 mg/g, 146.5 mg/g, and 133.33 mg/g, respectively [74]. The large specific surface area, large pore volume, and average pore diameter contribute to the excellent adsorption capacity of CNTs [93].

1.3. Graphene Family

Graphene and graphene oxide (GO) have also been widely used for the adsorption of EDCs because of their special properties such as extraordinary quantum hall effects, high mobility, excellent electronic and mechanical properties, specific magnetism, and high thermal conductivity [94]. The excellent adsorption capacity of GO is improved by the electrostatic interaction between the oxidation groups and the adsorbates, and GO is mainly used for the adsorption of metal ions, anionic dyes, and cationic dyes. Modified GO has a good adsorption capacity for different heavy metals (60.2–1076.65 mg/g) [78]. GO also has a specific adsorption capacity for steroids: the removal efficiency of 17α-ethinylestradiol by magnetic GO can reach more than 25 mg/g [95].

1.4. Magnetic Carbon Nanocomposites

Various magnetic nanocomposites, including nanomaterials such as magnetic carbon nanotubes, magnetic graphene oxide, and magnetic metal–organic frameworks, exhibit excellent adsorption capabilities [96]. The advantage of magnetic nanomaterials is that their magnetic properties allow them to be separated from solutions and regenerated using an external magnetic field. Recently, magnetic nanocomposites have been extensively applied to the adsorption of EDC pollutants such as metals, steroid hormones, alkylphenols, and dyestuff from water [80,81]. Nanocomposites are primarily magnetized using ferriferous oxide (Fe3O4) and manganese ferrite (MnFe2O4). Different modified magnetic nanomaterials have different adsorption properties for specific anions, cations, and macromolecular dyes [97]. After the modification of PS-EDTA resin with magnetic ferric oxide nanoparticles, the Cr adsorption rate reached 99.3% [98]. An amino-functionalized mesoporous silica-magnetic GO nanocomposite, which was synthesized using a unique magnetic nanomaterial, removed oxytetracycline more effectively than the original magnetic graphene oxide (mGO) [99].

1.5. Carbon Membranes

Carbon membranes have become one of the most important materials employed in wastewater treatment. Carbon membranes have a low production cost and are highly permeable, selective, and stable [100]. Carbon membrane techniques are used for adsorption and filtration in a variety of wastewater treatment plants. The retention rates of nanoparticle-modified polyamide membranes for bisphenol A reached 99.4% [101]. The adsorption capacity of biopolymer carbon membranes modified with lignin, oat, soybean protein, sodium alginate, and chitosan for Pb2+ was 35 mg/g [102]. In addition, the adsorption capacity of an electrospun lignin–carbon membrane for methyl blue was 10 times greater than that of active carbon [103].

1.6. Carbon Dots

Carbon dots are single-layer or multilayer graphite structures or polymer aggregate carbon particles with a diameter less than 10 nm. Carbon dots have been acknowledged as discrete, quasispherical, fluorescent carbon particles, most of which are sp2 or sp3 hybrid carbon structures [104]. According to their structure and composition characteristics, carbon dots could be divided into graphene quantum dots (GQDs), carbon quantum dots (CQDs), and carbonized polymer dots (CPDs). The synthesized carbon dots show water solubility, good chemical stability, low toxicity, and good biocompatibility. In the adsorption treatment of water pollution, GQDs have received increasing attention as excellent adsorbents. It was reported that GQDs have good adsorption properties in removing pesticides, dyes, heavy metals, and drugs from water [68,105]. Modifying GQDs improves the adsorption effect of nanocomposites by increasing the specific surface area for removing anionic and cationic dyes. Meanwhile, the oxygen-containing functional groups on GQDs also enhance the electrostatic interaction between dyes and nanocomposites. It is the contribution of the formation of hydrogen bonds to the surface between the adsorbate and GQDs. The removal efficiency of Hg2+ and Pb2+ by GQD adsorption were 98.6 and 99.7%, respectively [86]. The other kinds of carbon dot nanocomposites also have an excellent EDC removal ability. For example, the maximum adsorption capacities of carbon dot nanocomposites for carbamazepine and tetracycline could reach up to 65 mg/g and 591.72 mg/g, respectively [87]. GQDs present significant opportunities for the adsorption of EDCs and pose challenges for future work in environmental application fields.

1.7. Carbon Sponges

Carbon sponges are a spongy nanomaterial with a high temperature resistance, excellent elasticity, fast adsorption rate, and low cost [106,107]. Graphene-based and carbon nanotube-based materials with aerogel structures were developed in recent years for various adsorption applications. Graphene aerogels and carbon nanotube aerogels are macroscopic porous materials with a unique isotropic structure. Dubey et al. [108] synthesized the graphene aerogel, which is the lightest material with a density of 0.16 g/L, in 2013. Graphene aerogels have a high adsorption efficiency for EDC pollutants such as dyes. For example, Li et al. [89] reported a new graphene sponge by using polyvinyl alcohol cross-linked GO for adsorbing methylene blue. The results showed that the excellent adsorption performance for the GO/polyvinyl alcohol sponge captured methylene blue in the flow state. In addition, carbon nanotube sponges are widely used to treat water pollution. Wang et al. [106] used carbon nanotube sponges as adsorbents to enrich trace polychlorinated biphenyls (PCBs) in water samples; the recovery rates of this analysis method for carbon nanotube sponges for PCBs are 81.1% to 119.1%, which have a good application prospect.

2. Innovative Methods of Carbon Nanocomposite Synthesis

2.1. In Situ Polymerization

In situ polymerization is the most common method of nanocomposite synthesis. In situ polymerization prevents the agglomeration of nanocomposites and results in uniform distributions and structures [109]. Youssef et al. [110] added prepared polyvinyl alcohol (PVA) to a solution of MWCNT materials, stirring for 3 h at room temperature, and dripping in 0.01 g of citric acid over 30 min to obtain an MWCNT/PVA hybrid polymer nanocomposite film. The addition of 6% MWCNT to PVA resulted in a remarkable increase in tensile strength (to 11.45 MPa) prior to the formation of the nanocomposite film. The removal rates of Cr2+, Cd2+, and Pb2+ by this composite material were more than 90%. In addition, the adsorption performance of carbon nanomaterials was improved after modification using in situ polymerization, and this method may thus play an important role in environmental applications.

2.2. Direct Compounding

Direct compounding is a synthesis method that does not require an activator or special reaction conditions. Direct compounding is widely used because of its simple steps, relatively low cost, and ease of expansion. For example, nanocomposites can be synthesized directly by mixing the polymer matrix and the nanomaterials under mechanical forces [80]. Yang et al. [111] synthesized an anionic polyacrylamide-functionalized GO composite by pouring an anionic polyacrylamide solution into a GO solution with slight mechanical stirring. The maximum adsorption capacity of this composite for basic fuchsin was up to 1034.3 mg/g, which indicates that anionic polyacrylamide/GO aerogels are promising adsorbents for the removal of dye pollutants from aqueous solutions.

2.3. Solvothermal Synthesis

Solvent thermal synthesis, for which water or organic solvents are the reaction medium, is usually used in a closed environment to create a critical reaction state (i.e., high temperature and high pressure) to generate homogeneous nanomaterials. Because water molecules hydrolyze at high temperatures, solvothermal synthesis has the advantage of forming nanoparticles of ideal shape, uniform size, and specific surface area. In solvent thermosynthesis, a molecule can easily be functionalized by simply replacing the original organic ligand with functional groups. Solvothermal synthesis can be finished in one step without adding a catalyst, such as the green synthesis of functional GO. Ammonia-modified GO was synthesized by solvothermal reaction at 180 °C for 10 h [112]. Guo et al. [113] synthesized Fe3O4–GS composites by solvothermal reaction by mixing FeCl3·6H2O, ethylenediamine, and GO at 200 °C for 8 h.

2.4. Electrospinning

Electrospinning is a useful fabrication technique that produces NF membranes. Electrospinning relies on the electrostatic repulsion between surface charges to absorb nanofibers in a viscoelastic fluid. For example, Sun et al. [114] prepared a super-hydrophobic carbon fiber membrane by electrospinning. Carbon nanofibers were prepared by electrospinning for their special phase morphology, crystal structure, and surface geometry. Electrospinning provides a simple and versatile method for generating ultrathin fibers from a rich variety of materials that include polymers, composites, and ceramics. Electrospinning synthesis technology can greatly improve the production efficiency of carbonyl nanomaterials.

3. Application in Wastewater

3.1. Regeneration and Reuse

Due to the economic benefits of EDC pollution treatments, it is necessary to summarize the regeneration and reuse efficiency of various nanoadsorbents.
A variety of adsorbent regeneration technologies have been developed, including thermal, steam, chemical, microwave-assisted, electrochemical, and biological regeneration methods. It was shown that thermally regenerated MWCNT (incubated at 300 °C for 2 h) maintained its adsorption efficiency for cyclophosphamide, ifosfamide, and 5-fluorouracil in water. These results indicate that, when regenerating an adsorbent, a suitable regeneration technique should be selected according to the chemical and physical properties of the adsorbent itself [123]. The adsorption rates of neutral and Pb2+ by the MnFe2O4/GO nanocomposite were 94% and 98.8%, respectively, and these magnetic nanomaterials could be recycled five times with good stability [124].
Generally, the adsorption efficiency of a recycled carbon nanoadsorbent will decrease as the number of use-cycles increases. Carbon-based nanocomposites have a better regeneration ability. In studies on the adsorption removal of rhodamine B dye using GO-based nano-nickel composite materials, the adsorption efficiency decreased from 90% to 85% after the first recovery and decreased to 60% after the fifth recovery [125].

3.2. Carbon Nanoadsorbent Patents

Patented carbon nanocomposites were reflected upon to understand the development and applicability of carbon nanoadsorbents in wastewater treatment. Dai et al. prepared a novel GO/chitosan composite adsorbent (Dai et al., patent CN113318710A. 31 August 2021). The adsorption capacity of the GO/chitosan composite adsorbent for Cr6+ was significantly enhanced. Guo et al. reported a novel method to synthesize a polyamidine/carbon nanomaterial that could be used to remove some anionic dyes in wastewater (Guo et al., patent CN109174035B. 15 June 2021). A novel modified carbon nanotube was prepared by Huang et al. for the adsorption of Pb2+. The sulfhydryl functional groups on the surface of carbon nanotubes could strongly chelate with Pb2+. The adsorption rate of Pb2+ can reach 92.89% (Huang et al., patent CN110449132B. 25 March 2022). Carbon sponge blending by nanocellulose, polyvinyl alcohol, and polyvinylpyrrolidone could efficiently remove Cr6+ (9.3948 mg/g) and organic dyes from water (Ma et al., patent CN105597681B. 14 November 2017). The adsorbing capacity of a nitrogen-doped graphene quantum dot hybrid membrane for Pb2+ removal is 9 mg/g (Liu et al., patent CN112723346B. 24 June 2022).

3.3. Comparison with Other Adsorbents

Rhe EDC adsorbent efficacy among carbon nanocomposites and other materials based on previous studies was compared. Carbon nanocomposites show great promise owing to their many advantages: First, compared with other adsorbents, carbon nanocomposites have a larger surface area and better adsorption capacity [126]. For example, the adsorption capacity of most activated carbons for methyl blue is 100–500 mg/g, while the nanoadsorbent capacity for MB is often higher than 500 mg/g [127]. ACF derived from japonica seed hair fibers has an adsorption capacity for MB of 943.372 mg/g [128]. Second, the application of nanocomposites can greatly reduce the cost of water treatment. Beck et al. [103] reported that the use of carbon nanofiber membranes can reduce energy consumption by 87% during wastewater treatment processes. Third, some biodegradable polymer/multiwalled carbon nanotubes can effectively reduce environmental pollution and have good adsorption properties for EDCs [129]. These carbon nanomaterials can be biodegraded after adsorption and the nanomaterials can be recycled.

This entry is adapted from the peer-reviewed paper 10.3390/ijms232113148

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