Removal of Uranyl Ion from Wastewater by Magnetic Adsorption Material of Polyaniline Combined with CuFe 2 O 4

Abstract

The magnetic adsorption material of polyaniline (PANI) with amino functional group combined with CuFe₂O₄ (CuFe₂O₄/PANI nanocomposite) has been described in this work. It has been characterized by TEM, XRD, XPS, BET, FTIR, and VSM, respectively. Significantly, it exhibits extremely high maximum adsorption capacity (322.6 mg/g) for removal of uranyl ions from wastewater at a pH of 4. The adsorption process is consistent with the quasisecond-order kinetic equation, and the isotherm and kinetic data are accurately described by the Langmuir isothermal adsorption model. Furthermore, the magnetic CuFe₂O₄/PANI displays stable adsorption performance for uranyl ions after five cycles of recovery in acid medium, which indicates it possesses good recovery due to its magnetism and excellent regeneration ability for reusability.

1. Introduction

In recent years, nuclear power is widely considered as a sustainable solution to the global demand for energy [1]. With the rapid expansion of the atomic energy industry as well as nuclear science and technology, the development of new green energy such as nuclear energy not only brings huge social and economic benefits to human society but also arise increasingly serious environmental problems. Nuclear energy as one of the clean energy sources, its series of environmental and safety problems brought about by its sustainable development have been paid close attention to nowadays. Meanwhile, due to the increasing discharge of radioactive nuclides in wastewater and the increasingly complex composition, people are paying more and more attention to the harmful problem it arises for human health and the ecological environment as well. Environmental contaminant releases that contain uranium are among the more serious problems that must be confronted by the decontamination programs. Uranium with natural radioactivity is one of the most basic nuclides in the field of nuclear research and the core resource of nuclear energy development. [2]. As one of the most common pollutants, uranium also has the characteristics of strong radioactivity, high carcinogenicity, and toxicity, which will cause great radiation harm to the human organism and the ecological environment. Under oxidizing conditions, dissolved uranium is predominantly in the U (VI) (uranyl ions) form and is potentially quite mobile in the aquatic environment. Therefore, removal of uranyl ions from aqueous solution is becoming of great importance for not only sustainable development of nuclear energy but also the environment protection.

More and more research is focused on the removal and recycling of uranium in wastewater ([3, 4]; Ozdemir and Usanmaz, [5]). At present, the commonly used treatment methods for industrial wastewater containing uranium and heavy metal ions mainly include chemical precipitation method [6], extraction method [7], biological method [8], membrane filtration method [9], and adsorption method [10–12]. Adsorption method, as a type of environmental protection, belongs to a low harmful treatment to remove wastewater of radionuclides and heavy metal ion (lead, mercury, cadmium, chromium, etc.), due to its economic advantage, species diversity, good stability, high applicability, simple operation, high treatment efficiency, and better regeneration [13–17].

Screening suitable adsorption materials with high adsorption capacity is becoming extremely important to remove uranium efficiently from wastewater. [18–20]. The commonly used adsorption materials are including graphene, carbon nanotubes, some carbon materials, cellulose, polymer materials, kaolin, clay, mineral, organic-inorganic hybrid adsorption materials, ion-imprinted polymers, and other composite materials, but their limitations are focused on not very high adsorption efficiency, high cost, low selectivity, long preparation period, and difficulty of recycling. [21–23] [24]. Therefore, the development and utilization of new high efficiency of uranium adsorption material are one of the most important issues of concern to be solved at present.

Magnetic composite nanomaterials have been widely used in environmental protection, catalysis, and biomedicines and have broad application prospects. [25–28]. A large number of studies have been carried out on the removal of heavy metals in wastewater by using magnetic nanoparticles as magnetic core in the composite adsorption materials. It has also been proved that it has the characteristics of strong magnetism, good adsorption, easy separation, and collection under the action of an external magnetic field [29–33]. More importantly, the functional groups of magnetic nanocomposite which is proper prepared based on different matrix can be designed according to the adsorption selectivity of the adsorption material for specific radionuclides. The advantages of it combined with other materials can complete and improve the comprehensive performance, which would not be obtained by a single component. Many new combination properties can solve the problem much better than the single magnetic nanomaterial showing low adsorption performance for pollutants [34, 35].

Polyaniline (PANI) is a type of polymer compound with high conductivity, which contains a large number of amino and imine groups [36]. As the exists of the abundant amounts of primary and secondary amino groups, PANI is expected to have a strong affinity with heavy metal ions by redox reaction [37, 38]. Due to its low production cost, simple synthesis method, good chemical, and environmental stability, PANI has been widely applied to the adsorption of heavy metal pollutants from wastewater in recent years [39–41]. It has also been found that the magnetic PANI nanocomposite modified with GO composites would attract materials with exceptional ability in the selective extraction of trace U (VI) from aqueous solutions [42, 43]. It highlights the extensive applicability of these novel materials in the selective extraction and separation of trace uranyl ions from aqueous solution in nuclear fuel extraction processes.

Therefore, magnetic adsorption material of polyaniline (PANI) combined with CuFe₂O₄ (CuFe₂O₄/PANI nanocomposite) has been synthesized in this work. In the meanwhile, the amino functional groups with complexation for uranyl ions were introduced, which would improve the adsorption capacity of the novel materials. The new type of magnetic CuFe₂O₄/PANI nanocomposite for trace uranyl ions adsorption capacity in aqueous solution under different operating conditions was studied in detail. It was characterized by TEM, FTIR, XRD, XPS, and BET, respectively, and batch adsorption experiments were carried out as well to study the effects on the uranium adsorption of various experimental parameters, such as pH value, contact time, temperature, and initial concentration. The adsorption kinetics, isotherm models, and thermodynamics were evaluated in detail to understand the adsorption process. Finally, the recycling regeneration of the adsorption nanocomposite for its reusability was analysed in detail through the experiments of adsorption/desorption cycle regeneration.

2. Experimental

2.1. Materials and Reagents

The chemical reagents used in this study were all of analytical grade with 98-99% purity. It includes copper sulfate (CuSO₄·5H₂O), ferric chloride (FeCl₃·6H₂O), polyethylene glycol 6000 (PEG), potassium hydroxide (KOH), hydrochloric acid (HCl), aniline (C₆H₇N), ethyl alcohol (C₂H₆O), and ammonium thiosulfate ((NH₄)₂S₂O₃). All the analytical grade chemical reagents used in this study were without further purification. Freshly deionized water was used as the dispersion medium. The stock uranium (U (VI)) solution was prepared by dissolving the appropriate amounts of uranyl nitrate hexahydrate [UO₂(NO₃)₂·6H₂O] in deionized water. The concentration of uranium stock solution is 1000 mg/L, which is diluted to 5 ~ 300 mg/L by gradient dilution method.

2.2. Instrumentations

Surface morphological images were characterized by transmission electron micrograph (TEM) (FEI Tecnai G2) at an accelerating voltage of 200 kV. The functional groups of the materials were confirmed by Fourier transform infrared (FT-IR) (Vertex70, Bruker company). The materials were pelletized using KBr prior to FTIR measurement. XRD analysis was carried out on a D8 Advance instrument (Bruker company) with Cu Kα radiation source ( $λ = 1.5406 Å$ ). The operating condition was at a scan rate of 3°/min from 10° to 90° to obtain the XRD pattern. Surface areas of samples were determined from N₂ adsorption isotherms at 77.3 K with the BET method using a Micromeritics ASAP 2010 analyzer prior to the surface area measurement, and the samples were outgassed at 120°C for 27 h under a reduced pressure of $6.58 \times 10^{- 5} Torr$ . X-ray photoelectron spectroscopy (XPS) spectra were obtained on a VG Thermo Escalab 250Xi spectrometer operated at 120 W. VSM analysis was carried out on the condition of hysteresis loop, which normal temperature and the maximum magnetic field applied were 2 T. Temperature scanning rate was 1 K/min, vibration amplitude was 4 cm, and scanning twice each time. The uranyl ion concentration was determined by a trace uranium analyzer (WGJ-III, Institute of comparative geology of nuclear industry).

2.3. Synthesis of the Adsorption Materials

2.3.1. Synthesis of CuFe₂O₄ Nanoparticles

CuFe₂O₄ nanoparticles were prepared by thecoprecipitation technique. 4.05 g FeCl₃·6H₂O FeCl₃ and 2.93 g CuSO₄·5H₂O were dissolved in 200 mL 1 wt% PEG solution. Stir the solution continuously for about 60 minutes to ensure a balance between all ingredients. The pH of the mixture was adjusted to 8 with adding 3 mol/L KOH solution. The mixture continued to be stirred magnetically for three hours and then aged overnight. The precipitate was filtered and washed repeatedly with distilled water until there were no SO₄ ^2- and Cl^- ions. Then, it was dried in a constant temperature drying oven at 50°C for 12 h and calcined at 600°C for 4 h, and finally, CuFe₂O₄ nanoparticles were obtained in the end.

2.3.2. Synthesis of CuFe₂O₄/PANI Nanocomposite

CuFe₂O₄/PANI nanocomposite was prepared by chemical in situ polymerization. 2 g CuFe₂O₄ nanoparticles were dispersed in 200 mL 2 mol/L hydrochloric acid solution and stirred vigorously for 10 minutes. A certain amount of 1.2 g distilled aniline monomers was added to the above mixture and then stirred continuously for 60 min. Then, 20 mL 20 mmol (NH₄)₂S₂O₈ solution was added drop by drop to the mixture as a polymerization initiator. An immediate change in the color of the molecules was observed. The suspension was stirred to complete the polymerization process in about 12 h. Finally, the CuFe₂O₄/PANI nanocomposite was filtered, rinsed repeatedly with distilled water and anhydrous ethanol, and dried in a constant temperature drying oven at 70°C for 12 h.

2.4. Batch Adsorption Experiments

A series of uranium solutions with different concentrations (5 ~ 300 mg/L) were prepared. For adsorption studies, 5 mg CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite was mixed, respectively, with 9 mL uranium solution with a concentration of 100 mg/L in a 10 mL centrifuge tube. The pH value of uranium solution was adjusted to 2 ~ 6 by with 1 mg/L hydrochloric acid and 0.1 mg/L sodium hydroxide, and the solution was adsorbed at 25°C, 35°C, and 45°C, respectively, for 5 min to 120 min. The mixture was centrifuged to take out the supernatant after absolutely adsorption, without inhaling the solid particles for intermittent adsorption experiment. Adsorption capacity ( $Q_{e}$ ) is calculated according to Equation (1) $\begin{matrix} (1) & Q_{e} = (C_{0} - Ce) \times \frac{v}{m} . \end{matrix}$

In the above formula, $C_{0}$ and Ce were the initial concentration and equilibrium concentration of uranium solution (mg/L); $v$ was the volume of uranium solution (L), $m$ was the mass of adsorption material, and the unit was g.

2.5. Desorption Experiments

At the end of each adsorption experiment, the solution in the centrifuge tube was centrifuged to recover the adsorption material, which had adsorbed uranyl ions. The CuFe₂O₄/PANI nanocomposite was treated with ultrasound in 0.01 mol/L hydrochloric acid solution for 5 min to remove the uranyl ions adsorbed in the adsorption material. The uranyl ions in the solution were then separated from CuFe₂O₄/PANI nanocomposite by centrifugation. The recovered nanocomposite was washed thoroughly before the adsorption experiment. In the repeated adsorption experiment, the concentration of uranyl ions in the residual solution after adsorption was determined by the micro uranium analyzer. In order to further determine the recyclability of CuFe₂O₄/PANI nanocomposite, five adsorption/elution cycles of uranyl ions were repeated in the experiments [44].

2.6. Adsorption Kinetics

Adsorption kinetics was an important method to study the adsorption efficiency of uranium. In order to further study the adsorption kinetics and mechanism of CuFe₂O₄/PANI nanocomposite, the pseudosecond-order kinetic Equation (2) was used to fit the experimental data. $\begin{matrix} (2) & \frac{t}{Q_{t}} = \frac{1}{K_{2} \cdot {Q_{e}}^{2}} + \frac{t}{Q_{e}} . \end{matrix}$

In the above formula, $Q_{e}$ was the adsorption capacity of adsorption material for uranyl ions at equilibrium time (mg/g); $Q_{t}$ was the adsorption capacity of the nanocomposite for uranyl ions reaction $t$ time (mg/g); $K_{2}$ was the rate constant of quasi second order kinetics (g·mg^-1·min^-1).

2.7. Equilibrium Isotherm Modelling

In order to better study the adsorption mechanism of the adsorption materials for uranyl ions, Langmuir and Freundlich isothermal adsorption models were used to fit the experimental data for uranium adsorption. Langmuir and Freundlich isothermal adsorption equations were shown in Formulas (3) and (4), respectively. $\begin{matrix} (3) & \frac{C_{e}}{q_{e}} = \frac{1}{q_{\max} K_{L}} + \frac{C_{e}}{q_{\max}}, \\ (4) & \ln Q_{e} = \ln K_{f} + \frac{\ln C_{e}}{n} . \end{matrix}$

In the above formula, $C_{e}$ was the equilibrium concentration (mg/L); $q_{e}$ was the adsorption capacity (mg/g) of equilibrium time of uranyl ions; $q_{\max}$ was the maximum adsorption capacity (mg/g); $K_{L}$ was the adsorption isotherm parameter of Langmuir; $K_{f}$ represented adsorption strength (mg^1-n·g^-1·Lⁿ); $N$ was the adsorption capacity.

3. Results and Discussion

3.1. Characterization

The TEM images of magnetic CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite are shown in Figure 1. As can be seen from the TEM images in Figure 1(a), CuFe₂O₄ nanoparticles have irregular spherical shape with good dispersion and a particle size of about 100 nm. As shown in Figure 1(b), the generated polyaniline (PANI) coats with CuFe₂O₄ magnetic nanoparticles and forms a core-shell structure. The boundary between CuFe₂O₄/PANI nanocomposite is clear and presents regular distribution.

Figure 1

(a) TEM of CuFe₂O₄ nanoparticles and (b) TEM of CuFe₂O₄/PANI nanocomposite.

It shows in Figure 2 that the XRD pattern of magnetic CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite are set from 10° to 90°. According to the XRD pattern, the diffraction peak is consistent with the amorphous phase of polyaniline, and the characteristic peak of PANI is displayed at 24.2°. It can be seen from the XRD pattern of CuFe₂O₄ that the characteristic peak appears at 33.3°, and the diffraction peak is consistent with the square spinel of CuFe₂O₄, with good crystallinity [45, 46]. When PANI is successfully combined with CuFe₂O₄, it has no great influence on the crystal structure of CuFe₂O₄ nanoparticles.

Figure 2

XRD of CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

As shown in Figure 3(a), there are five peaks at 288.5, 399.1, 531.9, 710.7, and 950.2 eV, corresponding to C1s, N1s, O1s, Fe2p, and Cu2p, respectively. As shown in Figure 3(b), there are four peaks at 284.4, 532.1, 714.0, and 935.7 eV, corresponding to C1s, O1s, Fe2p, and Cu2p, respectively. It can be seen from the figure that a new peak of N1s with a binding energy of 400.7 eV appears, which proves the existence of nitrogen atoms. It indicates that polyaniline has been successfully compounded on the magnetic CuFe₂O₄ nanoparticles.

Figure 3

X-ray photoelectron spectroscopy of (a) CuFe₂O₄ nanoparticles and (b) CuFe₂O₄/PANI nanocomposite.

(b)

Figure 4 shows the total pore volume of magnetic CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite of the N₂ adsorption-desorption isotherm, which is shown in Table 1 for relevant parameters.

Figure 4

N₂ adsorption-desorption curves of CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

Table 1

Analysis of specific surface area and pore volume of CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

Sample	Surface area (m²/g)	Average pore volume (cm³/g)	Average pore diameter (nm)
CuFe₂O₄	91.1	0.258	3.06
CuFe₂O₄/PANI	153	0.280	3.83

Compared with CuFe₂O₄/PANI nanocomposites, the surface area of the material modified by polyaniline changes from 91.1 to 153 m²/g, and the total pore volume and nitrogen adsorption capacity increase as the introduction of polyaniline. The porous core-shell structure formed by polyaniline coating on CuFe₂O₄ increases the pore diameter of the nanocomposite.

It shows in Figure 5 the IR spectra of magnetic CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite. According to the IR of CuFe₂O₄ nanoparticles, the peak at 433 cm^-1 is the stretching vibration peak of Cu-O bond, and the peak at 597 cm^-1 is the stretching vibration peak of Fe-O bond. This indicates that CuFe₂O₄ nanoparticles have been successfully synthesized. According to the spectrum of CuFe₂O₄/PANI nanocomposite, the peak at 1301 cm^-1 represents C-N vibration absorption peak, the peak at 1481 cm^-1 is C-N vibration absorption peak, and the peak at 1567 cm^-1 is N-H vibration absorption peak ([47–49]; Jawad, [50]). In the IR spectrum of CuFe₂O₄/PANI nanocomposite, the characteristic peak of PANI can be seen, indicating the successful preparation of CuFe₂O₄/PANI nanocomposite.

Figure 5

FTIR analysis of CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

The magnetic properties of CuFe₂O₄ nanoparticles, CuFe₂O₄/PANI nanocomposite, and adsorbed CuFe₂O₄/PANI nanocomposite are characterized by vibrating sample magnetometer (VSM). The VSM diagram of them is shown in Figure 6.

Figure 6

VSM curves of CuFe₂O₄ nanoparticles, CuFe₂O₄@PANI nanocomposite, and adsorbed CuFe₂O₄@PANI nanocomposite.

As can be seen from Figure 6, the synthesized CuFe₂O₄ has magnetic properties (0.04 emu/g), but it is indeed very weak compared with other magnetic materials. It still appears “S” shaped hysteresis curve in CuFe₂O₄, which could be simply separated from a solution by external magnetic fields. After coating with PANI, the saturation magnetization value seems increased to a certain extent, but in fact, the actual value is very low, only as 0.07 emu/g. The slight increase may be due to the residual free radicals during the polymerization process. After adsorption, the saturated magnetization intensity of CuFe₂O₄@PANI nanocomposite is reduced to 0.02 emu/g, which may be caused by the quenching of free radicals. It is close to its “intrinsic” value (0.025 emu/g, $0.04 emu / g \times 0.625$ , the ratio of CuFe₂O₄ to PANI is 0.625).

3.2. Effect of pH on Adsorption of Uranyl Ions

Uranium has relatively active chemical properties. In alkaline media, uranium acid (UO₂ ^2-) or diuranic acid (U₂O₇ ^2-) anions are easily produced. Uranium grinding cations (UO₂ ²⁺) tend to be produced in neutral and acidic media. The pH value of the solution not only affects the content of uranyl ions but also affects the adsorption performance of the adsorption material. Under the conditions of initial concentration of 100 mol/L, the adsorption time of 60 min and temperature of 25°C, CuFe₂O₄/PANI nanocomposite was used to study the effect of initial pH of the solution on the adsorption capacity of uranyl ions, shown as in Figure 7.

Figure 7

Effect of initial pH value of solution on the adsorption of UO₂ ²⁺ by CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

In the initial solution, pH affects the adsorption experiment and the choice of pH range of 2 ~ 6 in the uranium adsorption experiments, and it can be seen that the adsorption quantity of magnetic CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite increases with the increase of pH value. At the condition of low pH, the adsorption capacity of CuFe₂O₄/PANI nanocomposite as well as magnetic CuFe₂O₄ nanoparticles is low, and it is because there is a lot of H⁺ that compete with uranyl ion adsorption. With the increase of pH, the adsorption rate increases. If the pH value continues to increase, at a higher pH value, UO₂ ²⁺ will hydrolyze to produce UO₂ (OH)₂ polynuclear hydroxide precipitation. So the pH value of 4 is selected for the following adsorption experiment.

As shown in Figure 7, the adsorption performance of CuFe₂O₄/PANI nanocomposite is higher than that of CuFe₂O₄ when the pH value is very low. When the pH value is in the range of 4 to 6, the adsorption performance gradually decreases.

3.3. Effect of Initial Concentration on Adsorption of Uranyl Ions

In order to evaluate the adsorbability of the materials and further to prove whether the introduction of amino groups could improve the adsorption properties. As can be seen from Figure 8, the adsorption capacity of CuFe₂O₄/PANI nanocomposite and CuFe₂O₄ nanoparticles is relatively small when the initial concentration of uranyl ions is low, and the adsorption capacity goes up with the increase of the initial concentration. When the initial concentration is low, more amino groups would be coordinated with uranyl ions, and up to saturation point as the initial concentration increases gradually. So, the adsorption rate of uranyl ions in CuFe₂O₄/PANI nanocomposite is relatively high at low concentration. As a large number of nitrogen exist in CuFe₂O₄/PANI nanocomposite, the adsorption amount is as high as almost 320 mg/g under the condition of $Ce < 100 mg / L$ in its quick equilibrium state which indicates the excellent adsorption performance for uranyl ions adsorption.

Figure 8

Effect of initial concentration value of solution on the adsorption of UO₂ ²⁺ by CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

3.4. Effect of Temperature and Adsorption Time on Adsorption of Uranyl Ions

It shows the adsorption capacity curve of the adsorption material at temperatures of 25°C, 35°C, and 45°C with the adsorption time of 5 ~ 120 min in Figure 9. It can be observed that the adsorption capacity of the adsorbent is basically balanced at about 20 min, and the adsorption equilibrium time is short. It can be seen from the results that the adsorption capacity of the adsorption materials is affected by the temperature. CuFe₂O₄/PANI nanocomposite adsorbing uranyl ions is the heat absorption process, the adsorption capacity is significantly lower when the temperature is low, and the adsorption capacity is greater when the temperature is high. This is mainly because with the increase of adsorption temperature, the reaction activity of amino groups and uranyl ions of CuFe₂O₄/PANI nanocomposite is enhanced, which is conducive to display its adsorption performance.

Figure 9

Effect of temperature and adsorption time value of solution on the adsorption of uranyl ions by CuFe₂O₄/PANI nanocomposite.

3.5. Regeneration

Recycling is an important index to evaluate the adsorption and regeneration performance of the adsorbents. It is of great significance to evaluate recycling in the practical application of adsorbents, which can not only save time but also reduce production costs. In order to evaluate the important index of recycling regeneration of CuFe₂O₄/PANI nanocomposite, 0.01 mol/L HCl solution was used as the elution solution of regeneration.

More significantly, as reflected in Figure 10, the magnetic adsorption material is used to remove uranyl ions after regeneration. It shows the adsorption rate of CuFe₂O₄/PANI nanocomposite recovered in each adsorption/desorption cycle. The adsorption capacity of uranyl ions displays more than 170 mg/g during five consecutive cycles. The slight influence on the adsorption capacity proves that the CuFe₂O₄/PANI nanocomposite has a high reuse rate and displays its practical application prospect.

Figure 10

U (VI) adsorption efficiency on recycled CuFe₂O₄/PANI nanocomposite at each adsorption/desorption cycle.

3.6. Adsorption Kinetics

Adsorption kinetics is an important method to study the adsorption efficiency of uranium. It can be seen from Figure 11 that CuFe₂O₄/PANI nanocomposite exhibits fast adsorption kinetics for uranyl ions.

Figure 11

Pseudosecond-order kinetic curves of uranium adsorption on CuFe₂O₄/PANI nanocomposite at different temperatures: (A) 25°C, (B) 35°C, and (C) 45°C, respectively.

It can be seen from Figure 11 and Table 2 that both adsorption capacity and reaction rate are affected by temperature. The quasisecond-order kinetic model to calculate the actual value theory adsorption capacity is closed to the experiment, and it shows that quasisecond-order kinetic model fits the linear correlation coefficient.

Table 2

Kinetic parameters for uranium adsorption by CuFe₂O₄/PANI nanocomposite.

T (°C)	Pseudosecond-order kinetics model
T (°C)	$q_{e}$ (mg/g)	$K_{2}$ (g·mg^-1·min^-1)	$R^{2}$
25	131.6	0.0064	0.9975
35	163.9	0.0081	0.9994
45	188.7	0.0055	0.9993

The correlation coefficient $R^{2}$ is more than 0.99; therefore, the quasisecond-order kinetic model can describe the adsorption behavior of CuFe₂O₄/PANI nanocomposite for uranyl ions.

3.7. Equilibrium Isotherm Modelling

In order to better study the adsorption mechanism of CuFe₂O₄ and CuFe₂O₄/PANI nanocomposite for uranyl ions, Langmuir and Freundlich isothermal adsorption models are used to fit the experimental data for uranyl ions adsorption of CuFe₂O₄ and CuFe₂O₄/PANI nanocomposite, respectively.

As shown in Figures 12 and 13 and Table 3, the correlation coefficient $R^{2}$ of the Langmuir model is greater than 0.999. The experimental data are closed to the theoretical model, indicating that it can well describe the adsorption process of uranyl ions by CuFe₂O₄/PANI nanocomposite. The isotherm is best described by Langmuir adsorption model in the process of adsorption kinetics.

Figure 12

Fitting curves of Langmuir isotherm adsorption model for uranium on CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

Figure 13

Fitting curves of Freundlich isotherm adsorption model for uranium on CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite.

Table 3

Langmuir and Freundlich isotherm adsorption constants of CuFe₂O₄ nanoparticles and CuFe₂O₄/PANI nanocomposite for uranium adsorption.

Adsorbent type	Langmuir			Freundlich
Adsorbent type	$K_{L}$ (mg/L)	$q_{m}$ (mg/g)	$R^{2}$	$K_{f}$ (mg^1-n·g^-1·Lⁿ)	$n$	$R^{2}$
CuFe₂O₄	0.0709	49.50	0.9996	5.57	2.38	0.8992
CuFe₂O₄/PANI	0.310	322.6	0.9998	102	3.74	0.8545

The maximum adsorption capacity for uranyl ions is about 322.6 mg/g, which is higher than many other types of uranyl ion adsorbents and has good adsorption performance comparing with other similar work [13].

It lists the comparison of maximum adsorption capacity ( $q_{m}$ ) of U(VI) using various adsorbents in Table 4 [49, 51–55]. The maximum adsorption capacity of CuFe₂O₄/PANI on U(VI) was higher than that of other adsorbents as shown in Table 4.

Table 4

Comparison of adsorption capacity of CuFe₂O₄/PANI nanocomposite with different adsorbents.

Adsorbents	Maximum adsorption capacity	Ref
Polypropylene (PP) nanofibers	83.24 mg/g	[55]
Ap-ZnO/PSBN	139.8 mg/g	[51]
AM/PDA	250.7 mg/g	[54]
MoS₂-IP6 NRA/CC	183.3 mg/g	[53]
SBA-15/NHSO₃H	140.5 mg/g	[52]
CuFe₂O₄/PANI	322.6 mg/g	This work

3.8. Magnetic Validation Study

As shown in Figure 13, the magnetic verification experiment results show that the synthesized CuFe₂O₄/PANI nanocomposite has good magnetic properties, which ensures that the adsorption material can be easily separated from the cleaning medium. It shows in the magnetic verification experiment the ideal magnetism under the action of magnet in Figure 14(a). On this basis, its dispersion is further verified by ultrasound. Results as shown in Figure 14(b), CuFe₂O₄/PANI magnetic nanocomposite has good dispersion after ultrasound, indicating that the particles are uniform and of good particle size. In the magnetic separation verification experiment of SiO₂ turbidity liquid, it has sufficient magnetic response to make it separated from the mixture immediately under the action of the external magnetic field. Therefore, CuFe₂O₄/PANI nanocomposite has been easily to be enriched under the action of magnetic field and can be used for magnetic separation, recovery, and reuse for its practical application prospect.

Figure 14

Pictures of magnetic validation of CuFe₂O₄/PANI nanocomposite.

(b)

4. Conclusion

In this study, a novel magnetic adsorption material CuFe₂O₄/PANI nanocomposite has been successfully prepared by polyaniline (PANI) combined with CuFe₂O₄ nanoparticles in situ polymerization and is used for the adsorption of radioactive uranium in an aqueous solution. When $pH = 4.0$ , magnetic CuFe₂O₄/PANI nanocomposite has the best adsorption effect, and the maximum adsorption capacity for uranyl ions is 322.6 mg/g. The introduction of amino functional groups makes the adsorption performance of CuFe₂O₄/PANI nanoparticles much higher than that of CuFe₂O₄ nanoparticles. The adsorption process is consistent with the quasisecond-order kinetic equation and Langmuir isothermal adsorption model, which indicates that the adsorption process is mainly chemisorption and monolayer adsorption. The recovery experiments show that magnetic CuFe₂O₄/PANI nanocomposite has good repeatability and stability due to its magnetic properties. After five cycles of recovery, the adsorption capacity of magnetic CuFe₂O₄/PANI nanocomposite would be maintained at more than 170 mg/g, which is expected to be a promising renewable adsorption material.

Footnotes

Data Availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

Additional Points

Highlights. A novel magnetic adsorption material CuFe₂O₄/PANI nanocomposite has been synthesized by polyaniline (PANI) combined with CuFe₂O₄ in situ polymerization. The prepared CuFe₂O₄/PANI nanocomposite exhibits extremely high maximum adsorption capacity (322.6 mg/g) for uranyl ion in wastewater at a pH of 4 and can quickly reach the equilibrium state. The magnetic CuFe₂O₄/PANI displays stable adsorption performance for uranyl ions after five cycles of recovery, which indicates it possesses good recovery due to its magnetism and excellent regeneration ability for reusability.

Conflicts of Interest

The authors declare that they have no conflicts of interest.

References

Manos

M. J.

Kanatzidis

M. G.

Layered metal sulfides capture uranium from seawater

Journal of the American Chemical Society 2012 134

5584158

39 16441 16446

10.1021/ja308028n

2-s2.0-84867091008

23009164

Chu

Majumdar

Opportunities and challenges for a sustainable energy future

Nature 2012 488

5584158

7411 294 303

10.1038/nature11475

2-s2.0-84865120266

22895334

Kathren

R. L.

Tolmachev

S. Y.

The US Transuranium and Uranium Registries (USTUR): a five-decade follow-up of plutonium and uranium workers

Health Physics 2019 117

5584158

2 118 132

10.1097/HP.0000000000000963

2-s2.0-85059947189

31225827

Wei

Zhao

Chen

Tang

The removal of uranium using novel temperature sensitive urea-formaldehyde resin: adsorption and fast regeneration

Science of the Total Environment 2020 735

5584158

139399

10.1016/j.scitotenv.2020.139399

ÖZdemir

Usanmaz

Use of poly(methyl methacrylate) in radioactive waste management: II. Monte Carlo simulations

Progress in Nuclear Energy 2009 51

5584158

8 845 848

10.1016/j.pnucene.2009.06.002

2-s2.0-68749090784

Mellah

Chegrouche

Barkat

The precipitation of ammonium uranyl carbonate (AUC): thermodynamic and kinetic investigations

Hydrometallurgy 2007 85

5584158

2-4 163 171

10.1016/j.hydromet.2006.08.011

2-s2.0-33846682689

Chen

M. M.

J. H.

Zhang

The extraction of uranium using graphene aerogel loading organic solution

Talanta 2017 166

5584158

284 291

10.1016/j.talanta.2017.01.070

2-s2.0-85011372366

28213236

Zheng

X. Y.

Wang

X. Y.

Shen

Y. H.

Wang

T. S.

Biosorption and biomineralization of uranium(VI) by _Saccharomyces cerevisiae_ --crystal formation of chernikovite

Chemosphere 2017 175

5584158

161 169

10.1016/j.chemosphere.2017.02.035

2-s2.0-85012996370

28211330

Torkabad

M. G.

Keshtkar

A. R.

Safdari

S. J.

Comparison of polyethersulfone and polyamide nanofiltration membranes for uranium removal from aqueous solution

Progress in Nuclear Energy 2017 94

5584158

93 100

10.1016/j.pnucene.2016.10.005

2-s2.0-84994017822

10.

De Decker

Folens

De Clercq

Meledina

Van Tendeloo

Du Laing

Van Der Voort

Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption

Journal of Hazardous Materials 2017 335

5584158

1 9

10.1016/j.jhazmat.2017.04.029

2-s2.0-85017441160

28414943

11.

Kirillov

S. A.

Lisnycha

T. V.

Pendelyuk

O. I.

Appraisal of mixed amorphous manganese oxide/titanium oxide sorbents for the removal of strontium-90 from solutions, with special reference to Savannah river site and chernobyl radioactive waste simulants

Adsorption Science & Technology 2006 24

5584158

10 895 906

10.1260/026361707781421979

2-s2.0-85011661208

12.

Liu

Song

Cheng

Xiong

Shi

Zhang

MIL-101(Cr) metal-organic framework functionalized with tetraethylenepentamine for potential removal of uranium (VI) from waste water

Adsorption Science & Technology 2018 36

5584158

7-8 1550 1567

10.1177/0263617418789516

2-s2.0-85053907668

13.

Alqadami

A. A.

Naushad

Alothman

Z. A.

Ghfar

A. A.

Novel metal-organic framework (MOF) based composite material for the sequestration of U(VI) and Th(IV) metal ions from aqueous environment

ACS Applied Materials & Interfaces 2017 9

5584158

41 36026 36037

10.1021/acsami.7b10768

2-s2.0-85031710082

28976726

14.

d’Halluin

Rull-Barrull

Bretel

Labrugère

Le Grognec

Felpin

F.-X.

Chemically modified cellulose filter paper for heavy metal remediation in water

ACS Sustainable Chemistry & Engineering 2017 5

5584158

2 1965 1973

10.1021/acssuschemeng.6b02768

2-s2.0-85011838799

15.

Ekoa Bessa

A. Z.

Ngueutchoua

Kwewouo Janpou

el-Amier

Y. A.

Njike Njome Mbella Nguetnga

O. A.

Kankeu Kayou

U. R.

Bisse

S. B.

Ngo Mapuna

E. C.

Armstrong-Altrin

J. S.

Heavy metal contamination and its ecological risks in the beach sediments along the Atlantic Ocean (Limbe coastal fringes, Cameroon)

Earth Systems and Environment 2020 1 12

10.1007/s41748-020-00167-5

16.

Rangabhashiyam

Balasubramanian

Characteristics, performances, equilibrium and kinetic modeling aspects of heavy metal removal using algae

Bioresource Technology Reports 2019 5

5584158

261 279

10.1016/j.biteb.2018.07.009

17.

Sharma

Naushad

Adsorptive removal of noxious cadmium ions from aqueous medium using activated carbon/zirconium oxide composite: isotherm and kinetic modelling

Journal of Molecular Liquids 2020 310

5584158

317

10.1016/j.molliq.2020.113025

18.

Liu

X. L.

Pang

H. W.

Liu

X. W.

Zhang

Mao

Qiu

Yang

Wang

Orderly porous covalent organic frameworks-based materials: superior adsorbents for pollutants removal from aqueous solutions

The Innovation 2021 2

5584158

1 100076

10.1016/j.xinn.2021.100076

19.

Zhang

Uchiyama

Asakura

Dynamic-state adsorption and elution behaviour of uranium (VI) ions from seawater by a fibrous and porous adsorbent containing amidoxime chelating functional groups

Adsorption Science & Technology 2003 21

5584158

8 761 773

10.1260/026361703773581812

2-s2.0-0347900461

20.

Zou

W. H.

Song

J. Y.

Han

Use of manganese oxide-coated sand for the adsorption of uranium(VI) ions from aqueous solution using a column mode

Adsorption Science & Technology 2010 28

5584158

4 313 325

10.1260/0263-6174.28.4.313

2-s2.0-79751510924

21.

Wongjaikham

Wongsawaeng

Hosemann

Kanokworakan

Ratnitsai

Enhancement of uranium recovery from seawater using amidoximated polymer gel synthesized from radiation-polymerization and crosslinking of acrylonitrile and methacrylic acid monomers

Journal of Environmental Chemical Engineering 2018 6

5584158

2 2768 2777

10.1016/j.jece.2018.04.016

2-s2.0-85045880156

22.

J. L.

Tian

Wang

J. L.

Adsorption of uranium (VI) by amidoxime modified multiwalled carbon nanotubes

Progress in Nuclear Energy 2018 106

5584158

79 86

10.1016/j.pnucene.2018.02.020

2-s2.0-85043377660

23.

Zong

Gou

Lei

Liu

Deng

Immobilization and recovery of uranium(VI) using Na-bentonite from aqueous medium: equilibrium, kinetics and thermodynamics studies

Journal of Molecular Liquids 2015 209

5584158

358 366

10.1016/j.molliq.2015.05.052

2-s2.0-84930960171

24.

Anirudhan

T. S.

Lekshmi

G. S.

Shainy

Synthesis and characterization of amidoxime modified chitosan/bentonite composite for the adsorptive removal and recovery of uranium from seawater

Journal of Colloid and Interface Science 2019 534

5584158

248 261

10.1016/j.jcis.2018.09.009

2-s2.0-85053290689

30227381

25.

Acharya

Padhi

D. K.

Parida

K. M.

Visible light driven LaFeO₃ nano sphere/RGO composite photocatalysts for efficient water decomposition reaction

Catalysis Today 2020 353

5584158

220 231

10.1016/j.cattod.2017.01.001

2-s2.0-85009912612

26.

Jawed

Saxena

Pandey

L. M.

Engineered nanomaterials and their surface functionalization for the removal of heavy metals: a review

Journal of Water Process Engineering 2020 33, article 101009

5584158

10.1016/j.jwpe.2019.101009

27.

Wang

Zhao

Wang

Efficient removal of Cr (VI) by magnetic and recyclable calcined CoFe- LDH/g-C₃N₄ via the synergy of adsorption and photocatalysis under visible light

Chemical engineering journal 2020 380

5584158

122600

10.1016/j.cej.2019.122600

28.

Serantes

Chantrell

Gavilán

del Puerto Morales

Chubykalo-Fesenko

Baldomir

Satoh

Anisotropic magnetic nanoparticles for biomedicine: bridging frequency separated AC-field controlled domains of actuation

Physical Chemistry Chemical Physics 2018 20

5584158

48 30445 30454

10.1039/C8CP02768D

2-s2.0-85058515966

30506075

29.

Chang

Y. P.

Ren

C. L.

J. C.

Chen

X. G.

Preparation and characterization of Fe₃O₄/graphene nanocomposite and investigation of its adsorption performance for aniline and _p_ -chloroaniline

Applied Surface Science 2012 261

5584158

504 509

10.1016/j.apsusc.2012.08.045

2-s2.0-84867741298

30.

Zhou

Cao

Liu

Yang

Lou

Mechanism and influence factors of chromium(VI) removal by sulfide-modified nanoscale zerovalent iron

Chemosphere 2019 224

5584158

306 315

10.1016/j.chemosphere.2019.02.109

2-s2.0-85062240221

30844587

31.

Zhang

Zhai

Xiao

Song

Tian

Pb (II) removal of Fe₃O₄@SiO₂-NH₂ core-shell nanomaterials prepared via a controllable sol-gel process

Chemical Engineering Journal 2013 215

5584158

461 471

10.1016/j.cej.2012.11.043

2-s2.0-84873035902

32.

Jawad

A. H.

Malek

N. N. A.

Abdulhameed

A. S.

Razuan

Synthesis of magnetic chitosan-fly _Ash/Fe3O4 composite for adsorption of reactive orange 16 dye: optimization by Box-Behnken design

Journal of Polymers and the Environment 2020 28

5584158

3 1068 1082

10.1007/s10924-020-01669-z

33.

A. E. I.-A.

Farag

R. S.

Abdel-Gawad

S. A.

Removal of contaminant metformin from water by using Ficus benjamina zero-valent iron/copper nanoparticles

Nanotechnology for Environmental Engineering 2020 5

5584158

3 23

10.1007/s41204-020-00086-w

34.

Gad

H. M. H.

Youssef

M. A.

Sorption behavior of Eu(III) from an aqueous solution onto modified hydroxyapatite: kinetics, modeling and thermodynamics

Environmental Technology 2018 39

5584158

20 2583 2596

10.1080/09593330.2017.1362036

2-s2.0-85027504532

28783004

35.

Quiroga-Flores

Noshad

Wallenberg

Önnby

Adsorption of cadmium by a high-capacity adsorbent composed of silicate-titanate nanotubes embedded in hydrogel chitosan beads

Environmental Technology 2020 41

5584158

23 3043 3054

10.1080/09593330.2019.1596167

2-s2.0-85063883725

30892147

36.

Sun

Zhang

Qian

Zhai

Characteristics of equilibrium, kinetics studies for adsorption of Hg(II) and Cr(VI) by polyaniline/humic acid composite

Desalination 2011 266

5584158

1-3 188 194

10.1016/j.desal.2010.08.025

2-s2.0-78649637234

37.

Bhaumik

Maity

Srinivasu

V. V.

Onyango

M. S.

Removal of hexavalent chromium from aqueous solution using polypyrrole-polyaniline nanofibers

Chemical Engineering Journal 2012 181

5584158

323 333

10.1016/j.cej.2011.11.088

2-s2.0-84856356358

38.

Shao

D. D.

Chen

C. L.

Wang

X. K.

Application of polyaniline and multiwalled carbon nanotube magnetic composites for removal of Pb (II)

Chemical Engineering Journal 2012 185

5584158

144 150

10.1016/j.cej.2012.01.063

2-s2.0-84862776921

39.

Ben Ali

Wang

F. Y.

Boukherroub

Lei

Xia

Phytic acid-doped polyaniline nanofibers-clay mineral for efficient adsorption of copper (II) ions

Journal of Colloid and Interface Science 2019 553

5584158

688 698

10.1016/j.jcis.2019.06.065

2-s2.0-85067694496

31252185

40.

Gapusan

R. B.

Balela

M. D. L.

Adsorption of anionic methyl orange dye and lead(II) heavy metal ion by polyaniline-kapok fiber nanocomposite

Materials Chemistry and Physics 2020 243

5584158

122682

10.1016/j.matchemphys.2020.122682

41.

Hashemi

S. A.

Mousavi

S. M.

Ramakrishna

Effective removal of mercury, arsenic and lead from aqueous media using polyaniline-Fe₃O₄- silver diethyldithiocarbamate nanostructures

Journal of Cleaner Production 2019 239

5584158

118023

10.1016/j.jclepro.2019.118023

2-s2.0-85070687673

42.

Saghatchi

Ansari

Application of magnetic polyaniline nanocomposite for separation of uranyl ions from aqueous solutions

Separation Science and Technology 2018 53

5584158

15 2486 2499

10.1080/01496395.2018.1459701

2-s2.0-85045262943

43.

Shao

D. D.

Hou

G. S.

J. X.

Wen

Ren

Wang

PANI/GO as a super adsorbent for the selective adsorption of uranium(VI)

Chemical Engineering Journal 2014 255

5584158

604 612

10.1016/j.cej.2014.06.063

2-s2.0-84904335903

44.

L. J.

Tian

Yang

Bai

Yang

Zhang

Jin

A catechol-like phenolic ligand-functionalized hydrothermal carbon: one-pot synthesis, characterization and sorption behavior toward uranium

Journal of Hazardous Materials 2014 271

5584158

41 49

10.1016/j.jhazmat.2014.01.060

2-s2.0-84896833750

24598030

45.

Gholinejad

Ahmadi

Najera

Silica microparticles supported gold and copper ferrite nanoparticles: a magnetically recyclable bimetallic catalyst for Sonogashira reaction

ChemistrySelect 2016 1

5584158

3 384 390

10.1002/slct.201600049

2-s2.0-85041942694

46.

Kurian

Mathew

M. J.

Structural, optical and magnetic studies of CuFe₂O₄, MgFe₂O₄ and ZnFe₂O₄ nanoparticles prepared by hydrothermal/solvothermal method

Journal of Magnetism and Magnetic Materials 2018 451

5584158

121 130

10.1016/j.jmmm.2017.10.124

2-s2.0-85033384636

47.

Jawad

A. H.

Abdulhameed

A. S.

Facile synthesis of crosslinked chitosan-tripolyphosphate/kaolin clay composite for decolourization and COD reduction of remazol brilliant blue R dye: optimization by using response surface methodology

Colloids and Surfaces A: Physicochemical and Engineering Aspects 2020 605, article 125329

5584158

10.1016/j.colsurfa.2020.125329

48.

Zujovic

Z. D.

Wang

Bowmaker

G. A.

Kaner

R. B.

Structure of ultralong polyaniline nanofibers using initiators

Macromolecules 2011 44

5584158

8 2735 2742

10.1021/ma102772t

2-s2.0-79955033410

49.

Malek

N. N. A.

Jawad

A. H.

Abdulhameed

A. S.

Ismail

Hameed

B. H.

New magnetic Schiff's base-chitosan-glyoxal/fly ash/Fe₃O₄ biocomposite for the removal of anionic azo dye: an optimized process

International Journal of Biological Macromolecules. 2020 146

5584158

530 539

10.1016/j.ijbiomac.2020.01.020

31917215

50.

Jawad

A. H.

Mubarak

N. S. A.

Abdulhameed

A. S.

Tunable Schiff's base-cross-linked chitosan composite for the removal of reactive red 120 dye: adsorption and mechanism study

International journal of biological macromolecules 2020 142

5584158

732 741

10.1016/j.ijbiomac.2019.10.014

51.

Cheira

M. F.

Synthesis of aminophosphonate-functionalised ZnO/polystyrene-butadiene nanocomposite and its characteristics for uranium adsorption from phosphoric acid

International Journal of Environmental Analytical Chemistry 2019 1 25

10.1080/03067319.2019.1686493

52.

Dousti

Dolatyari

Yaftian

M. R.

Rostamnia

Adsorption of Eu(III), Th(IV), and U(VI) by mesoporous solid materials bearing sulfonic acid and sulfamic acid functionalities

Separation Science and Technology 2019 54

5584158

16 2609 2624

10.1080/01496395.2018.1548483

2-s2.0-85058136827

53.

Kou

Zhang

Liu

Zhu

Duan

Phosphonate modified MoS₂ composite material for effective adsorption of uranium(VI) in aqueous solution

Journal of Radioanalytical and Nuclear Chemistry 2020 323

5584158

1 641 649

10.1007/s10967-019-06970-3

54.

Yang

Ding

Zhang

Luo

Zhang

Immobilization of dopamine on Aspergillus niger microspheres (AM/PDA) and its effect on the U(VI) adsorption capacity in aqueous solutions

Colloids and Surfaces a-Physicochemical and Engineering Aspects 2019 583, article 123914

5584158

10.1016/j.colsurfa.2019.123914

2-s2.0-85072671783

55.

Ashrafi

Firouzzare

Ahmadi

S. J.

Sohrabi

Khosravi

Preparation and modification of forcespun polypropylene nanofibers for adsorption of uranium (VI) from simulated seawater

Ecotoxicology and environmental safety 2019 186

5584158

109746

10.1016/j.ecoenv.2019.109746

2-s2.0-85072991164

Removal of Uranyl Ion from Wastewater by Magnetic Adsorption Material of Polyaniline Combined with CuFe 2 O 4

Abstract

1. Introduction

2. Experimental

2.1. Materials and Reagents

2.2. Instrumentations

2.3. Synthesis of the Adsorption Materials

2.3.1. Synthesis of CuFe2O4 Nanoparticles

2.3.2. Synthesis of CuFe2O4/PANI Nanocomposite

2.4. Batch Adsorption Experiments

2.5. Desorption Experiments

2.6. Adsorption Kinetics

2.7. Equilibrium Isotherm Modelling

3. Results and Discussion

3.1. Characterization

3.2. Effect of pH on Adsorption of Uranyl Ions

3.3. Effect of Initial Concentration on Adsorption of Uranyl Ions

3.4. Effect of Temperature and Adsorption Time on Adsorption of Uranyl Ions

3.5. Regeneration

3.6. Adsorption Kinetics

3.7. Equilibrium Isotherm Modelling

3.8. Magnetic Validation Study

4. Conclusion

Footnotes

Data Availability

Additional Points

Conflicts of Interest

References

2.3.1. Synthesis of CuFe₂O₄ Nanoparticles

2.3.2. Synthesis of CuFe₂O₄/PANI Nanocomposite