Efficient Removal of Copper(II) and Malachite Green from Aqueous

Article pubs.acs.org/jced

Efficient Removal of Copper(II) and Malachite Green from Aqueous Solution by Magnetic Magnesium Silicate Composite Huandong Liu, Zunli Mo,* Li Li, Fang Chen, Qijun Wu, and Lei Qi College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People’s Republic of China S Supporting Information *

ABSTRACT: The magnetic magnesium silicate composite (Fe3O4@MgSi) with efficient removal of Cu(II) and malachite green (MG) from aqueous solution were synthesized by hydrothermal approach. The synthetic flower-like particle size was about 2−3 μm. In the process of exploring the adsorption conditions, the isotherms were found to be well-fitted by Langmuir, Freundlich, and isotherm kinetics in accord with the pseudo-second-order model. In addition, the maximum adsorption capacity was 2198 mg·g−1 when the Cu(II) concentration of 800 mg·L−1. These results indicated that Fe3O4@MgSi can be used as a superadsorbent and recyclable adsorbent to effectively and rapidly remove Cu(II) and MG pollutants from industrial wastewater or drinking water. nanocomposites,20 natural zeolites,21 and kaolinite clay,22 etc.23−25 However, there were still some drawbacks such as low instability and separation difficult for most of the nanomaterials, which limited their application in wastewater treatment. Hierarchical magnetic materials, due to their large specific surface area26 and easy separation by an external magnetic field, were considered as a very promising adsorbent for the removal of heavy metal ions27 and organic dyes.28 Previous studies have focused on a single component of magnetic porous spheres.29,30 Compared with the sphere, one-dimensional nanorods31−37 have better mechanical strength and shorter diffusion path for mass transportation.38−40 Furthermore, silicate materials41−48 as ideal adsorbent had attracted widespread attention to remove contaminants in water, because of their large surface area, high porosity, and environmental protection, etc.; examples such as magnesium silicate nanotubes had excellent adsorption capacities for UO22+, Pb2+, methylene blue, and rhodamine B, respectively.38 The combination of two or more components may create better performance and novel properties by bringing together synergistic materials; for example, Liu et al.’s49 synthesis of barium silicate and barium titanium oxide shells possessed mixed hierarchical magnetic yolk−shell microspheres. This composite was confirmed to be an attractive candidate material for enhancement microwave absorption due to its high magnetization, tailored shells, and high porosity. At the same time,50 excellent magnetic recycle materials can effectively prevent the release of nanoadsorbent into the water,

1. INTRODUCTION With the increasing awareness of the need for environmental protection, the problem of toxic pollutants including heavy metals and organic dyes discharged into aqueous solution resulting from different activities such as industry and agriculture, has attracted wide attention. These phenomena seriously disrupt ecological systems.1 Cu(II) has been wellknown as one of the essential transition metals and for playing an important role in human body.2 But excessive Cu(II) discharged into the environment from diverse manufacturing, textile, and electroplating industries not only cause a major environmental issue but also affect human health and that of other organisms through the food chain.3 Malachite green (MG), an organic dye, was widely used in our life, for example, in fishery, medicine, and food industries and as a dye in silk, paper, leather, and printing industries.4 But high concentrations of MG in aqueous solution may cause carcinogenic, mutagenic, chromosomal fractures, and teratogenic and respiratory toxicity effects on humans.5 Therefore, suitable methods were needed to remove heavy metal ions and organic dyes from solution.6 Common techniques that have been used to remove the Cu(II) and MG from solution7 included chemical precipitation,8 solvent extraction,9 filtration,10 osmosis,11 electrolysis,12 oxidation/ reduction,13 ion exchange,14 and adsorption.15 Among these methods,16 adsorption was one of the most promising and an extensively used process due to simple operation,17 high removal rate,18 low operational associated cost, short detection period, no need for skilled personnel, and no byproduct in the treatment process. Thus, a wide variety of adsorbents were used to remove Cu(II) and MG in wastewater treatment, such as activated carbons,19 magnetic β-cyclodextrin−graphene oxide © 2017 American Chemical Society

Received: January 16, 2017 Accepted: July 26, 2017 Published: August 11, 2017 3036

DOI: 10.1021/acs.jced.7b00041 J. Chem. Eng. Data 2017, 62, 3036−3042

Journal of Chemical & Engineering Data

Article

Figure 1. (A) FTIR spectra of (a) Fe3O4, (b) SiO2@Fe3O4, and (c) Fe3O4@MgSi. (B) Typical XRD patterns of the samples: (a) Fe3O4, (b) SiO2@ Fe3O4, and (c) Fe3O4@MgSi;.

2.3. Preparation of the Fe3O4−SiO2 Nanorods. The Fe3O4−SiO2 nanorods were synthesized using a modified StÖ ber method.53 A 0.15 g amount of Fe3O4 precipitate obtained from the previous step was dispersed into a mixture of ethanol (160 mL) and water (40 mL); ammonia solution (2 mL) and TEOS (1 mL) were then added dropwise to the Fe3O4 suspension. The reaction mixture was stirred using a magnetic stirrer bar for 6 h. Fe3O4−SiO2 nanorods were thoroughly washed with deionized water, collected by magnetic separation, and dried under vacuum at 60 °C for 6 h. 2.4. Synthesis of the Flower-like Fe3O4@MgSi. Fe3O4@ MgSi was synthesized using a hydrothermal approach.54 A 0.05 g amount of Fe3O4−SiO2 nanorods, 1.35 g of urea, and 0.13 g of Mg(NO3)2·6H2O were dispersed into a mixture of 40 mL of deionized water and 20 mL of absolute ethanol, which were dissolved and transferred to an autoclave at 190 °C for 24 h. The synthesized Fe3O4@MgSi was separated from the solution by magnetic separation, rinsed with deionized water and absolute ethanol several times, and dried under vacuum at 60 °C for 4 h. 2.5. Characterization. Fourier transform infrared (FTIR) spectra were recorded in the spectral range of 400−4000 cm−1 on an EQUINOX55 FTIR spectrometer. The morphology features of products were measured with scanning electron microscopy (SEM; ULTRA plus, Germany), energy dispersive spectroscopy (EDS; Aztec-X-80, England), and transmission electron microscopy (TEM; USA FEI Tecnai G2TF20). The crystallographic structures of the products were examined by Xray diffraction (XRD; Japanese Physical Co.). 2.6. Adsorption Experiments. Cu(II) and MG adsorption experiments were carried out using a similar process. In a typical process, to obtain the adsorption isotherm, 5 and 18 mg of Fe3O4@MgSi were respectively mixed with 15 mL of Cu(II) and MG solutions of different initial concentrations, with ultrasonic treatment for 60 min. The adsorbent was removed by magnetic separation, and the separating liquid was analyzed by using WXY-402C flame atomic absorption spectrophotometer for Cu(II) (Shenyang, China) and UV/vis spectroscopy (λmax, 624 nm) for MG. Moreover, the effects of various parameters on sorption of Fe3O4@MgSi toward Cu(II) and MG were investigated such as solution pH, contact time, and initial concentration. After magnetic separation, the concentrations of Cu(II) and MG were measured.

which prevents the destruction of nanomaterials damage to the environment. Bearing this in mind, magnetic magnesium silicate composite (Fe3O4@MgSi) was synthesized by hydrothermal approach and was used as an adsorbent for removal of Cu(II) and MG from aqueous solution. In comparison to carbon-based nanomaterials, magnetic silicate-based materials have lower costs and large specific surface area for fabrication, can be better dispersed in water, and can be reused.51 Since Fe3O4@MgSi was negatively charged, it can only adsorb positively charged cationic contaminants. But Cu(II) and MG were positively charged. The morphology, structure and the adsorption properties of the composite were investigated. Moreover, the influences of various parameters such as solution pH, contact time, and initial concentration were investigated. The synthesized material had a high adsorption capacity for Cu(II) and could be easily separated from aqueous solution in the presence of external magnetic field.

2. EXPERIMENTAL SECTION 2.1. Materials. All chemicals were analytical grade and used as purchased. Ferric nitrate nonahydrate (Fe(NO3)3·9H2O), cupric chloride dihydrate (CuCl2·2H2O), malachite green, and tetraethyl orthosilicate (TEOS) were purchased from Tianjin Kaixin Chemical Industry Co., Ltd. Magnesium nitrate hexahydrate (Mg(NO3)2·6H2O) and ethanol (C2H5OH) were bought from Sinopharm Chemical Reagent Co., Ltd. (China). Hydrochloric acid (HCl) was supplied by BaiYin LiangYou Chemical Reagents Co., Ltd. Ammonia solution (NH3·H2O, 28 wt %), urea, and potassium hydroxide (KOH) were from Aladdin Industrial Corp. Shanghai (China). 2.2. Preparation of the Magnetic Fe3O4 Nanorods. The α-FeOOH nanorods were prepared via a hydrothermal method52 as follows: first, 0.01 mol of Fe(NO3)3·9H2O was dissolved in 40 mL of distilled water. Then, 10 mL of 4 mol/L KOH solution was dropped slowly into the Fe(NO3)3·9H2O solution under vigorous stirring. The slurry mixture was transferred into a stainless steel Teflon-lined autoclave for the hydrothermal treatment at 100 °C for 6 h. Finally, the autoclave was cooled to room temperature naturally, and the precipitate was filtered, repeatedly washed with absolute ethanol and distilled water, and then dried under vacuum at 60 °C for 6 h. The synthesized α-FeOOH nanorods were transferred into a tube furnace and heated at 500 °C for 2 h under a flowing nitrogen (N2) atmosphere. The materials obtained were referred to as Fe3O4 nanorods. 3037



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3. RESULTS AND DISCUSSION 3.1. Characterization of Fe3O4@MgSi. The FTIR spectra of Fe3O4, SiO2@Fe3O4, and Fe3O4@MgSi nanoparticles were compared in Figure 1A. For all three particles, absorption peaks around 570 cm−1 were observed, corresponding to absorption from magnetite Fe−O vibration. The absorption peak at 1633 cm−1 was the hydroxyl groups. The SiO2@Fe3O4 nanocomposite exhibited new bands at 1190, 1061, 798, and 952 cm−1 in Figure 1A(b), which were attributed to the stretching and deformation vibrations of Si−O−Si that coated silica on the surface of Fe3O4. After the hydrothermal treatment, the presence of new bonds appearing at 1014 and 643 cm−1 for the Fe3O4@MgSi composite confirmed the formation of MgSi, in Figure 1A(c).55 Fe−O and Si−O−Si absorption peaks still existed. The shoulder at 3424 cm−1 could be appointed to the stretching and bending modes of water. The band at 1629 cm−1 was associated with carboxylate groups of SiO2@Fe3O4. The XRD patterns of the synthesized Fe3O4@MgSi composite were shown in Figure 1B. The XRD pattern of Fe3O4, with diffraction peaks with 2θ at 30.3°, 35.9°, 43.4°, 57.12°, and 62.6°, was observed, indicative of a crystalline structure of the magnetite. Angles 30.3°, 35.9°, 43.4°, 57.12°, and 62.6° were coincident to 220, 311, 400, 511, and 440 lattice planes. The same set of characteristic peaks was also observed for SiO2@ Fe3O4 and Fe3O4@MgSi, indicating the stability of the crystalline phase of Fe3O4 nanoparticles. A broad peak appeared at 24° after coating the Fe3O4 nanorods with a SiO2 layer in Figure 1B(b). This indicated that the introduced SiO2 layer was amorphous. The peaks of MgSi and Fe3O4@MgSi were relatively broadened and overlapped with each other, but all peaks can be indexed to magnesium silicate. Low intensity peaks at 20.1°, 32.96°, and 60.84° in Figure 1B(c) were observed for [email protected] Figure S1 from the Supporting Information of EDS showed Fe3O4@MgSi contained Fe, O, Si, and Mg elements, It further proved the successful synthesis of Fe3O4@MgSi composites. The morphology of the as-prepared products were characterized by SEM and TEM, as shown in Figure 2. The

and XRD results. The thickness of the silica coating was 20−30 nm (Figure 2D of TEM). Compared to the original Fe3O4 nanorods, the Fe3O4@MgSi particles formed a flower sphere with hierarchical surfaces due to the agglomeration of nanorods and formation of incomplete Fe3O4 nanorods (as shown in panels E (SEM) and F (TEM) of Figure 2). The diameter of the Fe3O4@MgSi flower sphere was about 2−3 μm. 3.2. Adsorption Characteristic. Then, the parameters of the pH and the amount of Fe3O4@MgSi were discussed for its effect on adsorption. The influence of pH on the adsorption process was seen from Figure 3A,B. It was worth noting that over 99% of Cu(II) and MG were adsorbed within 60 min. When the solution was pH = 2, the removal efficiency was still 99%. This indicated that pH was not a critical influencing factor in the adsorption process. The low pH-independent properties were beneficial to its application in industrial production. However, with an increased of amount of Fe3O4@MgSi, the removal rate had apparently changed for Cu(II) and MG (Figure 3C,D). Therefore, Fe3O4@MgSi optimal quantities can be obtained, which were 5 and 18 mg in the adsorption processes for Cu(II) and MG. To investigate the adsorption capacities, the adsorption isotherms of Cu(II) and MG on Fe3O4@MgSi were shown in Figure 4. The linear form of Langmuir isotherm equation can be expressed as follows:56 Ce 1 1 = + Ce qe K aqm qm

(1)

The Freundlich isotherm equation can be expressed as the following formula:57 log qe = log KF +

1 log Ce n

(2)

where Ce is the equilibrium concentrations of Cu(II) and MG in the supernatant (mg·L−1); qm represents the maximum adsorption capacities of Cu(II) and MG per unit weight of adsorbent (mg·g−1); Ka is the Langmuir constant (L·mg−1); qe is the amount of Cu(II) and MG adsorbed per unit weight of adsorbent after equilibrium (mg·g−1); and KF and n are the Freundlich isothermal constant experience adsorptions, which are related to the adsorption capacity and adsorption intensity, respectively. Linear relationships are shown in Supporting Information Figure S2. Parameters of Langmuir and Freundlich isotherms were shown in Table 1. From Figure 4A, the adsorption capacity increased with increasing initial concentration of Cu(II). The removal efficiency was as high as 91% still even when the initial concentration of Cu(II) was 800 mg·L−1 after 60 min and the adsorption capacity was 2198 mg·g−1. On the basis of the Langmuir equation, the value of qm was calculated to be 1992 mg·g−1; these results indicated that the Fe3O4@MgSi had high adsorption capacity for Cu(II) (Table 2). It should be noted that the qm for Fe3O4@MgSi was about 8-fold higher than that of nanoparticles of zerovalent iron. However, the adsorption of Fe3O4@MgSi for MG was not ideal. When the concentration of MG was 150 mg·L−1, the removal rate was only 90% and the adsorption capacity was 112.83 mg·g−1 after 60 min (Figure 4B). qm was calculated by Langmuir equation to be 125.16 mg· g−1. As shown in Table 1, the adsorptions of Cu(II) and MG on Fe3O4@MgSi, both with the Langmuir and Freundlich models, fitted well with the adsorption data and possessed similar

Figure 2. SEM and TEM images of Fe3O4 (A and B), SiO2@Fe3O4 (C and D), and Fe3O4@MgSi (E and F).

200−300 nm nanorods were observed by hydrothermal method Fe3O4 particles, as SEM shown in Figure 2A. Figure 2B of TEM showed that as-prepared Fe3O4 exhibited a smooth surface. After the coating of TEOS, nanoparticles appear relatively rough, confirming the formation of silica nanoparticles (Figure 2C of SEM). It proved consistent with FTIR 3038



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Figure 3. (A and B) Effect of pH on adsorption behavior of Cu(II) and MG. (C and D) Influence of different amounts of Fe3O4@MgSi on the adsorption process for Cu(II) and MG (pH = 4.92 and 4.8, respectively). Initial concentration, 100 mg/L; 15 mL; contact time, 60 min.

Figure 4. Different initial concentrations of (A) Cu(II) and (B) MG solution adsorbed by Fe3O4@MgSi. The amounts of Fe3O4@MgSi were 5 and 18 mg; pH = 4.92 and 4.8, respectively. Time, 60 min.

Table 1. Parameters of Langmuir and Freundlich Isotherms Langmuir Cu(II) MG

Freundlich 2

1/n

qm (mg/g)

Ka (L/mg)

R

1992.03 125.15

0.2425 2.672

0.9682 0.9989

adsorbent magnetic polymer beads modified with ethylene diamine magnetic copolymer bead (PVBC) modified by click reaction EDTA functionalized magnetic nanoparticles chitosan nanoparticles of zerovalent iron humic acid (HA) coated Fe3O4 nanoparticles Fe3O4@MgSi

exptl conditions

51.7

pH = 3−5

58

61.2

pH = 5.5

59

46.25

pH = 6, 298 K

15

174.75 250 46.3 2198

pH = 6.0

n

R2

386.9 93

1.385 12.01

0.984 0.8865

correlation coefficients; it may be attributed to the successful preparation of Fe3O4@MgSi. So as to evaluate the adsorptive property of Fe3O4@MgSi. The adsorption kinetics of Cu(II) and MG on Fe3O4@MgSi was shown in Figure 5. After only 15 min of contact time, the aqueous phase concentrations of Cu(II) declined from 100 to 0.802 mg·L−1 and after 20 min MG declined from 100 to 0.195 mg·L−1, respectively. The removal efficiencies were above 99% in both scenarios after 30 min of contact time. The equilibrium was rapidly achieved, and fast adsorption made it an extensive application prospect in wastewater treatment.

Table 2. Comparison of the Adsorption Capacities of Copper(II) with Various Adsorbents adsorption capacity (mg g−1)

KF [(mg/g)(L/mg) ]

ref

60 61 62

t 1 t = + qt qe k 2qe 2

this work 3039

(3) DOI: 10.1021/acs.jced.7b00041 J. Chem. Eng. Data 2017, 62, 3036−3042


Article

Figure 5. Effect of contact time of (A) Cu(II) and (B) MG removal. Initial concentrations of Cu(II) and MG, 100 mg/L; pH = 4.92 and 4.8, respectively.

where k2 (mg·g−1·h−1) is the second-order rate constant and qt (mg·g−1) and qe (mg·g−1) represent the adsorption capacity at any time t (min) and at equilibrium, respectively.63 In order to examine the adsorption mechanism, the pseudosecond-order model was adopted to investigate the adsorption process. The adsorption kinetics equation of the curve was shown in Figure 6. From the results shown in Table 3, the

charged. Therefore, the electrostatic attraction was the main driving force for the adsorption process. In order to test the reusability and regeneration of Fe3O4@ MgSi, Fe3O4@MgSi was used, five times, in consecutive adsorption/desorption cycles for Cu(II) and MG of 100 mg· L−1. Desorption behavior was studied using 0.1 mol·L−1 HCl solution and ethanol as eluants for Cu(II) and MG, respectively. As shown in Supporting Information Figure S3, at the end of the fifth cycle, Fe3O4@MgSi retained more than 98% and 94% removal efficiency for Cu(II) and MG, respectively. It was further proved that the adsorption force between them was electrostatic adsorption.65

4. CONCLUSIONS In summary, Fe3O4@MgSi composite was synthesized by a hydrothermal approach for the removal of Cu(II) and MG from aqueous solution. XRD patterns, FTIR spectra, EDS, SEM, and TEM clearly indexed the crystallographic information and morphology features on the composite. The sorption conditions for Fe3O4@MgSi were investigated by varying several experimental parameters such as pH, the amount of the sorbent, the initial concentration, and the contact time. Fe3O4@MgSi composite had high adsorption capacities of 2198 and 112.8 mg·g−1 for Cu(II) and MG, respectively. The equilibrium data were well-fitted with the Langmuir and Freundlich isotherm models, and kinetic data showed good correlation to the pseudo-second-order equation. Moreover, Fe3O4@MgSi was easily separated and recycled. These unique attributes make valuable the Fe3O4@MgSi particle in potential application for effective removal of metal ions in wastewater treatment.

Figure 6. (A and B) Pseudo-first-order kinetic equation for adsorption of Cu(II) ions and MG. (C and D) Pseudo-second-order kinetic equation for adsorption of Cu(II) ions and MG.

correlation coefficient values indicated that it was a better fit with the pseudo-second-order equation of the experimental data for Cu(II) and MG. In addition, the calculated qcal values (297.6 and 83.26 mg·g−1) fitted well with the experimental data (297.8 and 83.29 mg·g−1), further indicating that the pseudosecond-order kinetic model was suitable to describe the adsorption process,64 indicating that the physical and chemical adsorption has played a major role in the adsorption process. It was reported that iron oxide@magnesium silicate was shown to be negatively charged54 and Cu(II) and MG were positively

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.7b00041. EDS pattern of the Fe3O4@MgSi, its adsorption isotherm, and cycle performance for Cu(II) and MG (PDF)

Table 3. Constants and Correlation Coefficients for the Kinetic Models pseudo-first-order model Cu(II) MG

pseudo-second-order model 2

qe,exp (mg/g)

qe,cal (mg/g)

k1 (1/min)

R

297.8 83.29

8.51 11.19

0.0684 0.122

0.317 0.626 3040

qe,cal (mg/g)

k2 [g/(mg·min)]

R2

297.62 83.26

0.339 0.499

0.9999 0.9999



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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Zunli Mo: 0000-0002-1269-3954 Funding

This work was supported by the National Natural Science Foundation of China (Grant 51262027), the Science and Technology Tackle Key Problem Item of Gansu Province (Grant 2GS064-A52−036−08), and the financial support of the Natural Science Foundation of Gansu Province (Grants 1104GKCA019 and 1010RJZA023). Notes

The authors declare no competing financial interest.

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Efficient Removal of Copper(II) and Malachite Green from Aqueous

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