Amino-Functionalized Mesoporous Silicas MCM-48 as Zn(II) Sorbents

Article pubs.acs.org/jced

Amino-Functionalized Mesoporous Silicas MCM-48 as Zn(II) Sorbents in Water Samples Ya Han,† Keming Fang,† Xingxing Gu,† Jinjin Chen,† and Jianrong Chen*,†,‡ †

College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, Zhejiang, 321004, China College of Geography and Environmental Sciences, Zhejiang Normal University, Zhejiang, 321004, China

‡

ABSTRACT: Amino-functionalized MCM-48 (NH2-MCM48) modified with 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (DTES) was synthesized by a cocondensation method and was characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectrum, and thermogravimetric analysis techniques. Batch adsorption studies of Zn(II) on NH 2-MCM-48 were investigated. The effect of experimental parameters including pH, adsorbent dose, Zn(II) concentration, and adsorption time was studied, and the research results indicated NH2MCM-48 has a higher adsorption capacity for Zn(II) than other adsorbents. The experimental data were fitted to Langmuir and Freundlich isotherm models, and the Langmuir equation showed better correlation with the experimental data than the Freundlich. According to the parameters of the Langmuir equation, the maximum adsorption capacities of Zn(II) onto NH2-MCM-48 were (83.33, 90.91, and 100.00) mg·g−1 at (303, 313, and 323) K, respectively. The adsorption kinetics data were found to follow the pseudosecond-order kinetic model. The thermodynamic parameters (ΔG0, ΔH0, and ΔS0) were measured, and the negative value of Gibbs energy indicated the adsorption process was spontaneous in nature. Moreover, the adsorbent was applied in environmental samples, and the removal rate and recovery of Zn(II) from water were high. These results indicate that NH2-MCM-48 is an efficient adsorbent to remove Zn(II) from polluted water. clays,28 zeolites,29 and other materials such as mesoporous silicas.2,30 In recent years, mesoporous silicas have attracted considerable attention for potential applications of adsorbents, due to their unique features, such as high surface area, large pore volume, and easy surface functionalization. The M41S of mesoporous silicas are prominent adsorbents for removing heavy metal ions from wastewater.31−34 High adsorption capacity is an important characteristic for good adsorbents. Many methods have been carried out to improve the adsorption capacity of mesoporous silicas. Surface functionalization and the incorporation of heteroatoms (Al, Ti, Zr, etc.) into the silica framework are two methods to improve adsorption capacity for heavy metals. Moreover, the surface functionalization of mesoporous silicas with organic groups was achieved by co-condensation35,36 and postsynthesis grafting methods.37,38 MCM-48, one member of the M41S family, contains two independent three-dimensional structures, and the special structure provides more favorable mass transfer kinetics

1. INTRODUCTION Zn(II) is an essential trace element for organisms. However, Zn(II) can accumulate in organisms and be toxic to such species and those that feed from them such as humans. Acute exposure to Zn(II) causes health problems such as stomach cramps, skin irritation, vomiting, nausea, and anemia.1,2 A large excess of Zn(II) can be carcinogenic.3 The main sources of Zn(II) pollutants are often from battery manufacturing processes, galvanizing facilities, production of paints and pigments, cosmetics, insecticides, and so on. Due to their toxicity, accumulation through food chain, and persistence in nature, heavy metal pollutants have attracted close attention among the world. Consequently, the removal of Zn(II) from wastewaters is essential to protect the environment and human health. Some technologies are used to remove Zn(II) from wastewaters, including ion-exchange,4 precipitation,5,6 solvent extraction,7,8 membrane filtration,9,10 and adsorption.11−31 Among these technologies, the adsorption method is a simple and rapid method for the removal of heavy metals from wastewaters. Adsorbents play a crucial role in the adsorption technology. Therefore, many studies commit to design adsorbents for the removal of heavy metal ions. The common types of adsorbents include biomass,26 activated carbon,27 © 2012 American Chemical Society

Received: March 19, 2012 Accepted: May 31, 2012 Published: June 14, 2012 2059

dx.doi.org/10.1021/je3003496 | J. Chem. Eng. Data 2012, 57, 2059−2066

Journal of Chemical & Engineering Data

Article

than MCM-41. Therefore, MCM-48 is a promising parent, and the functionalized MCM-48 has been applied in the adsorption field.32,39 The objective of this study was to investigate aminofunctionalized MCM-48 (NH2-MCM-48) as adsorbents for the removal of Zn(II) from aqueous solution. With cetyltrimethylammonium bromide (CTAB) and triblock poly(ethylene oxide)−poly(propylene oxide)−poly(ethylene oxide) (Pluronic P123) as a cotemplate and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (DTES) as an aminofunctional group, NH2-MCM-48 was synthesized by the cocondensation method for the first time. To study the adsorption process of Zn(II) onto NH2-MCM-48, the adsorption isotherms have been measured at different temperatures, and the Langmuir and Freundlich isotherm model parameters and the thermodynamic parameters were determined. The kinetic adsorption data have been analyzed using a pseudosecond-order model. The prepared material was applied to remove Zn(II) from environmental water samples

Scheme 1. Schematic Illustration of Synthesis Route of NH2MCM-48 Mesoporous Silica

2.3. Characterization and Analysis. X-ray diffraction (XRD) data was collected on a Philips PW3040/60 diffractometer, equipped with a graphite monochromator and using Cu Kα radiation (at 40 kV and 40 mA, λ = 0.154 nm). Infrared spectra were recorded on a Fourier transform infrared (FT-IR) spectrometer named Nicolet NEXUS 670 with the KBr pellet technique, and the range of scan mode is (400 to 4000) cm−1. The thermal stability of the modified mesoporous silicas was studied using a Netzsch STA 449 C thermogravimetric analyzer, and the sample cell (a dense alumina crucible pot) was loaded with ca. 15 mg of adsorbent. A synthetic air atmosphere was used by increasing the temperature from (30 to 800) °C at a speed of 10 °C·min−1. 2.4. Batch Adsorption Experiments. All batch experiments were carried out in a 100 mL conical flask with 20 mL of zinc nitrate aqueous solutions of certain initial concentration and adsorbent, and then the mixture was shaken on a shaking thermostat machine at 200 r·min−1. After adsorption, the final concentration of Zn(II) ions was determined by atomic emission spectrometer (ICP-AES), model IRIS Intrepid II XSP. The removal rate (R %) was defined as the following equation:

2. MATERIALS AND METHODS 2.1. Materials and Reagents. 3-[2-(2-Aminoethylamino)ethylamino]propyl-trimethoxysilane (DTES), triblock poly(ethylene oxide)−poly(propylene oxide)−poly(ethylene oxide) (Pluronic P123), were purchased from Sigma Chemical Reagent Company. Tetraethoxysilcane (TEOS) and cetyltrimethyl ammonium bromide (CTAB) were purchased from Sinopharm Chemical Reagent Co. Ltd. NaOH and NaF were purchased from Shanghai Chemical Reagent, and Zn(NO3)2·6H2O was purchased from Tianjin Guangfu Fine Chemical Reagent. All chemicals were used in their analytical grade without further purification. Deionized water was used for solution preparation and washing. Stock solutions (1000 mg·L−1) of Zn(II) were prepared by dissolving 4.5500 g of Zn(NO3)2·6H2O in 1000 mL of distilled water. The solutions of different concentrations used in various experiments were obtained by the dilution of stock solutions. 2.2. Synthesis and Characterization of MCM-48 and Amino-Functionalized Mesoporous Silicas (NH2-MCM48). MCM-48 was prepared by hydrothermal crystallization.40 In a typical synthesis, 5.22 g of P123 was added in 80.0 mL of deionized water at 40 °C. After 3 h of stirring, 3.28 g of CTAB was added into the solution. After 2 h of stirring, 1.4 g of NaOH and 0.3 g of NaF were added into the above mixture. The mixture was stirring for 30 min, and then 16.0 mL of TEOS was added. The mole ratio of TEOS/CTAB/P123/ NaOH/NaF/H2O was 1.0:0.125:0.0125:0.50:0.1:60. After 4 h of constant stirring, the mixture was autoclaved and kept at 100 °C for 72 h. Then the material was filtered and washed with distilled water, dried at 100 °C overnight, and calcined for 5 h at 550 °C in air. NH2-MCM-48 was synthesized by the co-condensation method, according to a process described in the literature.41 The synthesis procedure was improved as the following: 1.5 mL of DTES and 15.4 mL of TEOS were added together. The molar composition of the mixture was TEOS/DTES/CTAB/ P123/NaOH/NaF/H2O = 1.0:0.086:0.125:0.0125:0.50:0.1:60. After 24 h of constant stirring, the mixture was autoclaved and kept at 100 °C for 24 h. The resulted white powder was filtered, washed with water and ethanol, and dried. Then the template molecules were extracted with ethanol under reflux for 24 h and then dried at 50 °C. The synthesis route of NH2-MCM-48 mesoporous silica is shown in Scheme 1.

R% =

C0 − Ce ·100 % C0

(1)

where C0 and Ce are the initial and equilibrium concentrations of Zn(II) (mg·L−1), respectively. The adsorbed amount of Zn(II) per unit weight of NH2MCM-48 was determined by the following equation: qe =

(C0 − Ce) ·V m

(2)

where V is the volume of Zn(II) solutions (L) and m is the amount of adsorbent (g). To explore adsorption kinetics of the sorbent, 30 mg of NH2MCM-48 was added to 20 mL of Zn(II) solution with three different concentrations ((20, 40, 60, and 100) mg·L−1), and the samples were agitated for different contact times. To obtain adsorption capacity of NH2-MCM-48, the adsorption isotherm studies for Zn(II) removal were conducted by contacting 30 mg of NH2-MCM-48 with 20 mL of Zn(II) solution at the initial concentration range of ((10 to 200) mg·L−1) and shaking for 2 h. The experiments were performed at different temperatures. 2060



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3. RESULTS AND DISCUSSION 3.1. Structural Characterization of NH2-MCM-48. 3.1.1. XRD Analysis. The XRD patterns of MCM-48 and NH2-MCM-48 are shown in Figure 1. Figure 1a clearly shows

results indicated the existence of amino groups in mesoporous channels. 3.1.3. TGA Analysis. Thermogravimetric analysis (Figure 3) of NH2-MCM-48 shows a gradual weight loss up to 800 °C.

Figure 3. TGA weight loss curves of NH2-MCM-48.

The first weight loss (∼5.0 %) below 150 °C is observed, due to the desorption of physically adsorbed water. The weight loss in the second step can be attributed to the thermal removal of residual CTAB and P123 surfactant from MCM-48 materials. Moreover, a large weight loss (12 %) in the range of (250 to 450) °C is coincident to the decomposition temperature of the amino functional group. After 450 °C, the loss of weight was due to the decomposition of methylene. 3.2. Adsorption Experiment. 3.2.1. Effect of pH on Zn(II) Adsorption by NH2-MCM-48. Zn(II) adsorption from aqueous solution by NH2-MCM-48 depends on pH, and the effect of initial solution pH on the removal of Zn(II) is shown in Figure 4. The removal rate of Zn(II) was only about 55 % at low pH

Figure 1. X-ray diffraction (XRD) pattern of (a) MCM-48 and (b) NH2-MCM-48.

four diffraction peaks, (211), (220), (420), and (332), which are indexed to the Ia3d cubic structure of MCM-48. However, it can be seen from Figure 1b that the diffraction peak (211) intensity of NH2-MCM-48 is a little weaker than MCM-48, and three diffraction peaks (220, 420, and 332) of NH2-MCM-48 disappear. The changes can be attributed to a partial loss of the space correlation of the pores and the reaction between amino groups and Si−OH in mesostructures.42 These results indicate that amino groups successfully incorporate into the mesoporous channels. 3.1.2. FT-IR Analysis. Figure 2 shows the FT-IR spectra of MCM-48 and NH2-MCM-48. A broad absorption band at 3406

Figure 2. FT-IR spectra of (a) MCM-48 and (b) NH2-MCM-48.

Figure 4. Effect of initial solution pH on the removal of Zn(II) by NH2-MCM-48. Conditions: 50 mg of NH2-MCM-48, 10 mg·L−1 Zn(II) solution, 20 mL.

cm−1 is attributed to the stretching of the Si−OH group. The bands around (1074, 815, and 460) cm−1 are asymmetric stretching, symmetric stretching, and bending of Si−O−Si vibration, respectively. The adsorption bands at 2848 cm−1 (stretching) and 2923 cm−1 (bending) are vibrations of C−H and 1560 cm−1 (bending) is the vibration of N−H.43 These

around 3.0, and then with the increase of pH, the removal rate is enhanced and reached the maximum value of 99 % at pH 7.0 to 10.0. At low pH, the removal rate of Zn(II) was low, which was due to the protonated amino groups repulsing with the cations via electrostatic repulsion. With the increase of pH, the protonated amino groups decreased, electrostatic attraction resulting in a higher removal rate of Zn(II). At higher pH, the surface of NH2-MCM-48 has a negative charged, which is 2061



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chemical adsorption. The pseudosecond-order kinetic model has been employed to fit the experimental data, which is expressed as the following equation:44

favorable for the adsorption of Zn(II). However, hydroxyl complexes and precipitation of zinc hydroxide would be easily formed, and therefore we selected pH 7.0 as the experiment condition. 3.2.2. Effect of Sorbent Dose. From Figure 5a we can see that the removal rate of Zn(II) is enhanced as adsorbent dose

t 1 t = + qt qe K 2qe 2

(3)

where qe and qt is the adsorption capacity of Zn(II) (mg·g−1) at equilibrium and time t (min), respectively, and K2 is the pseudosecond-order rate constant (g·mg−1·min−1). Figure 7a shows that the pseudosecond-order model curves are linear at different concentrations when the concentration of Zn(II) was 100 mg·L−1. Figure 7b presents pseudosecondorder model curves which are linear at different concentrations when the temperature is 303 K. The kinetic model parameters are listed in Table 1. The correlation coefficients (r2) for the linear plots of the pseudosecond-order equation were close to 1, and the calculated qe values of the pseudosecond-order model are very agreement with the experimental qe values. These results suggested that Zn(II) adsorption by NH2-MCM48 followed the pseudosecond-order reaction, which inferred that the process controlling the rate may be chemical adsorption.45 From Table 1, it can be seen that the adsorption capacity increased with the increase of initial Zn(II) concentration and temperature, respectively. 3.2.4. Isotherm Studies. The adsorption isotherms describe the relationship between the mass of metal ions adsorbed per unit mass of the adsorbent qe and the liquid phase metal ion concentration Ce at constant temperature. The correlation coefficients (r2) were usually used to find the best fit adsorption isotherm model. From Figure 8a, it can been seen that the adsorption capacity (qe) increased with an rise of the equilibrium concentration (Ce) in solution and temperature, respectively. In the present work, Langmuir and Freundlich isotherm models were used to fit the equilibrium data of adsorption Zn(II) onto NH2-MCM-48 at different temperatures. The Langmuir isotherm assumes monolayer adsorption onto a surface with a finite number of identical sites.46 The equation of the Langmuir isotherm is given by:

Figure 5. Effect of adsorbent dose on the adsorption of NH2-MCM-48 to Zn(II). Conditions: 10 mg·L−1 Zn(II) solution, 20 mL; pH 7.0.

increased in the range of (5 to 30) mg, and then the removal rate reached a plateau (>99 %) in the range of (30 to 60) mg. However, adsorption capacity of Zn(II) onto NH2-MCM-48 decreased with the adsorbent dose increasing, as shown in Figure 5b. Therefore, we selected the 30 mg adsorbent dose in the present study. 3.2.3. Effect of Contact Time and Kinetic Studies. The Zn(II) adsorption rate is one of the most important factors for the adsorption process. As seen from Figure 6, the adsorption

qe =

qmbCe 1 + bCe

(4)

The linear form of the Langmuir model is given by the following equation: Ce C 1 = e + qe qm bqm

(5)

where qe and qm are the adsorption capacity and the maximum monolayer adsorption capacity (mg·g−1), Ce is the equilibrium concentration of Zn(II) (mg·L−1), and b is the Langmuir coefficients (L·mg−1). The Freundlich isotherm is an empirical equation assuming that the adsorption process takes place on a heterogeneous surface through a multilayer adsorption mechanism.47 The equation of the Freundlich isotherm is given by:

Figure 6. Effect of contact time on Zn(II) adsorption by NH2-MCM48. Conditions: initial Zn(II) concentration = ■, 20 mg·L−1; ●, 40 mg·L−1; ▲, 60 mg·L−1; ▼, 100 mg·L−1; pH 7.0, m = 30 mg.

qe = K f Ce1/ n

rate of Zn(II) was fast, and then the adsorption equilibrium was reached nearly in 5 min. With the increase of initial concentration, the time can be a little prolonged. The kinetics of the adsorption process can provide essential information on the reaction pathways. The adsorption of Zn(II) onto NH2-MCM-48 at a short time scale may involve

(6)

The linear form of the Freundlich model is given by the following equation: log qe = 2062

1 log Ce + log K f n

(7)



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Figure 7. Pseudosecond-order kinetic adsorption of Zn(II) by NH2-MCM-48 at (a) different initial concentrations: ■, 20 mg·L−1; ●, 40 mg·L−1; ▲, 60 mg·L−1; ▼, 100 mg·L−1; (b) different temperatures: ■, 30 °C; ●, 40 °C; ▲, 50 °C.

Table 1. Kinetic Adsorption Parameters Obtained Using Pseudosecond-Order Models of Zn(II) at Different Initial Concentrations and Different Temperatures Zn(II) concentration

K2

qe

K2

qe

mg·L−1

(g·mg−1·min−1)

mg·g−1

r2

T/K

g·mg−1·min−1

mg·g−1

r2

20 40 60 100

0.2011 0.1301 0.05569 0.01851

13.17 26.52 39.79 61.01

0.99993 0.99999 0.99993 0.99985

303 313 323

0.02204 0.02237 0.02427

60.58 62.15 64.18

0.9999 0.9998 0.9998

Figure 8. (a) Adsorption isotherms of the adsorption of Zn(II) on NH2-MCM-48. (b) Langmuir isotherms of the adsorption of Zn(II) on NH2MCM-48. ■, 30 °C; ●, 40 °C; ▲, 50 °C.

Table 2. Comparison of Two Isotherm Models for Zn(II) Adsorption on NH2-MCM-48 Langmuir constants

Freundlich constants

T/K

qm/(mg·g−1)

b/(L·mg−1)

r2

n

Kf/(L·g−1)

r2

303 313 323

83.33 90.91 100.00

0.4286 0.5500 0.7692

0.9957 0.9991 0.9976

2.849 2.558 3.086

24.32 26.98 36.22

0.8750 0.7834 0.9073

where qe is the amount of Zn(II) adsorbed at equilibrium (mg·g−1), Ce is the equilibrium concentration of Zn(II) (mg·L−1), Kf is the Freundlich adsorption constant related to adsorption capacity of the adsorbent ((mg·g−1)(L·mg−1)), and 1/n is the adsorption intensity. The two isotherm model constants and correlation coefficients for the adsorption of Zn(II) ions onto NH2MCM-48 are summarized in Table 2. The correlation coefficient values of the Langmuir model (0.9957, 0.9991, and 0.9976) were greater than the Freundlich model (0.8750, 0.7834, and 0.9073). Therefore, the experimental data were fitted better by the Langmuir model than by the Freundlich model, indicating that monolayer adsorption of Zn(II) occurred

on the surfaces of NH2-MCM-48. The maximum adsorption capacity obtained from the Langmuir isotherm model increased with the increase of temperature, demonstrating that the adsorption of Zn(II) on NH2-MCM-48 was an endothermic process. A comparison of Zn(II) adsorption capacities onto various adsorbents calculated using the Langmuir isotherm is given in Table 3. Adsorption capacities from this work (Table 2) were larger than other adsorbents (Table 3), which justified that NH2-MCM-48 was an effective adsorbent to remove Zn(II) from wastewater. The reasons for which NH2-MCM-48 has a high adsorption capacity may be that MCM-48 has two independent three-dimensional structures and an amount of amino groups was loaded on the surface of MCM-48. 2063



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Table 3. Comparison Adsorption Capacity for Zn(II) on Different Adsorbents adsorption capacity adsorbent

mg·g−1

references

hybrid precursor wet rice husk raw chicken feathers carrot residues sulfured orange peel natural bentonite untreated M. oleifera biomass single-walled carbon nanotubes MTTZ-MSU-2 MTTZ-SBA-15 mesoporous silica NH2-MCM-48

28.76 (303 K) 16.978 (298 K) 7.26 (303 K) 29.61 (298 K) 80 (303 K) 68.4931 (303 K) 40.99 (303 ± 1 K) 43.66 (298 K) 61.1 ± 0.65 62.4 23.4 83.33 (303 K)

11 12 14 15 17 23 27 18 25 31 32 this work

Figure 9. Effect of HCl concentration on the recovery rate of Zn(II). Conditions: initial Zn(II) concentration = 10 mg·L−1, m = 30 mg.

3.2.5. Thermodynamic Studies. To investigate the thermodynamic parameters, the adsorption of Zn(II) (C0 = 120 mg·L−1) on NH2-MCM-48 was measured at (303, 313, and 323) K. The thermodynamic parameters such as the distribution coefficient (K0), the Gibbs energy (ΔG0), enthalpy change (ΔH0), and entropy change (ΔS0) were calculated from the following equations:45,48

K0 =

Table 5. Application of NH2-MCM-48 in Real Water Samples (Mean ± Standard Deviation, n = 3) spike sample

Qe Ce

(8)

ΔG 0 = −RT ln K 0 0

ln K 0 =

deionized water tap water river water lap water

(9)

ΔS ΔH − R RT

(10)

ΔS0

kJ·mol

303 313 323

−3.16 −4.99 −6.90

mg·L−1

± ± ± ±

14.97 14.51 14.37 14.18

98.72 96.08 97.62 94.71

0.64 0.87 0.57 0.33

recovery (%) 99.76 96.60 95.71 94.21

± ± ± ±

2.83 0.28 0.73 0.49

4. CONCLUSIONS Amino-functionalized MCM-48 (NH2-MCM-48) was successfully synthesized by the co-condensation method. Batch experiments showed that Zn(II) could be effectively removed by NH2-MCM-48. The adsorption kinetics data were found to follow the pseudosecond-order kinetic model. The adsorption isotherms were fitted well with the Langmuir model. The maximum adsorption capacities of Zn(II) onto NH2-MCM-48 were (83.33, 90.91, and 100.00) mg·g−1 at (303, 313, and 323) K, respectively. The adsorption thermodynamic parameters (ΔG0, ΔH0, and ΔS0) inferred that the adsorption reaction of Zn(II) on NH2-MCM-48 was an endothermic and spontaneous process. Moreover, the adsorbent was applied in real water samples, and the removal rate and recovery of Zn(II) from water were high. These results indicate that NH2-MCM-48 is an efficient adsorbent to remove Zn(II) from polluted water.

Table 4. Thermodynamic Parameters for the Adsorption of Zn(II) on NH2-MCM-48 T/K

15 15 15 15

removal rate (%)

99.35) % and (93.75 to 100.36) %, respectively. This indicate that NH2-MCM-48 is an efficient adsorbent to remove Zn(II) from water and has a high recovery to Zn(II).

−1

where R is the gas constant (8.314 J·mol ·K ) and T is the temperature (K). According to eq 10, the values of ΔH0 and ΔS0 were obtained from the slope and intercept of the plot of ln K0 versus 1/T, respectively. The thermodynamic parameters are given in Table 4. The positive value of ΔH0 suggested that

−1

mg·L

Found

0

−1

ΔG0

−1

ΔH0 −1

(J·(mol·K) )

kJ·mol−1

r2

186.90

53.48

0.99963

the adsorption process of Zn(II) was endothermic, which was consistent with the case that the adsorption capacities of Zn(II) increased with the increase of temperature. The negative value of ΔG0 indicated the spontaneous nature of adsorption process. 3.2.6. Desorption Studies. To test the recovery rate of Zn(II) on NH2-MCM-48, the adsorbed Zn(II) of NH2-MCM48 were treated with different concentrations of HCl (10 mL); after shaking for 0.5 h, the recovery Zn(II) was tested by ICPAES. As shown in Figure 9, 0.1 mol·L−1 HCl is efficient, and the recovery rate is close to 100 %. 3.3. Application to Real Water Samples. The performance of NH2-MCM-48 was applied to recover Zn(II) from water samples, each spiked with 15 mg·L−1 Zn(II) to a solution, and the analytical results are given in Table 5. The removal rates and recoveries were found to be in the range of (94.4 to

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Funding

This research was supported by the Department of Science & Technology of Zhejiang Province (No. 2010C31024). Notes

The authors declare no competing financial interest. 2064



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(22) Sheta, A. S.; Falatah, A. M.; Sewailem, M. S. A.; Khaled, E. M.; Sallam, A. S. H. Sorption characteristics of zinc and iron by natural zeolite and bentonite. Microporous Mesoporous Mater. 2003, 61, 127− 136. (23) Sen, T. K.; Gomez, D. Adsorption of zinc (Zn2+) from aqueous solution on natural bentonite. Desalination 2011, 267, 286−294. (24) Alothman, Z. A.; Apblett, A. W. Metal ion adsorption using polyamine-functionalized mesoporous materials prepared from bromopropyl-functionalized mesoporous silica. J. Hazard. Mater. 2010, 182, 581−590. (25) Zhao, Y. L.; Gao, Q.; Tang, T.; Xu, Y.; Wu, D. Effective NH2grafting on mesoporous SBA-15 surface for adsorption of heavy metal ions. Mater. Lett. 2011, 65, 1045−1047. (26) Bhatti, H. N.; Mumtaz, B.; Hanif, M. A.; Nadeem, R. Removal of Zn(II) ions from aqueous solution using Moringa oleifera Lam. (horseradish tree) biomass. Process. Biochem. 2007, 42, 547−553. (27) Yanagisawa, H.; Matsumoto, Y.; Machida, M. Adsorption of Zn(II) and Cd(II) ions onto magnesium and activated carbon composite in aqueous solution. Appl. Surf. Sci. 2010, 256, 1619−1623. (28) Zhang, H. B.; Tong, Z. F.; Wei, T. Y.; Tang, Y. K. Removal characteristics of Zn(II) from aqueous solution by alkaline Cabentonite. Desalination 2011, 276, 103−108. (29) Pitcher, S. K.; Slade, R. C. T.; Ward, N. I. Heavy metal removal from motorway stormwater using zeolites. Sci. Total Environ. 2004, 334− 335, 161−166. (30) Quintanilla, D. P.; Sánchez, A.; Hierro, I. D.; Fajardo, M.; Sierra, I. Preconcentration of Zn(II) in water samples using a new hybrid SBA-15-based material. J. Hazard. Mater. 2009, 166, 1449−1458. (31) Yang, H.; Xu, R.; Xue, X. M.; Li, F. T.; Li, G. T. Hybrid surfactant-templated mesoporous silica formed in ethanol and its application for heavy metal removal. J. Hazard. Mater. 2008, 152, 690−698. (32) Benhamou, A.; Baudu, M.; Derriche, Z.; Basly, J. P. Aqueous heavy metals removal on amine-functionalized Si-MCM-41 and SiMCM-48. J. Hazard. Mater. 2009, 171, 1001−1008. (33) Heidari, A.; Younesi, H.; Mehraban, Z. Removal of Ni(II), Cd(II), and Pb(II) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica. Chem. Eng. J. 2009, 153, 70−79. (34) Wu, S. J.; Li, F. T.; Xu, R.; Wei, S. H.; Li, G. T. Synthesis of thiol-functionalized MCM-41 mesoporous silicas and its application in Cu(II), Pb(II), Ag(I), and Cr(III) removal. J. Nanopart. Res. 2010, 12, 2111−2124. (35) Liu, X. B.; Du, Y.; Guo, Z.; Gunasekaran, S.; Ching, C.-B.; Chen, Y.; Leong, S. S. J.; Yang, Y. H. Monodispersed MCM-41 large particles bymodified pseudomorphic transformation: Direct diamine functionalization and application in protein bioseparation. Microporous Mesoporous Mater. 2009, 122, 114−120. (36) Delacôte, C.; Gaslain, F. O. M.; Lebeau, B.; Walcarius, A. Factors affecting the reactivity of thiol-functionalized mesoporous silica adsorbents toward mercury(II). Talanta 2009, 79, 877−886. (37) Yokoi, T.; Yoshitake, H.; Tatsumi, T. Synthesis of aminofunctionalized MCM-41 via direct co-condensation and post-synthesis grafting methods using mono-, di- and tri-amino-organoalkoxysilanes. J. Mater. Chem. 2004, 14, 951−957. (38) Olkhovyk, O.; Antochshuk, V.; Jaroniec, M. Benzoylthioureamodified MCM-48 mesoporous silica for mercury(II) adsorption from aqueous solutions. Colloids. Surf. A: Physicochem. Eng. Aspects 2004, 236, 69−72. (39) Sadeghi, O.; Tavassoli, N.; Amini, M. M.; Ebrahimzadeh, H.; Daei, N. Pyridine-functionalized mesoporous silica as an adsorbent material for the determination of nickel and lead in vegetables grown in close proximity by electrothermal atomic adsorption spectroscopy. Food Chem. 2011, 127, 364−368. (40) Liu, C. Y.; Wang, S. Y.; Rong, Z. H.; Wang, X. Q.; Gu, G. N.; Sun, W. J. Synthesis of Structurally Stable MCM-48 Using Mixed Surfactants as Co-template and Adsorption of Vitamin B12 on the Mesoporous MCM-48[J]. J. Non-Cryst. Solids 2010, 356, 1246−1251.

REFERENCES

(1) Quintanilla, D. P.; Sánchez, A.; Hierro, I. D.; Fajardo, M.; Sierra, I. New hybrid materials as Zn(II) sorbents in water samples. Mater. Res. Bull. 2010, 45, 1177−1181. (2) Barczak, M.; Skwarek, E.; Janusz, W.; Dabrowski, A.; Pikus, S. Functionalized SBA-15 organosilicas as sorbents of zinc(II) ions. Appl. Surf. Sci. 2010, 256, 5370−5375. (3) Tamayo, M. M. G.; García, A. M.; Díez, M. A. D.; Correa, E. M. C. Adsorption of Zn(II) in aqueous solution by activated carbons prepared from evergreen oak (Quercus rotundifolia L.). J. Hazard. Mater. 2008, 153, 28−36. (4) Lin, L.-C.; Juang, R.-S. Ion-exchange equilibria of Cu(II) and Zn(II) from aqueous solutions with Chelex 100 and Amberlite IRC 748 resins. Chem. Eng. J. 2005, 112, 211−218. (5) Tokuda, H.; Kuchar, D.; Mihara, N.; Kubota, M.; Matsuda, H.; Fukuta, T. Study on reaction kinetics and selective precipitation of Cu, Zn, Ni and Sn with H2S in single-metal and multi-metal systems. Chemosphere 2008, 73, 1448−1452. (6) Jahanbin, T.; Hashim, M.; Mantori, K. A. Comparative studies on the structure and electromagnetic properties of Ni−Zn ferrites prepared via co-precipitation and conventional ceramic processing routes. J. Magn. Magn. Mater. 2010, 322, 2684−2689. (7) Shukla, R.; Rao, G. N. Solvent extraction of metals with potassium-dihydro-bispyrazolyl-borate. Talanta 2002, 57, 633−639. (8) Zhang, X. J.; Li, X. G.; Cao, H. B.; Zhang, Y. Separation of copper, iron (III), zinc and nickel from nitrate solution by solvent extraction using LK-C2. Sep. Purif. Technol. 2010, 70, 306−313. (9) Rouge, N. F.; Dupont, A.; Vidonne, A.; Dejeu, J.; Fievet, P.; Foissy, A. Removal of some divalent cations from water by membranefiltration assisted with alginate. Water Res. 2006, 40, 1303−1309. (10) Zhou, R.; Palmer, V.; Geckeler, K. E. Removal of inorganic ions by polymer-based colloid-enhanced membrane filtration in aqueous solution. Water Res. 1994, 28, 1257−1260. (11) Gupta, N.; Amritphale, S. S.; Chandra, N. Removal of Zn(II) from aqueous solution by using hybrid precursor of silicon and carbon. Bioresour. Technol. 2010, 101, 3355−3362. (12) Shafey, E. I. E. Removal of Zn(II) and Hg(II) from aqueous solution on a carbonaceous sorbent chemically prepared from rice husk. J. Hazard. Mater. 2010, 175, 319−327. (13) Naiya, T. K.; Chowdhury, P.; Bhattacharya, A. K.; Das, S. K. Saw dust and neem bark as low-cost natural biosorbent for adsorptive removal of Zn(II) and Cd(II) ions from aqueous solutions. Chem. Eng. J. 2009, 148, 68−79. (14) Villarreal, I. A. A.; Petricioleta, A. B.; Montoya, V. H.; Moránc, M. A. M.; Avila, H. E. R. Batch and column studies of Zn2+ removal from aqueous solution using chicken feathers as sorbents. Chem. Eng. J. 2011, 167, 67−76. (15) Nasernejad, B.; Zadeh, T. E.; Pour, B. B.; Bygi, M. E.; Zamani, A. Camparison for biosorption modeling of heavy metals (Cr(III), Cu(II), Zn(II)) adsorption from wastewater by carrot residues. Process. Biochem. 2005, 40, 1319−1322. (16) Shukla, S. R.; Pai, R. S. Adsorption of Cu(II), Ni(II) and Zn(II) on dye loaded groundnut shells and sawdust. Sep. Purif. Technol. 2005, 43, 1−8. (17) Liang, S.; Guo, X. Y.; Tian, Q. H. Adsorption of Pb2+ and Zn2+ from aqueous solutions by sulfured orange peel. Desalination 2011, 275, 212−216. (18) Lu, C.; Chiu, H. Adsorption of zinc(II) fromwaterwith purified carbon nanotubes. Chem. Eng. Sci. 2006, 61, 1138−1145. (19) Almaraz, V. B.; Trocellier, P.; Rangel, I. D. Adsorption of aqueous Zn(II) species on synthetic zeolites. Nucl. Instrum. Methods B 2003, 210, 424−428. (20) Ding, P.; Huang, K.-L.; Li, G.-Y.; Liu, Y.-F.; Zeng, W.-W. Kinetics of adsorption of Zn(II) ion on chitosan derivatives. Int. J. Biol. Macromol. 2006, 39, 222−227. (21) Covelo, E. F.; Á lvarez, N.; Couce, M. L. A.; Vega, F. A.; Marcet, P. Zn adsorption by different fractions of Galician soils. J. Colloid Interface Sci. 2004, 280, 343−349. 2065



Article

(41) Lou, L. -L.; Jiang, S.; Yu, K.; Gu, Z. C.; Ji, R. N.; Dong, Y. L.; Liu, S. X. Mesoporous silicas functionalized with aminopropylvia cocondensation: Effective supports for chiral Mn(III) salen complex[J]. Microporous Mesoporous Mater. 2011, 142, 214−220. (42) Yuan, Y. Z.; Cao, W.; Weng, W. Z. CuCl2 immobilized on amino-functionalized MCM-41 and MCM-48 and their catalytic performance toward the vapor-phase oxy-carbonylation of methanol to dimethylcarbonate. J. Catal. 2004, 228, 311−320. (43) Sert, S.; Eral, M. Uranium adsorption studies on aminopropyl modified mesoporous sorbent (NH2-MCM-41) using statistical design method. J. Nucl. Mater. 2010, 406, 285−292. (44) Chen, L. H.; Lü, L. L.; Shao, W. J.; Luo, F. Kinetics and Equilibria of Cd(II) Adsorption onto a Chemically Modified Lawny Grass with H[BTMPP]. J. Chem. Eng. Data 2011, 56, 1059−1068. (45) Zhang, Y.; Li, Y. F.; Yang, L.-Q.; Ma, X.-J.; Wang, L.-Y.; Ye, Z.-F. Characterization and adsorption mechanism of Zn2+ removal by PVA/ EDTA resin in polluted water. J. Hazard. Mater. 2010, 178, 1046− 1054. (46) Liu, Y.; Liu, Z. C.; Gao, J.; Dai, J. D.; Han, J.; Wang, Y.; Xie, J. M.; Yan, Y. S. Selective adsorption behavior of Pb(II) by mesoporous silica SBA-15-supported Pb(II)-imprinted polymer based on surface molecularly imprinting technique. J. Hazard. Mater. 2011, 186, 197− 205. (47) Chen, S. H.; Zhang, J.; Zhang, C. L.; Yue, Q. Y.; Li, Y.; Li, C. Equilibrium and kinetic studies of methyl orange and methyl violet adsorption on activated carbon derived from Phragmites australis. Desalination 2010, 252, 149−156. (48) Zhang, L.; Zhang, M.; Guo, X. J.; Liu, X. Y.; Kang, P. L.; Chen, X. Sorption characteristics and separation of tellurium ions from aqueous solutions using nano-TiO2. Talanta 2010, 83, 344−350.

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Amino-Functionalized Mesoporous Silicas MCM-48 as Zn(II) Sorbents

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