• About US +
• For Contributors +
• Journal Search +
Journal Search Engine
ISSN : 1225-0562(Print)
ISSN : 2287-7258(Online)
Korean Journal of Materials Research Vol.30 No.9 pp.447-452
DOI : https://doi.org/10.3740/MRSK.2020.30.9.447

Removal of Heavy Metals from Wastewater using α-Fe2O3 Nanocrystals

Bulgan Tsedenbal1, Ji Eun Lee1, Seok Hwan Huh2, Bon Heun Koo1, Chan Gyu Lee1
1School of Materials Science and Engineering, Changwon National University, Changwon, Gyeongnam 51140, Republic of Korea
2School of Mechatronics Convergence Engineerings, Changwon National University, Changwon, Gyeongnam 51140, Republic of Korea
Corresponding author E-Mail : chglee1225@gmail.com (C. G. Lee, Changwon Nat'l Univ.)

June 26, 2020 July 29, 2020 August 21, 2020

Abstract

In this work, α-Fe2O3 nanocrystals are synthesized by co-precipitation method and used as adsorbent to remove Cr6+, Cd2+, and Pb2+ from wastewater at room temperature. The prepared sample is evaluated by XRD, BET surface area, and FESEM for structural and morphological characteristics. XRD patterns confirm the formation of a pure hematite structure of average particle size of ~ 40 nm, which is further supported by the FESEM images of the nanocrystals. The nanocrystals are found to have BET specific surface area of ~ 39.18 m2 g−1. Adsorption experiments are carried out for the different values of pH of the solutions, contact time, and initial concentration of metal ions. High efficiency Cr6+, Cd2+, and Pb2+ removal occur at pH 3, 7, and 5.5, respectively. Equilibrium study reveals that the heavy metal ion adsorption of the α-Fe2O3 nanocrystals followed Langmuir and Freundlich isotherm models. The Cr6+, Cd2+, and Pb2+ adsorption equilibrium data are best fitted to the Langmuir model. The maximum adsorption capacities of α-Fe2O3 nanocrystals related to Cr6+, Cd2+, and Pb2+ are found to be 15.15, 11.63, and 20 mg g−1, respectively. These results clearly suggest that the synthesized α-Fe2O3 nanocrystals can be considered as potential nano-adsorbents for future environmental and health related applications.

초록

Changwon National University

This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

1. Introduction

Among inorganic minerals present in the environment, iron oxide nanoparticles with large surface area have the most reactive surface sites and organic contaminants including both cations and anions5). The small size of iron oxide was benign for the scattering of metal ions from solution onto the active sites of the adsorbents surface11). We considered α-Fe2O3 (hematite), is the most stable iron oxide and environmental safety. Hematite have attracted extensive attention in the area of materials science due to its well-known applications in pigments, rechargeable lithium ion batteries, catalyst, photocatalysis and waste water treatment12).

Many iron oxide (Fe3O4, γ-Fe2O3 and α-Fe2O3) nanostructures have been synthesized to remove heavy metals due to their high surface area, magnetic properties, chemical stability and low toxicity.10, 13,14, 15-17)

In this work, we synthesized the α-Fe2O3 (hematite) using co-precipitation method. The synthesized sample was characterized by physical and chemical properties. The α-Fe2O3 nanocrystals were used as nano-adsorbents for the removal of heavy metal ions Cr6+, Cd2+ and Pb2+ from water. The optimum pH, adsorption capacity and equilibrium parameters were investigated. The results obtained in the present work clearly suggest that the hematite nanocrystals can be used convenient and low costing material for the recovery of heavy metal ions from waste water.

2. Experimental

2.1 Synthesis of adsorbent and characterization

The sample was prepared using the method reported in our previous work.18) FeCl3 was added into a 2M HCl to form a solution with the concentration of 1M for FeCl3. Then pH of the solution was adjusted to 10 by using 2M NH4OH. The preparing precipitate was centrifuged and washed with ethanol and deionized water 3 times and dried in air at 70 °C for 12 h. Finally, the precursors were calcined at 400 °C temperatures for 2 h in air. X-ray diffraction (XRD) pattern of α-Fe2O3 nanocrystals was obtained using a BRUKER D8 Advance diffractometer with Cu Kα radiation of wavelength 1.5406 Å. The morphology of the α-Fe2O3 nanocrystals was studied by field emission scanning electron microscopy (FESEM, MERLIN-ZEISS). Surface area was analyzed by Brunauer- Emmet-Teller (BET) methods using an Autosorb iQ Station 1 gas sorption analyzer (Quantachrome Instrument Corp., USA). Nitrogen adsorption data were taken at five relative pressures and at a temperature of 77 K to calculate the surface area using BET theory. The sample was degassed at 150 °C for 5 h under vacuum prior to analysis.

Metal ions Cd2+ and Pb2+ solutions were prepared respectively from their nitrates, chlorides while Cr6+ solution was prepared by using K2Cr2O7 and DI water. The adsorption study was conducted by making the stock solutions (with initial concentration of 1000 mg L-1) and diluted heavy metal ions solution. For the adsorption, 0.15 g of the α-Fe2O3 nanocrystals was put on to 30 ml of the heavy metal ions solution with the initial pH value 5.5 ± 0.1. After 10 min, the adsorbent was separated by filtering the solution. Initial and final metal ions concentrations were analyzed by an inductively coupled plasma-optical emission spectrometer (ICP-OES, Optima 8300, PERKIN ELMER USA). The adsorption efficiency (AE) was calculated by analyzing initial and residual heavy metal ions concentrations in solution before and after contact with adsorbent through the following equation:

$AE % = ( C 0 − C e ) C 0 × 100$
(1)

where C0 and Ce (mg L−1) are the initial and final residual concentrations of heavy metal ions in aqueous solutions. The equilibrium adsorption capacity of heavy metal ions was calculated using the following equation:

$q e = ( C 0 − C e ) V m$
(2)

3. Results and discussion

3.1 Properties of prepared α-Fe2O3 nanocrystals

Fig. 1(a) and (b) shows the XRD and FESEM image of the synthesized sample respectively. The XRD analysis showed the formation of the hematite structure well indexed according to the JCPDS No. 89-2810. In the XRD pattern of the synthesized sample indicating no impurity peak was observed the complete reaction between the raw materials. The most intense (104) peak was selected to calculate the crystallite size. The average crystallite size of α-Fe2O3 nanocrystals as calculated from the Scherrer equation was found to be 17 nm. The FESEM image shows the morphology and the particle sizes of the sample which are very similar with those reported in Ref.18). Furthermore, the specific BET surface areas of the nanocrystal α-Fe2O3 was found to be 39.18 m2 g−1 by calculating the results of N2 adsorption. The large BET surface area is significant for adsorption process.5)

The effect of adsorbent amount, on heavy metals adsorption by α-Fe2O3 nanoparticles was studied in the 30 ml solution was mixed with different doses of while keeping other parameters constant. Initial concentration of heavy metals was kept at 10 mg L−1 with the contact time of 10 min. It can be seen from Fig. 2(a) that the removal efficiency of metal ions generally increased with an increase in the dosage of α-Fe2O3 nanoparticles. An increase in the adsorbent dosage from 0.05 to 0.15 g led to an increase in the removal efficiency of Cr6+, Cd2+ and Pb2+ from 32.6 to 74.3, 59.7 to 92.2, and 38.3 to 100 %, respectively. Adsorbent mass increased with the increase in removal efficiency. This can be attributed to the increasing number of binding sites with the increased amount of absorbent.14,19) The maximum adsorption of heavy metals with adsorbent was obtained to be 0.15 g which indicated the optimum dosage.

Time is the also major factor in defining the removal efficiency of adsorption system. In order to investigate the effect of contacting time on heavy metal ions, further experiments were carried out using 0.15 g of α-Fe2O3 nanocrystals at room temperature. Fig. 3(a) shows the effect of contacting time on the adsorption efficiency of heavy metal ions by α-Fe2O3. As can been in Fig. 3(a) the heavy metals solution concentration was reduced by above 90 % within the first 2 minutes of contact and remained constant up to 20 minutes. It is clear that adsorption rates of heavy metal ions were time independent. However, a slight increase in the all heavy metal ions adsorption rates observed at the 10 minutes in adsorption time.

In this study, the wastewater with initial heavy metal ions concentration of 20 to 160 mg L−1 was taken and adsorption time was settled at 10 min. As shown in Fig. 3(b) adsorption capacity depended on the initial metal ions concentration. It was found that the adsorption capacities increased with increase in initial concentrations of heavy metal ions. This can be attributed to the fact that more heavy metal ions could bind to the adsorption sites on the surface of the hematite nanocrystals. At the higher concentrations of heavy metal ions, the rate of increase adsorption capacity became gradually slow. These results are in good agreement with the already reported works.11,15) Both Langmuir and Freundlich isotherm models were used to evaluated the obtained data. Langmuir isotherm equation is derived from the adsorbent surface with a fixed number of binding sites, and the monolayer adsorption occurs on the surface of adsorbent isotherm20). The linearized Langmuir isotherm is given as:

$C e q e = 1 q m b + C e q m$
(3)

Where Ce is equilibrium concentration of the metal ions (mg l−1) and qe is the quantity of the heavy metal adsorbed at equilibrium of α-Fe2O3 nanocrystal (mg g−1), b Langmuir constant connected to the bond energy of adsorption (l g−1) and qm is maximum adsorption capacity (mg g−1).The constants b and qm can be determined from the intercept and slope of the linear plot Ce/qe versus Ce.21) Freundlich isotherm can be applied for heterogenous surfaces and multilayer adsorption can occurred. It is represented as:

$log q s = log K + 1 n log C e$
(4)

where K is the constant the relative adsorption capacity of the adsorbent (mg1-1/n L1/n g−1) and n represents the adsorption intensity. The constants n and K can be determined from the slope and intercept of the linear plot logqe versus logCe.10) The quantitative relationship between initial Cr6+, Cd2+ and Pb2+ ions concentration and the adsorption capacity analyzed with two different isotherm models are illustrated in Fig. 4(a, b). The calculated correlation coefficients (b, qm, n and K) and linear regression coefficient (R2) values for each Langmuir and Freundlich model are outlined in Table 1. The calculated linear regression coefficient (R2) values for the plots in Fig. 4(a) are well greater than 0.99 suggesting a strong linear relationship between Ce and Ce/qe. It is indicating that the Langmuir model was more applicable than Freundlich model.

In particular, metal ions of Pb2+ have more affinity to iron oxide nanocrystal and are more favorable for adsorption than Cr6+ and Cd2+ ions. This may be attributed to the comparatively higher electronegativity value of lead.22) The more electronegative metals should form the strongest covalent bond with oxygen atoms on nanoparticles surfaces.19) A comparison of the maximum adsorption capacities of Cr6+, Cd2+ and Pb2+ ions onto different morphologies of α-Fe2O3 are given in Table 2. The adsorption capacity of heavy metals ions on α-Fe2O3 nanocrystals was significantly higher than that of other adsorbents. This may be due to the morphology, surface area and particles size of our prepared nanocrystals which are quite different from those reported in literatures.12,23,24)

4. Conclusions

In summary, α-Fe2O3 nanocrystals were well synthesized by a simple co-precipitation method. The fabricated sample was tested for the removal of heavy metals from wastewater. Heavy metal ions adsorption activities of α-Fe2O3 nanocrystals were examined with different experimental conditions. The pH was played important role in heavy metal ion adsorption. Maximum removal of Cd2+, Cr6+ and Pb2+ ions occurred at pH 3, 7 and 5.5, respectively. The adsorption is a physico-chemical process which affecting significant electrostatic attractions between α-Fe2O3 nanocrystals and heavy metal ions. The results show that the capacity of heavy metal ions increased as the contact time and initial metal ions concentration increased. The Langmuir adsorption isotherm model provided the better fit as revealed by the higher linear regression coefficient values compared to the Freundlich model which confirmed the monolayer adsorption of the studied metal ions onto α-Fe2O3 nanocrystals surface. Langmuir adsorption capacities of 11.63, 15.15, and 20 mg g−1 were obtained for Cd2+, Cr6+ and Pb2+ ions respectively. The findings of the present work showed that α-Fe2O3 nanocrystals can be used as good adsorbents for the removal of heavy metal ions from waste water.

Acknowledgement

This research was supported by Changwon National University, 2019-2020.

Figure

(a) The powder XRD pattern, (b) FESEM image of α-Fe2O3 nanocrystals

(a) Effect of mass, (b) Effect of pH on adsorption efficiency for heavy metal ions by of α-Fe2O3 nanocrystals

(a) Effect of adsorption time, (b) Effect of initial concentration of heavy metal ions on adsorption capacity by α-Fe2O3 nanocrystals

(a) Langmuir isotherm model, (b) Freundlich isotherm model

Table

The Langmuir and Freundlich isotherm models parameters for the adsorption of Cd2+, Cr6+ and Pb2+ ions onto α-Fe2O3 nanocrystals

The adsorption capacities of different morphologies of α-Fe2O3 adsorbents

Reference

1. K. M. S. Surchi, Int. J. Chem., 3, 103 (2011).
2. F. Rozada, M. Otero, A. Moran and A. I. Garsia, Bioresour. Technol., 99, 6332 (2008).
3. Y. Bagbi, A. Sarswat, D. Mohan, A. Pandey and P. R. Solanki, Sci. Rep., 7, 1 (2017).
4. P. Yuan, D. Liu, M. Fan, D. Yang, R. Zhu, F. Ge, J. Zhu and H. He, J. Hazard. Mater., 173, 614 (2010).
5. M. A. Ahmed, S. M. Ali, S. I. El-Dek and A. Galal, Mater. Sci. Eng., B, 178, 744 (2013).
6. V. M. Boddu, K. Abburi, J. L. Talbott and E. D. Smith, Environ. Sci. Technol. Lett., 37, 4449 (2003).
7. J. T. Mayo, C. Yavuz, S. Yean, L. Cong, H. Shiple, W. Yu, J. Falkner, A. Kan, M. Tomson and V. L. Colvin, Sci. Technol. Adv. Mater., 8, 71 (2007).
8. Z. Elouear, J. Bouzid, N. Boujelben, M. Feki, F. Jamoussi and A. Montiel, J. Hazard. Mater., 156, 412 (2008).
9. G. Vijayakumar, R. Tamilarasan and M. Dharmendirakumar, J. Mater. Environ. Sci., 3, 157 (2012).
10. W. Jiang, M. Pelaez, D. D. Dionysiou, M. H. Entezari, D. Tsoutsou and K. O’Shea, Chem. Eng. J., 222, 527 (2013).
11. H. Karami, Chem. Eng. J., 219, 209 (2013).
12. X. L. Fang, C. Chen, M. S. Jin, Q. Kuang, Z. X. Xie, S. Y. Xie, R.B. Huang and L. S. Zheng, J. Mater. Chem., 19, 6154 (2009).
13. S. Rajput, C. U. Pittman Jr and D. Mohan, J. Colloid Interface Sci., 468, 334 (2016).
14. Y. F. Shen, J. Tang, Z. H. Nie, Y. D. Wang, Y. Ren and L. Zuo, Sep. Purif. Technol., 68, 312 (2009).
15. A. Roy, J. Bhattacharya, Chem. Eng. J., 211-212, 493 (2012).
16. X. L. Cheng, J. S. Jiang, C. Y. Jin, C. C. Lin, Y. Zeng and Q. H. Zhang, Chem. Eng. J., 236, 139 (2014).
17. H. Liang, B. Xu and Z. Wang, Mater. Chem. Phys., 141, 727 (2013).
18. B. Tsedenbal, M. S. Anwar, I. Hussain and B. H. Koo, J. Nanosci. Nanotechnol., 17, 7682 (2017).
19. S. Mahdavi, M. Jalali and A. Afkhami, J. Nanopart. Res. 14, 846 (2012).
20. B. E. Reed, M. R. Matsumoto, Sep. Sci. Technol., 28, 2179 (1993).
21. L. Giraldo, A. Erto and J. C. Moreno-Pirajan, Adsorption, 19, 465 (2013).
22. D. Fialova, M. Kremplova, L. Melichar, P. Kopel, D. Hynek, V. Adam and R. Kizek, Materials, 7, 2242 (2014).
23. D. He, Y. Xiao, D. Liang, H. Zhou, L. Du and L. Liu, Mater. Sci. Appl., 2, 215 (2011).
24. S. Zeng, K. Tang, T. Li, Z. Liang, D. Wang, Y. Wang and W. Zhou, J. Phys. Chem. C, 111, 10217 (2007).