Synthesis and application of mixed manganese - Iron oxide nanoparticles for adsorption of as(v) from aqueous solutions

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SYNTHESIS AND APPLICATION OF MIXED MANGANESE-IRON 
OXIDE NANOPARTICLES FOR ADSORPTION OF As(V) 
FROM AQUEOUS SOLUTIONS 
Synthesis of adsorbent and its adsorption 
Le Ngoc Chunga*, Le Thanh Quoca 
aThe Faculty of Chemistry, Dalat University, Lamdong, Vietnam 
Correspoding author: Email: chungln@dlu.edu.vn 
Abstract 
A simple method has been used to synthesize nanoparticles of mixed manganese-iron oxide 
for the adsorption of As(V) metal ions from aqueous solutions. Transmission Electron 
Microscopy (TEM), X-Ray diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier 
transform infrared spectroscopy (FTIR), BET analysis were used to determine particle size 
and characterization of produced nanoparticles. The x-ray diffraction pattern indicated that 
the as-synthesized adsorbent is amorphous with 288.268 m2/g surface area; the amorphous 
synthesized products were aggregated with many nanosized particles. The crystallinity of the 
Mn2O3/Fe2O3 were obtained at 400°C and 600°C calcination temperature. The FTIR spectra 
confirmed the presence of -OH group and H-O-H group localized at 3200 - 3400 cm–1 and 
1618-1653 cm−1; theses intense bands is weak (fade) at the high calcination temperature of 
the mixed manganese-iron oxide nanoparticles. In addition, when the calcination 
temperature of the mixed manganese-iron oxide nanoparticles was 400OC, the weak 
absorption bands at 630 cm−1 due to the vibrations of (Fe-O). The results showed that the 
mixed manganese-iron oxide nanoparticles has high selectivity for As(V). 
Keywords: Mixed manganese-iron oxide nanoparticles; Amorphous; As(V). 
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TỔNG HỢP VÀ ỨNG DỤNG HỖN HỢP NANO OXID MANGAN-
SẮT ĐỂ HẤP PHỤ As(V) TỪ DUNG DỊCH NƯỚC 
Tổng hợp chất hấp phụ và tính chất hấp phụ 
Lê Ngọc Chunga*, Lê Thành Quốca 
aKhoa Hóa học, Trường Đại học Đà Lạt, Lâm Đồng, Việt Nam 
*Tác giả liên hệ: Email: chungln@dlu.edu.vn 
Tóm tắt 
Một phương pháp đơn giản cho sự tổng hợp chất hấp phụ hỗn hợp nano oxid mangan-sắt để 
hấp phụ ion kim loại As(V) từ dung dịch nước. Phương pháp kính hiển vi điện tử truyền qua 
(TEM), nhiễu xạ tia X (XRD), kính hiển vi điện tử quét (SEM), phổ hồng ngoại (FTIR), phân 
tích BET được sử dụng để xác định kích thước hạt và đặc trưng của hỗn hợp nano oxid 
mangan-sắt. Nhiễu xạ tia X cho thấy chất hấp phụ tổng hợp là hỗn hợp nano oxid mangan-
sắt có cấu trúc vô định định hình có diện tích bề mặt 288.268 m2/g và bị hiện tượng 
aggregation. Khi nung hỗn hợp nano oxid mangan-sắt ở nhiệt độ 400OC và 600OC sẽ xuất 
hiện cấu trúc của tinh thể Mn2O3/Fe2O3. Phổ hồng ngoại FTIR cũng xác nhận hỗn hợp nano 
oxid mangan-sắt được tổng hợp có sự hiện diện của nhóm –OH và nhóm H-O-H tại dải hấp 
thụ 3200 - 3400 cm–1 và 1618-1653 cm−1; cường độ của dải hấp thụ này sẽ yếu đi khi hỗn 
hợp nano oxid mangan-sắt nung ở nhiệt độ cao. Hơn nữa, khi hỗn hợp nano oxid mangan-
sắt nung đến nhiệt độ 400OC thì xuất hiện peak hấp thụ yếu tại 630 cm−1 gây nên do nhóm 
Fe-O. Kết quả cũng chỉ rằng hỗn hợp nano oxid mangan-sắt có tính chọn lọc cao đối với 
As(V). 
Keywords: Mixed manganese-iron oxide nanoparticles, Amorphous , As(V). 
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1. INTRODUCTION 
Water plays important roles in the natural environment, human activities, and 
social development. However, the presence of arsenic in natural waters has become a 
worldwide problem in the past decades [1,2]. Arsenic pollution has been reported recently 
in USA, China, Chile, Bangladesh, Taiwan, Mexico, Romania, United Kingdom, 
Argentina, Poland, Canada, Hungary, New Zealand, Vietnam, Cambodia, Japan and India 
[1-7]. 
Arsenic commonly exists as two inorganic forms of arsenite (AsO33−) and arsenate 
(AsO43−) which are the popular forms in water and referred to as As(III) and As(V). In 
general, As(V) is stable in aerobic environment and As(III) often exists in anaerobic 
environment. The toxicity of arsenic species is different, generally the toxicity of 
inorganic arsenic compounds is about 100 times higher than organic arsenic compounds, 
and the toxicity of inorganic As(III) compounds are approximately 60–80 times higher to 
humans than As(V) compounds [4-10]. They causes skin, lung, bladder and kidney cancer 
as well as pigmentation changes, skin thickening (hyperkeratosis), neurological disorders, 
muscular weakness, loss of appetite and nausea [5-12]. Therefore, it is really necessary to 
remove arsenic from water to make sure that our environment is safe. 
Adsorption has been recognized as a promising technique for removing arsenic 
from drinking water due to its high removal capacity and ease of operation. However, 
As(III) is less efficiently removed than As(V) from aqueous solutions by almost all of the 
arsenic removal technologies and pre-oxidation of As(III) to As(V) is required [4-17]. 
Recently, increasing attention has been focused on metal oxide sorbents such as 
iron, aluminum, titanium, manganese, and zirconium. Among these iron oxides were the 
mostly studied because of their high affinity to arsenic species, low cost and 
environmental friendliness [8-21]. 
Most recently, many researchers used metal composite materials (containing two 
or more metals) as adsorbents to remove As from contaminated water. The results showed 
that the composite metal oxides can not only inherit the advantages of parent oxides but 
also show a synergistic effect of higher adsorption capacity than that of individual metal 
oxides (Lata and Samadder 2016). For instances, Zhang et al. (2005) developed an Fe-Ce 
bimetal oxide sorbent, which has a much higher As(V) adsorption capacity than the 
individual Ce and Fe oxide. Zhang et al. (2007) prepared an Fe-Mn binary oxide sorbent, 
exhibiting a greater enhancement in both As(V) and As(I ... posite particles (the 
synthesized products) with different magnification 
 From the SEM photographs, it was understood that the grains are connected with 
each other. (It was found that the grains present jointly with each other). In few places, 
bigger grains are also seen. It is seen that the synthesized products consists of 
nanoparticles aggregated together to form large clusters. It is a common phenomenon 
when amorphous nanoparticles are annealed [31]. 
Fig. 5. The TEM image of the manganese-iron oxide nanocomposite 
The TEM analysis shows the particles size of the mixed manganese-iron oxide 
nanoparticles are in the range of 20-30nm (fig.5). The surface area of the mixed 
manganese-iron oxide nanoparticles were measured by a BET analyzer, and the surface 
area of the samples was calculated to be 288.268 m²/g. 
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3.2. Adsorption of As (V) onto mixed manganese-iron oxide nanoparticles 
3.2.1. Affecting Factors 
 Effect of pH 
Determination of optimum pH is very important since the pH value affects not 
only the surface charge of adsorbent, but also the degree of ionization and speciation of 
adsorbate during reaction. Adsorption experiments were carried out in the pH range of 2-
6 for the synthesized products by keeping all other parameters constant (As(V) 
concentration = mg/l; stirring speed = 240 rpm; contact time = 120 min, adsorbent dose 
= 0.1g, room temperature = 25°C). 
The result showed that more adsorption at acidic pH indicates that the lower pH 
results in an increase in H+ ions on the adsorbent surface that results is significantly strong 
electrostatic attraction between positively charged adsorbent surface and As(V) arsenate 
ions (divalent HAsO42- or monovalent H2AsO4-). Lesser adsorption of As(V) at pH values 
greater than 6.0 may be due the dual competition of both the anions (HAsO42- and OH-) 
to be adsorbed on the surface of the adsorbent of which OH- predominates. 
Figure 6. Effect of pH on the As(V) adsorption 
 Effect of contact time 
The effect of contact time was studied at optimum condition of dose, pH, and 
agitation speed. From Fig. 7, it is observed that the adsorption of As(V) increased as 
contact time increased. The adsorption percentage of metal ions approached equilibrium 
within 120 min. After this equilibrium period, the amount of adsorbed metal ions did not 
significantly change with time. 
50
60
70
80
90
100
0 1 2 3 4 5 6 7
A
ds
or
pt
io
n,
 (%
)
pH
250 ppm
300 ppm
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Figure 7. Effect of contact time on the As(V) adsorption 
 Effect of initial As(V) concentration 
The adsorption of As(V) with synthesized products was studied by varying As(V) 
concentration (100ppm - 1000ppm) keeping other parameters (adsorbent dose, stirring 
speed, solution pH, temperature and contact time) constant. As illustrated in Fig. 8, As(V) 
uptake reduced from 99.89% to ~ 30%, as the As(V) concentration increased from 
100ppm to 1000ppm. 
Figure 8. Effect of initial As(V) concentrations on the As(V) adsorption 
3.2.2. Comparation of Bivalent Cationic Metals Adsorption Cd(II), Co(II), 
Cu(II), Zn(II) and As(V) on mixed manganese-iron oxide nanoparticles 
The results of Table 1 showed that the mixed manganese-iron oxide nanoparticles 
have not successfully used for the adsorption of Cd(II)
, Cu(II), Co(II), Zn(II) ions from 
aqueous solution on concentration of 20ppm for each (or more), inversely strongly 
adsorption of As(V) on mixed manganese-iron oxide nanoparticles. This remarkable 
0
10
20
30
40
50
60
70
80
90
0 20 40 60 80 100 120 140 160 180 200
A
ds
or
pt
io
n,
 (%
)
The contact time (min)
262,97ppm
304,41ppm
0
20
40
60
80
100
0 200 400 600 8001000A
ds
or
pt
io
n,
 (%
)
Co (ppm)
0.1
g
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difference is probably due to the difference ionic radius (table 2) and the greater the valence. 
Danny et al. (2004) and Lee and Moon (2001) explained that the smaller the ionic radius 
and the greater the valence, the more closely and strongly is the ion adsorbed [32-34]. 
Therefore, the mixed manganese-iron oxide nanoparticles have successfully used for the 
adsorption of As(V) from aqueous solution. 
Table 1. Adsorption percentage of metal ions on to mixed manganese-iron oxide 
nanoparticles 
pH Adsorption of metal ions on to mixed manganese-iron oxide nanoparticles, (%) 
As(V) 
(150ppm) 
Cd(II) 
(20ppm) 
Co(II) 
(20ppm) 
Cu(II) 
(20ppm) 
Zn(II) 
(20ppm) 
Adsorption 
percentage, % 
SD* 
2 99.89 0.01 non-ads. non-ads. - - 
3 98.45 0.09 non-ads. non-ads. - - 
4 95.28 0.05 non-ads. non-ads. non-ads. non-ads. 
5 96.46 0.06 non-ads. non-ads. - - 
6 96.51 0.01 non-ads. non-ads. - - 
Note: (*) Standard deviation (SD) 
Table 2. Effective ionic radii in pm of elements 
Ion As(V) Cd(II) Co(II) Cu(II) Zn(II) 
Effective ionic radii (pm) 46 95 65 73 74 
4. CONCLUSION 
A simple method has been used to synthesize nanoparticles of mixed manganese-
iron oxide for the adsorption of As(V) metal ions from aqueous solutions under batch 
conditions. Transmission Electron Microscopy (TEM), X-Ray diffraction (XRD), 
Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), 
BET analysis were used to determine particle size and characterization of produced 
nanoparticles. Moreover, the effects of pH, contact time and adsorbent weight on 
adsorption process were investigated. The high uptake of As(V) by the mixed manganese-
iron oxide nanoparticles may be due to its relatively high surface area. 
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