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ICEAMM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 343 (2018) 012003 doi:10.1088/1757-899X/343/1/012003
1234567890‘’“”

Characterization of fabricated MnO2-amberlite photocatalyst

by FTIR, XRD and SEM for alizarin removal
Rita Sundari1, Sagir Alva1, Darwin Sebayang1, Haris Wahyudi1, Soleha Jonit2,
Atiqah Kamaruddin2

1
Faculty of Engineering, Universitas Mercu Buana, 11650 Jakarta, Indonesia
2
Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM
Johor Bahru, Malaysia

[email protected]

Abstract. This study investigates the characterizations of fabricated MnO2-amberlite using for
alizarin photocatalytic degradation. Mixtures of fabricated MnO2-amberlite were magnetically
stirred for 6-, 12-, 18-, 24-, and 30h, respectively. Some functional groups of amberlite like C-
O, C-C and N-H were eliminated after doping with MnO2 as shown by FTIR (Fourier
Transform Infrared) spectra in the range of 1600 – 900 cm-1, change in crystalline structures
due to linkage of MnO2 with amberlite was observed at 2θ of 25o in the XRD (X-ray
diffraction) analysis, and change in surface morphology due to MnO2 doping in amberlite was
investigated in SEM (Scanning electrone microscope) examination. Since alizarin is a harmful
material causing environmental problem, this preliminary study found that the 18h-stirred
fabricated MnO2-amberlite showed the best photocatalytic properties, which enabled to
degrade 23.4% alizarin under 1h UV exposure without heating.

1. Introduction
Nowadays the development of catalysts has taken greater interest especially in purification of
wastewater for human health reason. Among the environmental catalysts, MnO2 photocatalyst is the
most promising one due to thermocatalytic activity for the decomposition of organic pollutant in
wastewater [1]. Several publications reported MnO2 as photocatalyst for dyestuff degradation [2 – 5].
As we have known advance oxidation process is associated with free radicals generated by irradiation
of UV and/or visible light on semiconducting material such as MnO2, which are responsible for the
decomposition of organic compound and changed it into harmless products such as CO2 and H2O. The
utilization of photocatalyst has attracted great interest due to its simple, low cost, and friendly
environmental technology.
Amberlite or resin has largely used as solid phase adsorbent for removing contaminants in aqueous
solution. Previous investigations reported amberlite used for extracting selected heavy metals (copper,
cadmium and lead) from dairy cow’s milk, and fractionized amberlite for removing boron from water,
as well as amberlite XAD 7 for extracting bismuth (III) from hydrochloric acid solution [6-8]. In
addition, several sensors have used modified amberlite as immobilized matrix [9-11]. The utilization
of amberlite as strong acid cationic exchanger has attracted considerable interest due to its stability
and low cost. As resin produced by many plant particularly woody plants made resin in greater utility.
Industrial effluents contain various chemicals including synthetic dyes, which are carcinogenic in
nature. Several dyes decompose aerobically and anaerobically yielding the formation of carcinogenic
compounds. Alizarin or mordant red is known as an organic compound, which is largely used as dye

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ICEAMM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 343 (2018) 012003 doi:10.1088/1757-899X/343/1/012003
1234567890‘’“”

in textile industries yielding environmental problems. Roopaei et al. [12] used hematite (Fe2O3)/NiS
photocatalyst to degrade alizarin in aqueous solution on account of chemical stability and
environmental friendliness, however, this study used MnO2 immobilized in amberlite, which is more
stable and has broader band gap for alizarin photocatalytic degradation. Different stirring times (6h,
12h, 18h, 24h and 30h) of MnO2 and amberlite solution mixture followed by calcinations was used for
the synthesis of MnO2-amberlite. The mixture of MnO2-amberlite and alizarin solution was exposed
to UV light at 265 nm to degrade alizarin. Characterization study of MnO2-amberlite photocatalyst by
FTIR, XRD and SEM was investigated.

2. Experimental

2.1 Materials
All chemicals were purchased and used without further purification. Deion distilled water was used
throughout the experiments. MnO2 (Merck OHG, 99.5 %) for the synthesis of photocatalyst, amberlite
IRA 400 (Sigma Aldrich GmbH, ≥ 95%) for immobilized matrix, and alizarin for assayed dyestuff
(Fluka Chemie, 99%) were used in this study.

2.2 Methods

2.2.1 Synthesis of MnO2-amberlite. About 15g amberlite was grinded to fine powder and dried in an
oven at 98-99oC and then 0.500g dried amberlite was dissolved in 15 ml deion distilled water and
stirred for 5h. 0.200g MnO2 was added to amberlite solution and stirred vigorously with magnetic
stirrer at different time (6-, 12-, 18-, 24-, and 30h), respectively. All MnO2-amberlite solutions with
respect to different stirring times were centrifuged at 3700 rpm for 15min. to obtain
suspended solid, respectively. The MnO2-amberlite products were dried in an oven at 98-99oC
followed by calcination at 250oC for 5h, respectively.

2.2.2 Characterizations. The fabricated MnO2-amberlite was characterized using the following
instruments. The functional group of the MnO2-amberlite was determined by FTIR (Perkin Elmer)
with potassium bromide as the reference sample. The structural property of the fabricated MnO 2-
amberlite was investigated by XRD (Siemens D5000) using CuKα radiation. The surface morphology
of the fabricated MnO2-amberlite was examined by SEM (Philips XL 40) using gold sputter (Polaron
Division SEM coating system) to coat the material powder.

2.2.3 Photocatalytic degradation test. The catalytic degradation of alizarin by the fabricated MnO2-
amberlite was investigated by UV-Vis spectrometer (Perkin Elmer Lambda 25). Standard solutions of
alizarin from 10 ppm to 50 ppm were prepared for calibration at 265 nm. A mixture of fabricated
MnO2-amberlite and alizarin solution of 50 ppm (part per million) placed in a bottle covered by
aluminium foil was exposed to UV light at 265 nm for 1h stirring. The aluminium foil protects the
sample from other contaminants.

3. Results and discussion

3.1 Functional group of the MnO2-amberlite

The functional groups of the fabricated MnO2-amberlite was determined by FTIR spectroscopy. As
shown in Figure 1 (c), the peaks presence at 3421 cm-1, 1614 cm-1, 1488 cm-1and 1475cm-1 are
corresponding with benzene sulphonic groups in cross-linked amberlite polymer. The pure amberlite
shows the aromatic rings at 3022 cm-1 and C-H stretching at 2921 cm-1 (Figure 1c), while the N-H
stretching at 3421 cm-1 (Figure 1c) was getting weaker and showed at 3426 cm-1 in Figure 1b due to
MnO2 doping in amberlite. Furthermore, the FTIR spectrum range of 1600 – 900 cm-1 of pure

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ICEAMM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 343 (2018) 012003 doi:10.1088/1757-899X/343/1/012003
1234567890‘’“”

amberlite shows vibration of C-O and C-C stretching, and N-H bending in the amberlite polymer.
When pure amberlite mixed and magnetically stirred with MnO2, almost all of the functional groups
initially present were eliminated due to mechanical effect and the inclusion of MnO 2 in the cross-
linked polymer. The presence of remarkable peaks at 588 cm-1 (Figure 1b) and 589 cm-1 (Figure 1a)
was due to the formation of Mn-O linkage in relation to tetrahedral and octahedral structure [13 – 15].

Figure 1. FTIR spectra of (a) 6h-stirred MnO2-amberlite, (b) 18h-stirred MnO2-amberlite,

and (c) pure amberlite. KBr reference sample.

3.2 Structure of the MnO2-amberlite

The structural property of the MnO2-amberlite was investigated by the XRD. Figure 2 shows a peak
cluster at 2θ of 25o, which forms unstable structure. It is apparent that the stirring action on the MnO2-
amberlite did not give meaningful effect on the crystalline structure of pure MnO 2. Previous work
reported that the diffraction angles of 25o, 37o and 57o are corresponding with (211), (400) and (440)
planes, respectively [15].

Figure 2. XRD spectra of (a) pure MnO2, (b) 6h-stirred MnO2-amberlite,

and (c) 18h-stirred MnO2-amberlite (50 nA, 40 kV, and angular range of 20.80o).

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ICEAMM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 343 (2018) 012003 doi:10.1088/1757-899X/343/1/012003
1234567890‘’“”

3.3 Surface morphology of MnO2-amberlite

The surface structure of the fabricated MnO2-amberlite was exmined by SEM. Theoretically, the
longer stirring time yields finer particles, however, agglomeration of particles may occur during
stirring process due to polarization and induction effects. Previous work reported manganese
distribution on the ferrite surface were varied due to thermal effect [15-16], however, this study shows
the particles distribution on the material surface due to mechanical effect. Figure 3 shows the SEM
imaging of pure amberlite and fabricated MnO2-amberlite at different stirring times.

3.4 Photocatalytic degradation of alizarin

The utilization of fabricated MnO2-amberlite for photocatalytic degradation of alizarin was conducted
by using UV-Vis spectrometer. Based on the surface adsorption test of BET (Brunauer Emmett Teller)
(not shown), the 18h-stirred MnO2-amberlite showed the largest surface area (65.11m2 g-1 of 0.032g
sample), which assumed to yield the best catalytic property in this study and therefore, this sample was
used in the examination of degradation of alizarin. Based on the calibration curve of UV-Vis
absorption at 265 nm the fabricated MnO2-amberlite might degrade 23.4% of alizarin in aqueous
solution under non heat condition and 6.8% of alizarin under heat condition.

(a) Pure amberlite (b) 6h-stirred MnO2-amberlite

(c) 18h-stirred MnO2- (d) 30h-stirred MnO2-

amberlite amberlite

Figure 3. SEM imaging of pure amberlite and fabricated MnO2-amberlite.

50 µm working distance. 500 x magnification. 25.0 kV.

4. Conclusion

The study presented important features related to the characterization study of FTIR, XRD and SEM
of fabricated MnO2-amberlite, which gives meaningful information for photocatalytic degradation of
alizarin. Some important functional groups were removed and replaced by remarkable peaks at 588 -
589 cm-1 due to MnO2 inclusion as shown in the study of FTIR spectra, however, the XRD

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ICEAMM 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 343 (2018) 012003 doi:10.1088/1757-899X/343/1/012003
1234567890‘’“”

characterization at 2θ of 25o showed that amberlite matrix and stirring process did not give significant
effect on the crystalline structure of pure MnO2. The SEM imaging showed finer particle distribution
on the material surface after MnO2 mixed with amberlite under stirring process.

Acknowledgement

This study was sponsored and financially supported by the Research Management Center
(RMC), Universiti of Technologi Malaysia through FAV Grant 77545, which is gratefully
acknowledged.

References

[1] Qiliang J, Hiroshi A, Musashi F and Hiroaki T 2013 Catalysts 3 444

[2] Li S J, Ma Z, Wang L and Liu J Z 2008 Sci. China Series B: Chem. 51 179
[3] Lifang Z, Daiping H and Ping J 2009 Catalysis Commun. 10 1414
[4] Liu Y, Luo C, Sun J, Li H, Sun Z and Yan S 2015 J. Mater. Chem. A 3 5674
[5] Xue M, Huang L, Wang J O, Wang Y, Gao L, Zhu J and Zhou Z G 2008 Nanotechnol. 19 5604
[6] Hoque M I, Didarul A C, Holze R, Nakib C and Azam M S 2015 J.Environ.Chem.Engineer. 3 831
[7] Nawaf D, Victor K and Nidal H 2015 Desalination 370 1
[8] Navarro R, Ruiz P, Saucedo I and Guibal E 2014 Separation. Purifi. Tech. 135 268
[9] Moghaddam M K, Hellmann J and Lang W 2016 Procedia Engineer. 168 1110
[10] Bliznyuk V N, Duval C E, Apul O G, Seliman A F and DeVol T A 2015 Polymer 56 271
[11] Bairi A, Nithyadevi N, Bairi I, Garin A M and Garcia J A M 2017 Energy Build. 141 218
[12] Roopaei H, Zohdi A R, Abbasi Z and Bazrafkan M 2014 Indian J Sci. Technol. 7 1882
[13] Pradeep A and Chandrasekaran G 2005 Mater. Lett. 60 371
[14] Pradeep A, Priyadharsini P and Chandrasekaran G 2008 J Magnetism & Magnetic Mater. 320
2774
[15] Hua T I and Sundari R 2012 Malaysian J. Fundamental Appl. Sci. 8 149
[16] Sundari R, Hua T I, Aziz M and Nizar U K 2014 Malaysian J. Anal. Sci. 18 485