Synthesis and photocatalytic activity of

nanocomposite based on sodium alginate

from brown algae with ZnO impregnation
Cite as: AIP Conference Proceedings 2023, 020107 (2018); https://doi.org/10.1063/1.5064104
Published Online: 23 October 2018

H. Helmiyati, and K. D. Wahyuningrum

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AIP Conference Proceedings 2023, 020107 (2018); https://doi.org/10.1063/1.5064104 2023, 020107

© 2018 Author(s).
 Synthesis and Photocatalytic Activity of Nanocomposite
Based on Sodium Alginate from Brown Algae
with ZnO Impregnation
H. Helmiyati a) and K. D. Wahyuningrum

Department of Chemistry, Faculty of Mathematic and Natural Sciences (FMIPA),

Universitas Indonesia, Depok 16424, Indonesia
a)
Corresponding author: helmiyati@sci.ui.ac.id

Abstract. The objective of this research is to synthesize nano sodium alginate-ZnO nanocomposite as photocatalyst to
degrade methylene blue compounds. The successful synthesis of nano sodium alginate-ZnO nanocomposite was
supported by the characterization of XRD (X-Ray Diffraction), FTIR (Fourier Transform Infrared), SEM (Scanning
Electron Microscope) and TEM (Tunneling Electron Microscope). The first stage of the research was the synthesis of
nano sodium alginate with particle size 140 nm and crystallinity index 38.78 % by XRD and TEM characterization, the
obtained particle size was 146 nm x 61 nm. Nano ZnO particle size 38 nm, by XRD and TEM characterization the
obtained particle size was 56.6 nm x 33.3 nm. The next stage of nanocomposite synthesis of nano sodium alginate was
the impregnation with nano ZnO particle size 130 nm, by XRD and TEM characterization the particle size was 228.0 nm
x 134.2 nm. The success was also supported by FTIR and SEM characterization. The final stage was the degradation of
blue methylene using nano-sodium alginate-ZnO nanocomposite. The highest degradation percentage by nano sodium
alginate-ZnO nanocomposite with zinc nitrate concentration of 0.075 M was 51.68% with the first order rate constant of
9.5 x10-3 /min.

Keywords: nanocomposite, nano sodium alginate, nano ZnO, degradation, methylene blue.

INTRODUCTION

The water pollution has become one of the main issues because it contains heavy ions and reactive dyes from the
industry over the last few decades [1,2]. The dyes are the most versatile chemicals widely used in pharmaceuticals,
rubber, pesticides, dyestuffs and textiles industries. The industry is using large amounts of dye with residues that
cause large quantities of the colored, toxic and even carcinogenic liquid wastes. The dye pollution causes the
reduction of dissolved oxygen required by aquatic life. The pollutions are resistant to mild and moderate oxidation
materials hence pose a serious danger to the aquatic organisms. The wastes containing synthetic dyes with complex
aromatic molecular structures are recalcitrant with carrier inhibiting properties that cannot be treated with
conventional wastewater treatment methods [3-5].
Recently, there has been an increasing interest in the development of organic / inorganic hybrid materials in the
nanometer scale that has evolved due to their various potential applications. Nanocomposite materials consisting of
biopolymers and metal oxides have opened up more areas of application such as drug delivery, conductive paint,
rechargeable batteries, toner in photocopying, smart windows, and so on. Similarly, it is also happened in the
inorganic substances in the nanoscale which exhibits very different optical and electronic properties compared to its
products that is not nanoscale. [6-9].
The research conducted by Sivakumar et al. [9] made poly (aniline-co-o-anisidine)/ZnO nanocomposites and
their applications as photocatalysts. As well as Qin et al. [10] with the title ZnO microspheres-reduced graphene

Proceedings of the 3rd International Symposium on Current Progress in Mathematics and Sciences 2017 (ISCPMS2017)
AIP Conf. Proc. 2023, 020107-1–020107-6; https://doi.org/10.1063/1.5064104
Published by AIP Publishing. 978-0-7354-1741-0/$30.00

020107-1
oxide nanocomposite for photocatalytic degradation of methylene blue dye, which obtained the rate of methylene
blue degradation reaction in the first order reaction [10].
In this research, the synthesis and characterization of nanocomposite biopolymer based on nano sodium alginate
impregnated with nano ZnO and its application as photocatalyst to degrade methylene blue compounds were
performed. The first stage was to synthesize nano sodium alginate and nano ZnO, then, the synthesis of
nanocomposite based on nano sodium alginate by impregnation with ZnO. Further, the characterization with XRD
(X-Ray Diffraction), FTIR (Fourier Transform Infrared), SEM (Scanning Electron Microscope), TEM (Tunneling
Electron Microscope), and application as photocatalyst to degrade methylene blue compounds.

EXPERIMENTAL

Materials
Sodium alginate (Sigma Aldrich) was used to synthesize nano sodium alginate. Calcium chloride (Merck Co)
and poly-L-lysine (Sigma Aldrich) were used to synthesize nano sodium alginate, zinc nitrate (Merck Co.) and
ammonium hydroxide (Merck Co) were used to synthesize nano-ZnO, methylene blue as degraded dye.

The Synthesis of Nano Sodium Alginate

The synthesis of nano sodium alginate refers to Moradhaseli et al. [11], prepared with an ionic gelation method.
A certain volume of calcium chloride was added to the sodium alginate solution to form the gel. Then, poly-L-lysine
was added to stabilize the suspended nanoparticles. Then, the suspension of the nanoparticles was stirred for 2 hours
and left overnight for stabilization. Then, centrifuged at 13000 rpm for 30 minutes with freeze-drying and kept at
low temperature about 4 °C.

The Synthesis of Nano ZnO

The synthesis of nano ZnO refers to Varaprasad et al. [12], a certain amount of zinc nitrate was dissolved in 50
mL distilled water under a constant stirring at room temperature for 1 h. Ammonium hydroxide was slowly added
until a white precipitate formed at pH 9, then it was stirred for 3 hours. The precipitate was washed with distilled
water until the pH was neutral then the filtrate was dried at 200 °C for 2 hours.

Synthesis of Nanocomposite Based Nano Sodium Alginate with ZnO Impregnation

The synthesis of sodium alginate-ZnO nanocomposite refers to Varaprasad et al. [12] with slight modification. A
certain amount of nano sodium alginate was dissolved in 100 mL of water, then, stirred for 3 hours. The mixture was
sonicated for 45 minutes, then dried at 70 °C for 24 hours. ZnO concentration was performed with mass variation of
0.025, 0.05 and 0.075 g.

Photocatalytic Activity Using Methylene Blue

Photocatalytic activity refers to Sivakumar et al. [9]. A methylene blue solution 10 ppm was prepared in 100 mL
of deionized water. Then, 0.05 g of nanocomposite was added to the methylene blue solution with a constant stirring
using magnetic stirrer for 30 minutes under UV light. Then, 10 mL sample was taken every 10 minutes to determine
the concentration of the non degradated methylene blue using UV-Vis spectrophotometer.

RESULTS AND DISCUSSION

Analysis of Crystallinity Index of Sodium Alginate by XRD

The XRD pattern of nano sodium alginate (red), nano ZnO (black) and sodium-ZnO alginate nanocomposite
(green) is shown in Fig. 1. From the XRD pattern of nano ZnO, it can be seen the maximum intensity at 2θ 36.06°
and amorphous intensity at 2θ 35.35°. The degree of crystallinity obtained for nano ZnO is 91.42 % and the obtained

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 FIGURE 1. XRD pattern of nano sodium alginate (red), nano ZnO
(black), and nano sodium alginate-ZnO nanocomposite (green)

FIGURE 2. FTIR spectra of (a) nano ZnO, (b) nano sodium

alginate-ZnO nanocomposite, and (c) and nano sodium alginate

particle size using the Debye-Scherrer equation is 38.00 nm. In the XRD pattern of nano sodium alginate, it can be
seen the maximum intensity at 2θ 13.19° and amorphous intensity at 2θ 18.18°. The degree of crystallinity obtained
is 38.78 %, shows that the nano sodium alginate has a semi crystalline structure and particle size of 140 nm. In the
sodium alginate-ZnO nanocomposite, it can be seen the maximum intensity at 2θ 36.22° and amorphous intensity at
2θ 35.30°. The degree of crystallinity obtained is 45.48 % and particle size is 130 nm.

Analysis of Functional Groups by FTIR

The spectra of FTIR for nano ZnO (a), nano sodium alginate-ZnO nanocomposite (b) and nano sodium alginate
(c) in Fig. 2. In Fig. 2a, it can be seen the absorption bands of the nano ZnO at 473 cm-1 wave number, which is the
identical absorption band of the Zn-O bond, similar to the research conducted by Ahangar et al. [13] who has done
the synthesis of nano ZnO and obtained Zn-O bond absorption bands at 470 cm-1 wave number. From Fig. 2c, it
can be seen the main absorption band at 750-850 cm-1 wave number, which is the identical absorption band of
sodium alginate, that is the absorption band of mannuronic acid. The absorption band at 960 cm-1 and 1030 cm-1 are
the C-O stretching vibration of uronic acid. This result is similar to the previous research conducted by Helmiyati et

020107-3
al. [14] and Fertah et al. [15]. The absorption band of the asymmetric O-C-O vibration at 1400-1650 cm-1 wave
number is the vibration of the symmetric carboxylate stretching. The absorption band of the O-H vibration at 3200-
3400 cm-1 wave number. In Fig. 2b, it can be seen that the absorption bands of the sodium alginate-ZnO
nanocomposites show the identical absorption bands of sodium alginate and nano ZnO. It was obtained the main
absorption bands which is identical absorption band from sodium alginate, that is C-O stretching vibration from
uronic acid and mannuronic acid, and obtained Zn-O bond bands at 470 cm-1 wave number, showed that nano ZnO
is bonded to the surface of nano-sodium alginate by forming a bond between Zn and O in nano sodium alginate. It
showed that nano sodium alginate has been successfully modified with nano ZnO.

Analysis of Surface Morphology by SEM

The surface morphology by SEM of nano sodium alginate and nano sodium alginate-ZnO nanocomposite can be
seen in Fig. 3. Figure 3a shows that the surface morphology of nano-sodium alginate have short fibrous which are
scattered evenly, indicating that nano sodium alginate is formed. Figure 3b shows that the surface morphology of
nano alginate-ZnO nanocomposite is seen on fibrous nanocomposite surfaces from nano sodium alginate and
appears in square form of nano ZnO on the surface of the nanocomposite, indicating that ZnO nano has been
successfully modified on the surface of nano sodium alginate.

Analysis of Surface Morphology by TEM

The surface morphology by TEM of nano sodium alginate, nano ZnO, and sodium alginate-ZnO nanocomposite
can be seen in Fig. 4.

(a) (b)
FIGURE 3. SEM images nano sodium (a) alginate, and (b) nano alginate-ZnO nanocomposite

(a) (b) (c)

FIGURE 4. TEM images of (a) nano sodium alginate, (b) nano ZnO, and (c) sodium alginate-ZnO nanocomposite

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 FIGURE 5. Percent degradation with zinc nitrate concentration
0.025 M (red), 0.05 M (blue) and 0.075 M (green)

FIGURE 6. Kinetics of methylene blue degradation with zinc

nitrate 0.025 M (red), 0.05 M (blue) and 0.075 M (green)

Figure 4a shows that the nano sodium alginate have short fibrous with particle size of 146 nm x 61 nm. Figure
4b shows that the nano ZnO have a square structure of 56.6 nm x 33.3 nm. Nano ZnO has been successfully
impregnated on nano sodium alginate which can bee seen in Fig. 4c. It shows that nano ZnO is bonded to the surface
of nano-sodium alginate. The particle size of sodium alginate-ZnO nanocomposite obtained is 228.0 nm x 134.2 nm.
The results of TEM morphology support the success of FTIR and SEM as previous characterization.

Degradation of Methylene Blue

The nanocomposites that have been made were applied for the degradation of the methylene blue dye stuff,
which is a dye with a residue that is toxic and even carcinogenic. The dye pollution causes the dissolved oxygen
reduction required by aquatic life and pose a serious danger to organisms [3, 5, 10]. In this study, variations of
nitrate zinc impregnation on nano sodium alginate was conducted to observe the degradation ability against the
methylene blue compound. The percent degradation of methylene blue can be seen in Fig. 5. Figure 5 shows that
nanocomposites of zinc nitrate concentration 0.025 M (red) obtained the optimum percent of degradation of blue
methylene at 36.74 %. Figure 5b shows that nanocomposites of zinc nitrate concentration 0.05 M (blue) obtained
optimum percent of degradation of methylene blue at 43.45%. Figure 5c shows that nanocomposites of zinc nitrate
concentration of 0.075 (green) obtained percent of blue methylene degradation at 51.68 %. The same equilibrium
time at 60 minutes was observed.

Kinetics of Methylene Blue Degradation

The determination of blue methylene degradation kinetics used the first order kinetic equation as can be seen in
Fig. 6. Figure 6 shows that plot ln (C0/C) to the time (min) obtained a straight line, so that the methylene blue
degradation reaction fits to the first order kinetics. From the slope of the line in Fig. 6, it can be obtained the reaction

020107-5
rate constants. The values of reaction rate constant obtained for nanocomposites with zinc nitrate concentrations of
0.025 M (red), 0.05 M (blue), and 0.075 M (green) are 4.3x10-3/min, 7.1x10-3/min and 9.5 x10-3/ min, respectively.
It means by increasing the concentration of zinc nitrate,the rate of blue methylene degradation will increase.

CONCLUSIONS
This research has successfully synthesized nano sodium alginate with particle size 140 nm and crystallinity index
38.78 % using XRD characterization, it is a semi-crystalline structure. and particle size of 146 nm x 61 nm using
TEM characterization. The particle size of nano ZnO 38 nm and crystallinity index 91.42 %, with XRD and TEM
characterization the obtained the particle size was 56.6 nm x 33.3 nm. The nanocomposite synthesis of nano sodium
alginate with nano ZnO impregnation with particle size of 130 nm, crystallinity index 38.78 % using XRD, it is
semi-crystalline structure, and TEM characterization obtained the particle size of 228.0 nm x 134.2 nm. The
successful characterization was also supported by FTIR and SEM. The largest percentage of blue methylene
degradation was produced by nanocomposites with 0.075M zinc nitrate which was 51.68 %. The highest
degradation percentage of nano sodium alginate-ZnO nanocomposite has the first order rate constant of 9.5 x10-3
/min.

ACKNOWLEDGMENTS

This research was supported by Universitas Indonesia PITTA Grant for fiscal year 2017 with contract No:
657/UN2.R3.1/HKP.05.00/2017.

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