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SHORT COURSE ON PHOTOCATALYST CHEMISTRY

PRINCE OF SONGKLA UNIVERISTY

PHOTOCATALYTIC DEGRADATION of RHODAMINE B DYE


by ZnO NANOPARTICLES

Created by:

Budi Hartono 14612009 2014

Eka Akbar Kurniastuti 14612022 2014

Rivaldo Herianto 14612158 2014

Sugesti Nur Amaliah 15612184 2015

Rico Nurillahi 15612201 2015

Rizky Putra 15612210 2015

UNIVERSITAS ISLAM INDONESIA

YOGYAKARTA

2017
1. Introduction
Nowadays, semiconductor photocatalysis attracts increased interest since it has a great
potential to contribute to such environmental problems. The application of semiconductors
such as ZnO and TiO2 in the area of photocatalysis has grownconsiderably, primarily because
of their physical and chemical stability, high oxidative capacity, low cost and ease of
availability. The usage of ZnO, TiO2 and SnO2 has been widely applied in the removal of
organic contaminants Moreover, some studies have confirmed that ZnO exhibits a better
efficiency than TiO2 in photocatalytic degradation of some dyes, even in aqueous solution
(Behnajady et al., 2006; Daneshvar et al., 2004; Daneshvar et al.,2007; Lizama et al.,
2002).As a well-known photocatalyst, ZnO has received much attention in the degradation
and complete mineralisation of environmental pollutants. Since ZnO has almost the same
band-gap energy (3.2 eV) as TiO 2, its photocatalytic capability is anticipated to be similar to
that of TiO2. Moreover, ZnO is relatively cheaper compared to TiO 2 whereby the 2 usage of
TiO2 and platinum catalyst are uneconomic for large scale water treatment operations
(Daneshvar et al., 2004). In addition, ZnO can be a suitable alternative photocatalyst other
than TiO2 since its photodegradation mechanism has been proven to be similar to that of TiO 2.
In some cases, ZnO shows higher photocatalytic tendency towards photodegradation and
mineralisation of environmental organic or inorganic pollutants.
ZnO semiconductors are known to be an excellent material for the fabrication of
various efficient electronic, optoelectronic devices, photovoltaic devices and photocatalysts
Moreover, ZnO is also known as a promising material for spintronics because of its
ferromagnetic properties .Recently, ZnO nanomaterials applications in photocatalysis have
received a great deal of interest because of its impressive catalytic activity and quantum
efficiency compared to widely used TiO2 nanomaterials.
Rodamine B is a chemical compound and a dye. It is often used as a tracer dye within
water to determine the rate and direction of flow and transport. Rhodamine dyes fluoresce
and can thus be detected easily and inexpensively with instruments called fluorometers.
Rhodamine dyes are used extensively in biotechnology applications such as fluorescence
microscopy, flow cytometry, fluorescence correlation spectroscopy. Rhodamine B is used in
biology as a staining fluorescent dye, sometimes in combination with auramine O, as the
auramine-rhodamine stain to demonstrate acid-fast organisms, notably Mycobacterium.
Rhodamine B is tunable around 610 nm when used as a laser dye. Its luminescence quantum
yield is 0.65 in basic ethanol 0.49 in ethanol 1.0 and 0.68 in 94% ethanol. The fluorescence
yield is temperature dependent (Karstens, T.; Kobs, K.1980)
A dye is a coloured substance that has specific affinity to a given substrate. Dyes are
applied to various substrates (textiles, leather, paper, hair etc.) from liquid in which they are
completely, or at least partially soluble (Zollinger, 2003).Dyes are classified according to
their chemical structure or according to the method of application (Christie, 2001). According
to Christie, dyes contain two groups which are responsible for their colour. They consist of a
group of atoms responsible for the dye colour, called chromophores and the other group
isauxochromes, which can be defined as an electron withdrawing or donating substituents
that essential for the colour enhancement of the chromophores.

2. Materials and methods

2.1 Raw materials and tools


Raw materials used in this study are aquadest, a solution of Rhodamine B pH 7, and
ZnO. The tools used in this experiment are UV-Vis Spectrophotometer single beam,
Analytical Balance Ohaus, Magnetic Stirer, glass beaker (Pyrex) glass measuring (Pyrex),
Pipette drops, centrifugation, Shelving, test tubes and test tube.

2.2 Preparation of photocatalyst ZnO


Before starting the photocatalyst, firstly we have to prepare a solution of Rhodamine
B pH 7 and weigh as much as 0:15 gram ZnO. After that, ZnO put in a 250 mL glass beaker
and added a solution of Rhodamine B, 150 mL and a magnetic strirer. Then, put the solution
in a box with a stirrer without light for about 15 minutes. After that, take the solution for
about 3 mL and put into centrifuges for a minute. Then the solution is put back into the box
with an extra light for 5 minutes. While waiting for 5 minutes, a solution which has been
centrifuged to form layers of sediment. The solution is separated from sediments and put into
another test tube. furthermore, issued distirer solution with light for 5 minutes, then take and
put 3 mL of the solution into centrifuge for 1 menit. Then, the solution is put back into the
box with an extra light for 5 minutes. While waiting for 5 minutes, a solution which has been
centrifuged to form layers of sediment. The solution is separated from sediments and put into
another test tube. carried on until a colorless solution. When we have some samples, the
samples are test absorbance with uv-vis spectrophotometer with a wavelength of 900nm-
400nm.
3. Results and discussion

3.1 Analysis Uv results


Time irradition with Uv rays, the value of the resulting adsorption getting down
because ZnO adsorb Rhodamine B with the help of Uv rays. Where uv rays serve to enlarge
the bandap value, the maximum adsorption at minute 60.

1.2

1 irr 60 min
irr 50 min
0.8
irr 40 min
0.6 irr 30 min
0.4 irr 20 min
irr 10 min
0.2
ads
0 Co
300 400 500 600 700 800 900
-0.2

3.2 Rhodamine B pH 7 result

Based on experiments conducted at rhodamine B ph 7 the data result have R2 = 0,9911

1 2 3
time pH 7 C/Co pH 7 C/Co pH 7 C/Co
-15 1 0 orde 1 C/C0
0 0,9341126 -0,06816 0 orde 2 ln C/C0
10 0,3674283 -1,00123 -0,93307 orde 3 ln C/C0
20 0,1691463 -1,77699 -1,70883
30 0,0781084 -2,54966 -2,4815
40 0,0419766 -3,17064 -3,10248
50 0,0218739 -3,82246 -3,7543
60 0,0054906 -5,20472
pH 7 C/Co
0 pH 7 C/Co
f(x)10
= -20
0.08x
-1 0 30 40 50 60 Linear (pH 7
R = 1
C/Co)
-2
-3
-4

3.3 A comparison results of Rhodamine B pH3, pH7 and Ph11

Then the comparison solution with variations Rhodamine B namely Ph3, Ph7 and
ph11 suggests that the solution Rhodamine B ph 3 is more suitable in helping adsorption ith
Uv who have R2 = 0,9997 compared with Ph7 and ph11. It could happen because of
Rhodamine B ph has a H+. While the catalyst is alkaline and has the O- group. So, there as an
interaction that bring results become better. In theory, the surface of ZnO on condition acid
positive charge, its easier to adsorption of colors that have negative charge. This the
condition is getting a lot of the number of colors adsorption on the surface of ZnO. While, at
the base photoderadation less effective.
0
0 f(x)
10= 20
- 0.06x
0.08x
30 40 50 60
-0.5 R = 1
-1
pH 3 C/Co
-1.5 Linear (pH 3 C/Co)
-2 pH 7 C/Co
Linear (pH 7 C/Co)
-2.5
pH 11 C/Co
-3 Linear (pH 11
C/Co)
-3.5

-4

-4.5

4. Conclusions

Based on the research that has been done, its concluded that the optimum conditions
of rhodamine B degradation is at the time if irradition for 60 minutes. Photodegradation with
Uv ray systems in optimum condition most effectively degrades Rhodamine B ph with a
value of R2 = 0,9997.

References

Behnajady, M.A., Modirshahla, N., Hamzavi, R., 2006. Kinetic study on photocatalytic
degradation of C.I. Acid Yellow 23 by ZnO photocatalyst. J. Hazard. Mater. 133,226
232.doi:10.1016/j.jhazmat.2005.10.022.
Daneshvar, N., Rasoulifard, M.H., Khataee, A.R., Rasoulifat, M.H., 2007. Removal of C.I.
Acid Orange7 fromaqueous solution by UV irradiation in the presence of ZnO
nanopowder.J. Hazard. Mater. 43 (12), 95 101.doi:10.1016/j.jhazmat.2006.08.072
.
Daneshvar, N., Salari, D., Khataee, A.R., 2004. Photocatalytic degradation of azo dye acid
red 14 in water on ZnO as an alternative catalyst to TiO2. J. Photochem. Photobiol.
A.162, 317322.doi:10.1016/S1010-6030(03)00378-2.

Lizama, C., Freer, J., Baeza, J., Mansilla, H., 2002. Optimal photodegradation of reactive
blue 9 on TiO2 and ZnO suspension, Catal. Today 76, 235246.doi:10.1016/S0920-
5861(02)00222-5.

Karstens, T.; Kobs, K. (1980). "Rhodamine B and rhodamine 101 as reference substances for
fluorescence quantum yield measurements". The Journal of Physical Chemistry. 84
(14): 18711872. doi:10.1021/j100451a030