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Degradation of dye photocatalysis in aqueous solvent using metal oxide photocatalysis

I. Aim (s)
The aims of this experiment are as the following; to understand the principle of
photocatalysis degradation using a semiconductor material; to compare the effectiveness of
dye degradation of dye photocatalysts using metal oxides; and to understand the awareness of
environmental and alternative waste treatment that is environmentally friendly and
inexpensive.
II. Theoretical background
Metal oxides are of great technological importance in environmental remediation
and electronics because of their capability to generate charge carriers when simulated
with required amount of energy. Metal oxides such as oxides of vanadium, chromium,
titanium, zinc, tin, and cerium having these caracteristics follow similar primary
photocatalytic processes such as light absorption, which induces a charge separation
process with the formation of positive holes that are able to oxidize organic substrates
(Khan, et al., 2015).
The TiO2, a wide band-gap semiconductor oxide, is an exceptional material that
is widely applied in photocatalysis, electrochromic devices, and dye-sensitized solar cells
(Wang, et al., 2006). TiO2 powders have been commonly used as white pigments from
ancient times. They are inexpensive, chemically stable and harmless, and have no
absorption in the visible region. Therefore, they have a white color. However, the
chemical stability of TiO2 holds only in the dark, Instead, it is active under UV light
irradiation, inducing some chemical reactions. Such activity under sunlight was known
from the flaking of paints and the degradation of fabrics incorporating TiO2 (Hashimoto,
K, et al., 2005).
Photocatalysis is a science of employing catalyst that is utilized for speeding up
chemical reactions that requires or engages light. A photocatalyst is defined as a material
that is capable of absorbing light, producing electron-hole pairs that enable chemical
transformations of the reaction partic ipants and regenerate its chemical composition after
each cycle of such interactions. There are two types of photocatalytic reactions;
homogeneous photocatalysis and heterogeneous photocatalysis. The significant features
of the photocatalytic systems are the desired band gap, suitable morphology, high surgace
area, stability and reusability (Khan, et al., 2015). The photocatalytic properties of certain
materials have been used to convert solar energy into chemical energy to oxidize or
reduce materials to obtain useful materials including hydrogen and hydrocarbons, and to
remove pollutants and bacteria on wall surfaces in air and water (Hakata, et al.,2012).
TiO2 photocatalysis is widely used in a variety of applications and products in
the environmental and energy fields, including self-cleaning surfaces, air and water
purification systems, sterilization, hydrogen evolution, and photochemical conversion.
The photocatalytic properties of TiO2 are derived from the formation of photogenerated
charge carriers (hole and electro) which occurs upon the absorption of ultraviolet (UV)
light corresponding to the band gap. The photogenerated holes in the valence band
diffuse to the TiO2 surgace and react with adsorbed water molecules, forming hydroxyl
radicals ([dot]OH)(Nakata, et al., 2012).
Methylene blue or now called, methylthionium chloride is use
III. Experimental method
a. Materials
The materials used in this experiment were as the following; TiO2 or ZnO, source of UV,
and pigment.
b. Equipment
The equipment used in this experiment were as the following; UV-VIS
Spectrophotometer,
c. Procedure
IV. Result and discussion
a. Experimental Result
b. Discussion
Each dye solution will be degraded using a TiO2 photocatalyst. The process of
photocatalysis is done by using a room that irradiated UV lamps within a certain period
of time. Ultraviolet radiation which is often abbreviated as UV is electromagnetic
radiation to the shorter wavelength of the area with visible light.

Absorption of UV rays by TiO2 will form electrons (e) in the conduction band
and hole (h +) in the valence band. The electrons react with oxygen in the sample to form
anions (O2-), while the holes react with hydroxyl ions to form hydroxyl radicals (OH).
This OH (OH) radical strikes the dye molecule, creating intermediate molecules so that it
can be degraded into a CO2 and H2O molecule for some time. The degradation rate is
related to the formation of OH radicals (OH) which is the most important species in the
degradation process. The reaction of OH radical formation (OH) and dye degradation is
expressed in the following equation.

The degradation value of methylene blue is increasing at dark conditions, UV


rays to sunlight with a variety of photocatalysts. In dark conditions, the degradation
values are low because there is no light source so that the photon energy to produce the
radical • OH is weak, therefore the methylene blue is only adsorbed on the catalyst
surface and its degradation becomes not optimal. In sunlight conditions obtained sunlight
results degradation is higher than UV light. This is because the sun has the intensity and
wavelength between (310-2300 nm) is greater than the wavelength of light UV (200-380
nm). In addition, sunlight is a combination of ± 45% visible light and ± 5% of UV light
so that sunlight has a relatively large energy and can provide a lot of photon energy on
the photocatalyst. When the photocatalyst is exposed to light with a greater energy than
the band gap it will produce strong oxidizing holes to form radicals • OH and such
radicals degrade methylene blue into simpler compounds.
The radiation time in the photodegradation process illustrates the duration of
interaction (contact) between the photocatalyst and the light (hv) in generating the OH
radical and the contact between the radicals OH with the methylene blue substrate in the
degradation process. Methylene blue degradation increases with increasing duration of
sunlight and UV light. At irradiation for 5-50 minutes there is a considerable increase in
degradation, whereas at 50-120 minutes the resulting degradation tends to be constant.
This is because the longer the coloration of the solution becomes faded, so to reach the
photocatalyst becomes easier. Increased degradation in sunlight reaches up to 99.18%
while in UV light only 79.29% for 120 minutes, it shows that photon energy from
sunlight can cause photocatalysts to produce radical radical • OH more than photon
energy. The longer the irradiation time, the adsorption and desorption process will run
continuously, until it reaches the optimum condition where adsorption and desorption are
equilibrium so that the degradation tends to be stable close to 100%.

The amount of dyestuff concentration that has undergone photocatalysis


degradation can be known using UV-Vis spectrophotometry method. This method can be
used because of the nature of the two dyes containing chromophores, so that it can be
analyzed using this method. The UV-Vis spectrophotometric method used is using a
calibration curve. It is therefore necessary to prepare a standard solution for each type of
dye solution. Standard solutions are made in concentration variations (1, 2, 3, 4, and 5
ppm).
Determination of maximum wavelength was done using standard solution of
methyl orange 15 ppm with wavelength 440-460 nm with interval 5 nm. Based on the
wavelength curve vs. absorbance above it is known that at the highest absorbance value is
indicated at 445 nm wavelength. This means that the optimum wavelength for the 445 nm
orange methyl analysis. As is known that the orange methyl orange color is an observed
color, but the absorbed color is the complementary color. The orange color has a
complementary blue color with a wavelength of 440 - 470 nm . Thus, the result of 445
nm as the optimum wavelength is correct because it is in the blue wavelength range
which is the complementary color of the analyte. At that wavelength it was then used for
further orange methyl analysis. Similarly, the wavelength used in alizarin red solution
that uses a wavelength of 530 nm. The color of red alizarin is purplish, so its
complementary color is yellowish green with wavelength 520-550 nm. Thus, using the
530 nm wavelength is correct. Based on the making of the methyl orange calibration
curve obtained the curve of the relationship between concentration (C) vs. absorbance
(A). Based on the curve, it is seen that the greater the concentration of the solution the
greater the absorbance.

V. Conclusion
VI. References
Khan, M. M., Adil, S. F., Al-Mayouf, A. 2015. Metal oxides as photocatalysts. Journal of
Saudi Chemical Society, 19 (5), 462-464, pp.
Hashimoto, K., Irie, H., Fujishima, A. 2005. TiO2 Photocatalysis: A Historical Overview and
Future Prospects. Japanese Journal of Applied Physics, 44(12), 8269-8285 [Part 1], pp.
Nakata, K., Fujishima, A. 2012. TiO2 photocatalysis: Design and applications. Journal of
Photochemistry and Photobiology C: Photochemistry Reviews, 13, 169-189, pp.
Wang, N,. Lin, H., Li, J., Zhang, L., Lin, C., Li, X. 2006. Crystalline Transition from
H2Ti3O7 Nanotubes to Anatase Nanocrystallines Under Low-Temperature Hydrothermal
Conditions, J. Am. Ceram. Soc., 89 (11), 3564-3566, pp.