SYNTHESIS NANO PHOTOCATALYST ZNO-NATURAL ZEOLIT TO

DEGRADE PROCION RED DYE

Tuty Emilia Agustina, Rianyza Gayatri, Indah Fitriany Purwaningtyas *

* Chemical Engineering Department, Faculty of Engineering, Sriwijaya University

Jl. Raya Palembang-Prabumulih KM32 Indralaya, Ogan Ilir, South Sumatra 30662

Abstract
The development of the textile factory has an impact on the environment because
the dye waste is difficult to be degrade. Procion red is one of the most commonly used on
synthetic dyes such as in the home industry or batik factory. Now a days the handling of
textile waste usually uses the adsorption method, but the results are less effective and as
an alternative solution, photodegradation method is develop using photocatalyst material
and ultraviolet irradiation whose energy corresponds to or greater than the photocatalyst
gap energy. In this method, dye substance will be broken down into simpler and safer
components for the environment. This invention is using ZnO as a photocatalyst material
that combined with adsorbents natural zeolites to increase adsorption ability. In this
invention, materials were varied to degrade procion red, such as nano photocatalyst ZnO-
natural zeolite, ZnO, and natural zeolite, where the procion red concentration were varied
into 50, 100, 150, 200 and 250 ppm. This invention also used three different conditions of
light intensity, by using ultraviolet (UV), sun, and in dark conditions. BET
characterization results showed that the specific surface area of nano photocatalysts ZnO-
natural zeolite is 14,84 m2/ g, pore size is 32,71 nm, and pore volume is 0,12 cm 2/ g.The
highest degradation results were obtained from red procion samples which concentrated
50 ppm and using nano photocatalyst ZnO-natural zeolite by using sunlight during 120
minutes, with the degradation percentage is 96,23%.

Keywords: procion red, photodegradation, nano photocatalyst, ZnO, natural zeolite.

1. INTRODUCTION are harmful to the environment. This

The development of the textile
industry certainly has an impact on the
environment because the dye waste
produced by the textile industry is
difficult to degrade. Waste containing
these dyes usually consists of non-
biodegradable organic compounds that
can cause pollution to the environment,
especially in the aquatic environment.
Procion red is one of the most
commonly used synthetic dyes such as
in the fabric home industry or batik.
However, wastewater produced from
this industry contains synthetic dyes that
synthetic dye procion red in its
application will be difficult to remove
because of the strong covalent bond
between the carbon atoms of the
dyestuff and the O, N or S atoms of the
hydroxy, amino or thiol groups of the
polymer (Hunger, 2003).
At present, various techniques
for tackling textile waste have been
developed, one of which is the
adsorption method, but this method has
turned out to be less effective because of
that textile dyes still accumulates in the
adsorbent which at one time can cause
new problems. As a new alternative
method, a photodegradation method that
uses photocatalyst materials and
ultraviolet light irradiation is developed,
whose energy is same or more than the
photocatalyst gap energy. If the
degradation process of dye waste is
carried out using this method, the
dyestuff will be decomposed into a
simple and safe component for the
environment (Corrent et al., 1999).
ZnO as a photocatalyst also has
low adsorption ability so that ZnO
photocatalysts can be combined with
adsorbents such as zeolite to face this
problem (Wismayanti et al., 2015).
Therefore, this study aims to synthesize
photocatalysts of nano-sized natural
ZnO-zeolites which are expected to be
more effective in degrading procion red
textile dye waste.
2. LITERATURE REVIEW
2.1. Dye
Dye is a compound that is used
in the form of a solution or dispersion in
another material so that it is colored
(Rambe, 2009). Based on the source of
dyes for textiles can be divided into two
types, namely natural dyes and synthesis
dyes. Textile industry waste which is
directly thrown into rivers can cause
pollution in the form of changes in color,
odor and taste in water, obstruction and
loss of aquatic biology activities, soil
and groundwater pollution, and physical
changes in plants, animals, and even
humans due to chemical substances
(Laksono , 2012).
2.2. Zeolite
2.2.1. Natural Zeolite
Natural zeolite is formed due to
the existence of complex chemical and
physical processes from rocks which
undergo various changes in nature.
Geochemists and mineralogists estimate
that zeolite is a product of frozen
volcanoes that becomes volcanic,
sedimentary and metamorphic rocks
which undergo weathering due to the
effects of heat and cold (Lestari, 2010).
As a natural product, natural
zeolite is known to have a very varied
composition, but its main components
are silica and alumina. In addition,
zeolite also contains various minor
elements, including Mg, Fe, Na, K, Ca
(Bogdanov et al, 2009).
2.2.2. Chemical Regeneration
In general, zeolite activation is
divided into physical and chemical
activation. The activation of natural
zeolite is physically carried out by
heating. The heating process of natural
zeolite is carried out at a temperature of
200-400˚C and the heating time in a
vacuum system is 2-3 hours, whereas if
in an open space it is around 5-6 hours
(Suyartono and Husaini, 1992).
Chemical activation is activation
by using acidic or basic chemicals. The
function of acids or bases is to wash
cations that pollute the surface of
zeolites. Chemicals that can be used for
the activation process of natural zeolite
are acid solutions such as H 2SO4, HCl
and HNO3 and alkaline solutions such as
NaOH and also KOH (Humam, 1996).
The purpose of chemical
activation is to clean the pore surface,
dissolve impurities including free silica
and aluminum and rearrange the location
of the atom and dissolve some alkali and
alkaline earth metals so that zeolite-H +
or zeolite-Na + can form. Zeolite can
hold all hydrocarbons, nitrogen, and all
gases that are permanent except
ammonia. Zeolite as an absorbent
because of the cations around the zeolite
cavity, so that zeolite can absorb
different molecules of charge. The size
of the pore depends on the type of ion
contained in the zeolite. K + ions have
the largest ionic radius when compared
to ions such as Na +, Mg2 +, and Ca2 +
(Pandapotan, 2012).
2.2.3. Zeolite Working Mechanism As
an Adsorbent
Under normal condition, the
vacuum in zeolite crystals is filled with
free water molecules around the cation.
When zeolite is heated, then the water
will come out so that the zeolite can
function as a gas absorber or liquid
vapor. Dehydration causes the zeolite
pore to be very open and has an internal
surface area capable of adsorbing a
number of substances other than water
and is able to separate substances
molecules based on their molecular size
and polarity.
Zeolite is able to separate based
on differences in the size, shape and
polarity of the filtered molecule.
Zeolites are able to separate molecules
in gases or substances from a particular
mixture because they have large cavities
with diameters varying in size between
2- 3A (Humam, 1996).
2.3. ZnO (Zync Oxide)
2.3.1.,,,Chemical and Physical
Properties of ZnO
ZnO is a white powder that is
soluble in alkaline or acidic but almost
insoluble in alcohol and water. ZnO is
also available abundantly in nature,
cheap, and the chemical structure is
stable (Widodo, 2013). ZnO can only
break down into its constituent elements,
namely zinc and oxygen vapor at a
temperature of 1975 ° C and this shows
that the nature of ZnO is very stable.
ZnO or zincite minerals usually contain
a number of elements of manganese and
others and change from yellow to red.
Thermo-chromate zinc oxide can change
from white to yellow when heated and in
the air switches to white in the cooling
process (Nugroho, 2004).
ZnO has characteristics that can
be combined with other compounds.
ZnO in the form of crystals can be used
in various purposes such as
semiconductor materials and can also be
used as a catalyst. The characteristics of
ZnO depend on the size and also the
preparation method (Rustan et al, 2015).
The ZnO boiling point is 2360°C, the
flash point is 1436 ° C, and the melting
point is 1975 °C. The solubility of ZnO
in water is 0.16 mg/100 ml at 30°C. The
index is refractive 2.0041 and the
density of ZnO is 5.606 gr/cm3. The
formation enthalpy of the ZnO standard
is -348 kJ/mol (Nugroho, 2004).
2.3.2. Application of Using ZnO
Applications of using ZnO
usually exploit oxide reactivity as a
precursor for other zinc compounds. For
material science applications, zinc oxide
has a high refractive index, high thermal
conductivity, binding properties,
antibacterial and ultraviolet light
protection. Because of these things, ZnO
was added to various materials and
products, including plastics, ceramics,
glass, cement, rubber, lubricants, paints,
ointments, adhesives, pigments, food,
batteries, and many other uses.
ZnO can be used in making
rubber. The use of ZnO in the rubber
industry can reach 50%. Zinc oxide
along with stearic acid is used in
vulcanizing rubber (Dini et al., 2014).
2.3.3. ZnO Crystal Structure
 ZnO has a diamond structure
with a network of covalent bonds. Based
on this structure, the chemical bonds
between zinc and oxygen atoms are
more directed to ionic bonds because of
the strong polarization system between
the two atoms. The Zn-O bond causes
the Zn atom to be very positive and the
O atom becomes very negative. But then
the two atoms form neutral molecules.
ZnO crystals have three general
forms, namely hexagonal wurtzite,
zincblende cube, and rockalt cube. The
ZnO wurtzite crystal structure is the
most stable and most common structure
(Adi et al., 2007). The zincblende form
of ZnO is formed at the time of crystal
growth and reaches stability when
forming a cube structure. Furthermore,
the rocksalt form can only be found at
10 GPa pressure (Eya et al, 2005).
2.4. ZnO Nanoparticles
Basically the orientation of the
nanocrystal that forms a thin film is very
dependent on the type of substrate used,
this is related to the surface energy
formed between the substrate and the
layer that is grown. The use of a
substrate that has a small lattice
mismact, will facilitate the formation of
crystals to become more regular and also
more uniform (Abdullah et al., 2008).
2.4.1. Sol-Gel Method
The sol-gel method is one of the
most successful methods in the
preparation of nano-sized metal oxide
materials. The sol-gel method is known
as one of the simple and easy methods
of nanoparticle synthesis, usually using
precursor starting materials. The sol-gel
method is included in the wet method
because the process involves solution as
a medium. In this sol-gel method, the
solution undergoes a phase change into
sol (colloid which has suspended solids
in the solution) and then becomes a gel
(colloid but has a solid fraction larger
than the sol (Mahmudah, 2017).
2.5. ZnO Photocatalyst
Photocatalysts are materials that
can accelerate the rate of oxidation and
reduction reactions through a
photochemical reaction. This
photocatalyst is semiconductor which
when exposed to sunlight the photon
energy is equal to or greater than the
electron excitation energy will form a
hole in the valence band which will be
hydroxyl radical. This radical can
degrade an organic compound
(Wulandari et al., 2014).
The photocatalyst process using
nanostructured semiconductors is a
technology to oxidize organic
compounds such as dyes. Photocatalyst
oxide semiconductor materials which
are often used in degrading liquid waste
are TiO2 and ZnO compounds. ZnO is
one of the catalysts used for
photodegradation with bandgap energy
values or band gap 3.17 eV.
ZnO as a photocatalyst also has a
low adsorption ability so that ZnO
photocatalysts can be combined with
adsorbents such as activated charcoal
and zeolite to overcome this problem
(Wismayanti et al., 2015).
The efficiency of ZnO
photocatalysts is higher than TiO2
because of the strong absorption of
sunlight and UV. In addition, ZnO is an
efficient photocatalyst material for the
detoxification process of waste water
because it produces H2O2 more efficient
than the other photocatalysts (Hidayanto
et al., 2013).
2.6. Procion Dye
 Procion is one of the reactive wavelength of sunlight is around 310-
dyes. The first reactive dyes were 2300 nm. The spectrum of solar
produced in 1956. Reactive dyes are radiation itself consists of short
difficult to remove because of strong wavelength (ultraviolet light) and long
covalent bonds between carbon atoms of wavy ray (infrared light). This shows
dyes with O, N, or S atoms of hydroxy, that the conditions of irradiation or light
amino or thiol groups from polymers. intensity with light from UV lights and
Reactive dyes have a small molecular direct sunlight also different because the
weight. The advantages of reactive dyes wavelengths are also different
are lighter colors, their absorption (Fraditasari et al., 1996).
spectra are sharp and clear, and have a
2.8. Karakterisasi SEM-EDX dan
simple structure (Hofmann et al, 1995).
BET
2.7. Light Intensity
Masuk sini
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radiation consists of three types, namely
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