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