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15th Indonesian Scholars International Convention

London, 3 - 4 October 2015

ENVIROMENTALLY INSTRUMENT OF PRESERVATIVE FISH WITH ENERGY SAVING


BASED ON PHOTOCATALYTIC AS SOLUTION FOR PROVISION OF FRESH FISH IN
INDONESIA
Annizah Rahmatya Gerhana
Department of Chemical Engineering
Diponegoro University
Semarang, Jl. Prof. Soedarto SH Tembalang
INDONESIA
anisa.gerhana@che.undip.ac.id

Alfin Darari
Department of Physichs Science
Diponegoro University
Semarang, Jl. Prof. Soedarto SH Tembalang
INDONESIA
alfindarari@st.fisika.undip.ac.id

Yochi OktaAndrawina
Department of Oceanography
Diponegoro University
Semarang, Jl. Prof. Soedarto SH Tembalang
INDONESIA
yochiokta@gmail.com

ABSTRACT
The case of environmental pollutioncaused many deaths.This dangerous pollution caused by heavy
metal due to industrial waste such as Hg , the Cd ,Zn nature are toxic and which are in the tissues of
the body of marine organisms as of fish in a high concentration , then it used as food and will be
dangerous to human health. The purpose of this innovation is to create an instrument -friendly
cooling system of thermodynamics and Photocatalytic nanoparticel CO doped ZnO.This device called
a potfrigator because shaped like a pot. the variety of data that the instrument can be used as a
material consideration for fishermen as fish preservation instrument as a solution providing fresh fish
with sea products in Indonesia was more safe and fresh.
Keywords: potfrigator, photocatalytic, nanoparticel
1. INTRODUCTION
Fish is foodstuffs which is quite popular by indonesian society . Very good fish consumed because
meet the needs of nutrition and compound containing important as essential amino acid , a saturated
fatty acid , omega 3 ( vikosa , pentanoat ) and dha ( dokosa heksa enoat ) ( lloyd , 1992 ) . But in its
use of fishes having weakness namely its easy foul after arrested ( nurhadi dkk , 2011 ) and having
heavy metal content dangerous as pb , hg , the cd , cu , cr and zn high enough ( sutarto , 2007).
Preserving fish for this accomplished by some method of which is freezing with freezer or
refrigerators , fogging , salting and the addition of a preservative ( nurhadi dkk , 2011 ) . Each of the
the process of preserving have weaknesses as in the process of freezing necessary high energy and
gives rise to a by-product in the freon as dangerous for the environment . To the process fogging
produced the emission of dangerous gas co ( carbon monoxide ) and taste and texture of fish to
change . To the process of marinating evidence for changes taste , and the use of a preservative in fish
will cause a danger to the consumer ( winarno , in 2004 . Weakness various systems has to be
preserving can be overcome with a technological innovations right to energy efficiency and
environmentally friendly who keep fish stay fresh , spared from the process of putrefaction
( preserving fish ) as well as reduce dangerous heavy metal in fish without changing the sense of
taste , texture and nutrition from the food .
Nano technology in today's world is growing so rapidly. One example is nano ZnO materials.
Zinc oxide is economically valuable substance fotokatalis (Daneshvar, 2007). Fotokatalis process of
ZnO is nano-sized zinc oxide when exposed to UV rays, it will form a super oxide compounds that

Gerhana1, Darari2,and Andrawina3

can degrade the heavy metal, eliminating harmful microbes and bacteria (Seery et al, 2008). Effect of
fotokatalis can reduce the harmful heavy metals like Cr (VI) to 80% (Slamet, 2003). Jones Seery
(2008) and (2008) report on nanoparticle ZnO has high antibacterial activity and was able to reduce
the heavy metals, so that when the ZnO superimposed other substances such as glass then
nanoparticles ZnO can reduce heavy metals and kill microbes and bacteria in the surrounding
environment when initiated by UV rays. Because the zink oxide is itself a catalyst then the zink oxide
will never run out and will continue to experience such reactions(Seery et al, 2008).
Zink oxide ( zno ) have weaknesses which can only be initiated with uv rays ( zhang , et al ,
2010). The weakness that can be overcome by doing a modification to the materials to work on the
range visible light . One of the solution of this problem is with cobalt lining zno ( co ) ( reddy ,
2013 ) . Coating zno with cobalt ( co will reduce bandgap of zno zno nano size of that material could
work on the wavelength of light visible to nm 550 , as a result the activity of pendekomposisian
microbes and bacteria and the reduction of heavy metal is getting faster and can use light from a lamp
that we use daily ( reddy , co or 2013 to be doped zno as a preservative fish effective and safe to eat
fish preserved.
Of various the fact above then one of innovation that of going into solution towards the system
preservation pollution and handling dangerous heavy metal in fish is to build a device a preservative
and the reducing agent dangerous heavy metal in fish with cooling system dinamic and fotokatalitik
co doped zno.This device named potfrigator, serves preserve and keep freshness fish with prevent cell
respiration with refrigeration system cooling dinamic, antibacterial activity high as well as can reduce
heavy metal dangerous heavy in fish.Potfrigator this energy efficiency because in a system of
pengawetannya needing only to energy from the bulbs of the usual, more of these and also not harm
taste, texture and nutrition because fish will only illuminated visible light.In addition to that was a
preservative and the reducing agent dangerous heavy metal is readily applied and environmentfriendly because they did not produce results aside.
2. RESEARCH METHODS
2.1. Materials
The materials used in this research were Zinc acetate, isopropanol, cobalt nitrate, glass, acetone,
deionized water, monoethanolamine, fruit and vegetable storage containers, automatic water spray.
2.2. Equipments
The equipment used are a set of glassware, thermometer, magnetic stirrer, sprayer and compressors,
UV-Vis
Spectroscopy,
SEM
(Scanning
Electron
Microscopy),
and
AAS(Atomic
adsorbtionSpectroscopy).
2.3. Procedure
2.3.1. Syntesis Co doped ZnO nanoparticles coated on glass
ZnO nanoparticles was synthesized by sol-gel method using Zn(CH3COO)2.2H2O as sources of
Zn and then addition of isopropanol (IPA: (CH3) 2CHOH), monoethanolamine (MEA:
HOCH2CH2NH2) and cobalt nitrate (CoNO3.6H2O). Manufacture of nanoparticles ZnO by
dissolving Zn acetate into a solution of propanol and monoethanolamine at room temperature with
concentration of 0.5 M. Zn acetate by comparison 1:1 molar and then distirer for 30 minutes.. Result
solution formed translucent white. After cobalt nitrate was added by comparison 4% and stirrer for 2
hour. The result is a homogenous solution purple clear. The next process is the coating on the thin
glass used temperature 450oC , then a thin layer was analized using Scanning Electron
Microscopy(SEM),and EDS, next place thin film on storage pot.

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Figure 1: Co doped ZnO Thin Film


2.3.2. Storage system
After creating a thin layer of Co doped ZnO, then followed by the tools assembly
totally.First, prepare the clays pot (Big and Small), silica sand, and lamp. Second, put a small clays
pot into big pot and then add silica sand:water(1:10) in between space big pot and small pot. Then,
place fish in storage system for 18 hours. The next step assay fish quality.

Glass Coated by ZnO Co


nanoparticles
Silica sand

Figure 2: Potfrigator
The testing of heavy metals is conducted by some steps. First, Samples are dried in an oven at
temperature of 100oC for 24 Hours and cooled in desiccator, second, weighted as much as 2 grams
then put them into closed container. Thirds, add 1,5ml of concentrated HCl 4 and 3,5mL of
concentrated HNO3 then closed and left for 24 hours. Fourth, the obtained solution was heated over a
water bath at temperature of 60-70 oC for about 2-3 hours (Until become a clear solution).
Fifth, if the samples are not dissolved at all, add concentrated HClO 4 and HNO3 and stirred slowly,
then add 9mL of aquadest. Samples are ready to be measured by AAS (Atomic Absorption
Spectrophotometer).
3. RESULT
3.1. Energy Slits Analysis from ZnO Material
The purpose of this analysis is to find a slips energy from the synthesis of compounds formed
.From the slits energy, it can be analysed whether this compound can work on visible light ( light of a
lamp ) or not .

0.8

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0.6

ABS

0.4

0.2

0.0

400

500

600

700

800

nm
. Testing ABS results of DR UV-VIS spectrophotometry

Figure 3: Chart of Testing Result of Spektrofotometri UV-VIS


From the charts it can be seen that crest formed on the range visible light at 546nm.If it converted
with an equation max planck
Eq:
It can be obtainednanoparticleZnOdoppedCo amounting to 2.25ev.The results of testing above
shows that ZnOdopped Cothat covered can work on visible light efficiency of the utilization of visible
light.
3.2. Crystal Morfology Analysis
The analysis purpose of SEM( scanning electron microscopy ) is to analyze the surface and
texture of Co that covered byZnO, analyzes morphology and the size of crystalline that covered in
lamp glass.

Figure 4: Zoom in 1000x SEM in Material

Figure 5: Zoom in 10.000x SEM in Material

Figure 6: Zoom in 20.000x SEM in Material


From the result of SEM (Scanning Electron Microscopy) can be obtained that :
a. At Figure 1 is 1.000x Zoom in can be seen, material covered evenly distributed and have a good
appearance.

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b. At Figure 2 is 10.000x Zoom in can be seen that nanoparticle ZnO doping Co has Round-Sphere
Crystall form, Strongly covered, and evenly distributed,
c. At Figure 3 is 20.000x Zoom in can be seen that material covered with the almost-similar size
,amount in average 63nm.
3.3. Material Composition Covered Analysis
Analysis purpose of EDS (Energy Dispersed Spectroscopy) is to know the composition of
covered compound in lamp glass.

Figure 7: Testing Result of EDS (Energy Dispersed Spectroscopy)


From the testing result of EDS, it can obtained the composition in the lamps layer. Start from
glass lamp material and the compound that covered in glass lamp. ZnO:Co compound has been
covered with the composition of ZnO compound at 94.71% and Co at 4.64%. So that it can be
conclude , the compound of ZnO:Co covered perfectly
3.4. Fish Result Analysis physical

Figure 8: The Result of Fish Preservation using Instrument

Gerhana1, Darari2,and Andrawina3

In figure 8 shows that the fish is cut into 4 pieces. The benefits of fish cutting into 4 pieces is
to optimize the reduction of heavy metals in fish. With the opening of the inside of the fishs body, the
photocatalyst effect of Co doped ZnO can reduce heavy metals inside the fishs body. Thus, the Co
doped ZnOphotocatalyst works optimally. Because of the greater the large of fish surface affected by
a Co doped ZnOphotocatalyst, the greater the heavy metals are reduced
With the opening of the inside of the fish's body, it will also maximize the amount of salt water
absorbed by the fish. After the fish is processed using this tool for 12 hours, the result is the texture of
the fish is not damaged, the stench of the fish is gone, salt water is absorbed evenly across the whole
part of the fishs body. It can be concluded from the physical parameters, the process of the fish
salting occurs perfectly.
After 18 hours, the preservation fish using instrument has a smell that not nettled. Beside that, the
fish has a chewy texture. While from fish the parameters of mucus preserved with the instrument have
a little bit of mucus so that it can be inferred from the parameters of physical fish is still in the
condition of worthy to be eaten
3.5. Fish Result Analysis and Heavy Metal in Fish
The purpose of the AAS analysis is to determine the levels of heavy metals before and after the
photocatalyst process.
Table 1:Result of Heavy Metals In Fish

No

Sample
Before

Pb
(ppm)
0.5

Hg
(ppm)
2.1

Cd
(ppm)
0.3

1
2

After

0.11

1.3

0.05

Results of analysis AAS (Atomic Absorbtion Spectrophotometer) show a reduction of heavy


metals on Pb with a concentration of 0.5 ppm become 0.11 ppm, Cr with a concentrations of 2.1 ppm
become 1.3 ppm and Cd with a concentrations of 0.3 ppm become 0.05 ppm after the fish is placed
on the salting system. So it can be concluded that these tools can reduce the levels of heavy metals in
fish that is processed into salted fish.
4. DISCUSSION
This instrument is name Potfrigator was an instrument with a preservative fish dynamic cooling
system , had an ability to keep the temperature of system reached 15 oC so that could keep the fish
freshness .This potfrigator were composed of a large pot filled with the smaller pots.The space
between two of the clay pots filled with sand , created a layer of insulation that surrounded the inside
of pot. Then made the sand kept wet by poured the water periodically , this instrument was based on
simple physics principle of water contained in the sand would evaporate toward the outer surface of
large pots where the dry air circulates then closed the cap using a thin glass that had been coated by
CO-Doped ZnO and installed the visible light in the upper part. The decrease of temperature had
going to happen consistently make a cold fish and fresh and the use of photocatalyst CO doped ZnO
that reduced heavy metal and deprived of bacteria.
ZnOPhotocatalyst Reaction:
ZnO + hv hVB+ + eCB-

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B+ + H2O
OH
eCB- + O2 O2
hV

(1)

From that photocatalytic reaction when exposed to light, the thin layer will form negative
electrons that are flowing from the valence band to the conduction band. This electron will be released
into the air and forms a superoxide formed a compound of superoxide that released O 2 and radical
OHwhich can oxidizebacteria, and reduce various heavy metals, thie result test heavy metals was
comply with a standart SNI 7387:2009 UNI EUROPE for value of Pb minimum is 0.3ppm, minimum
Cr is 2 ppm, minimum Cd is 0.1 ppm.so that the instrument of preservative fish with photocatalytic
was a fresh fish with a good texture and not contained heavy metal.

Figure 9: Photocatalytic reaction with ZnO


This device was very useful for the society of indonesia especially the fishs traders, The
restaurant that presented various food of seafood, and the Delivery of fresh fish im regional traffic or
cross country.Withpotfrigator , the fish waxs fresh, not decayed, springy texture and safed from the
dangers of heavy metal pollution, so that potfrigator could be the solution of the fresh fishs
provision in Indonesian. Potfrigator could be developed further to preserve aside from fish , such as
fruit, meat, as well as others material organic that easily foul.
5. CONCLUSIONS
1. Potfrigator is a preservative fish with a dynamic cooling system capable of maintaining the
temperature of the system reached 150C and fotokatalitik Co doped ZnO nanoparticles are able to
preserve the fish by way of killing bacteria and microorganisms cause cancer and reduction
of
heavy metal contaminated on the fish so that the product is fresh fish, great texture, and free
from heavy metals
2. Co doped ZnOnano-sized, can work in 542nm wavelength, visible light,
3. perfect coated on the glass with average particles 63nm .
4. The results of photocatalitic showed a reduced heavy metal that had been with 0.5 ppmPb;
2,1ppm Cr;0.3ppm Hg concentration illuminated with visible light became 0.11 ppm;
1,3ppm;0.05ppm was comply standart UNI EUROPE SNI 7387:2009.
5. With this instrumentPotfrigator fish stay fresh, no foul, chewy texture and safe from the dangers of
the pollution of heavy metals, so that potfrigator be a solution providing fresh fish
in
Indonesia was. Potfrigrator can be developed further to preserve other than fish, meat, fruits and
other organic materials that are easily rotten.
ACKNOWLEDGMENTS
The authors would like to thank Dr. Agus Subagjo, M.Si and Nano World Indonesia for
supporting this research.
REFERENCES

Gerhana1, Darari2,and Andrawina3

Daneshvar. 2007. Preparation and Investigation of Photocatalytic Properties of ZnO Nanocrystals:


Effect of Operational Parameters and Kinetic. World Academy of Science. Engineering and
Technology. pp. 29.
Jones, Nicole, Binata Ray, Koodali T. Ranjit, Adhar C. Manna. 2008. Antibacterial activity of ZnO
nanoparticle suspensions on a broad spectrum of microorganisms. FEMS Microbiology Letters.
Volume 279, Issue 1, pages 7176, February 2008
Karunakaran, C., V. Rajeswari, P. Gomathisankar. 2010. Antibacterial and photocatalytic activities of
sonochemically prepared ZnO and AgZnO. Journal of Alloys and Compounds. Volume 508, Issue
2, 22 October 2010, Pages 587591
Reddy, Sankara, Venkatramana Reddy, Koteeswara Reddy and Pramoda Kumari. 2013. Synthesis,
Structural, Optical Properties and Antibacterial activity of co-doped (Ag, Co) ZnO Nanoparticles.
Research Journal of Material Sciences. Vol. 1(1), 11-20, February (2013)
Seery, Michael K., Reenamole Gorgekutty, and Suresh C. Pillai. 2008. A Highly Efficient Ag-ZnO
Photocatalyst: Synthesis, Properties, and Mechanism. Dublin : School of Chemical and
Pharmaceutical Sciences, Dublin Institute of Technology.