International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
Effect of PH Variation on Particle Size and Purity
of Nano Zinc Oxide Synthesized by Sol-Gel
Method
Radyum Ikono, Putri Riskia Akwalia, Siswanto, Wahyu Bambang W, Agus Sukarto, Nurul Taufiqu Rochman*
Abstract -- In recent years, there have been many methods
developed to synthesize Zinc Oxide (ZnO) nanoparticles.
Nevertheless, a simple yet cheap method to prepare single
crystal with high purity nano ZnO was still yet to be
established. In this research, nano Zinc oxide (ZnO) was
prepared by sol-gel method. The pH variation effect to the
resulting ZnO product was also observed.
(CH3COOH)2Zn.2H2O powder and NaOH solution were used
as precursors. NaOH solution was added to
(CH3COOH)2Zn.2H2O solution by titration until colloids with
different pH were obtained, then precipitates of nano ZnO
were formed. From the precipitation profile, it can be observed
that increasing pH led to shortened precipitation time, which
also means increasing particle size. It was also further
confirmed that particle size at pH 7 and pH 12 was 1.3 nm an d
73.8 nm, respectively. XRD profile showed that increasing pH
led to increasing purity of nano ZnO: 42.9%, 62.2%, 64.7%,
and 100% at pH 7, pH 8, pH 10, an d pH 12, respectively. To
conclude, nano ZnO synthesized by S ol-Gel method was highly
affected by pH of the working solution. Increasing pH led to
increasing particle size, however led to higher purity of nano
ZnO produced.
Index Term-- Nano ZnO; sol-gel; pH variation
I. INTRODUCTION
Zinc Oxide (Zn O) ceramics have gained much attention due
to their d istinct properties and characteristics. ZnO ceramics
in various forms are used extensively in electronic
applications, such as LED, sensor, or solar cells [1]. In
recent years, it has also been found that ZnO can be used in
other potential applications like photocatalysis and anti-
bacterial substance, thus ma king them excit ing co mmodities
for industries [2].
Radyum Ikono is with Nanotechnology Research and Business Center,
T angerang Selatan, Indonesia, and with Department of Metallurgy, School
of Engineering and T echnology Sumbawa (ST T S), Sumbawa, Indonesia
(email: rikono@nano.or.id)
Putri Riskia Amalia is with Department of Physics, Airlangga
University, Surabaya, Indonesia
Siwanto is with Department of Physics, Airlangga University,
Surabaya, Indonesia (siswanto_fst@yahoo.co.id)
Wahyu Bambang is with Research Center for Physics, Indonesian
Institute of Science (LIPI), T angerang Selatan, Indonesia (email:
wahyubw@gmail.com)
Agus Sukarto is with Research Center for Physics, Indonesian Institute
of Science (LIPI), T angerang Selatan, Indonesia (email:
agussukarto@yahoo.com)
*Nurul T aufiqu Rochman is with Research Center for Metallurgy,
Indonesian Institute of Science (LIPI), T angerang Selatan, Indonesia
(Corresponding Author. Ph: +62 21 7587 0479 fax: +62 21 7560553 email:
ufiq2000@yahoo.com)
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At the same t ime, nanotechnology becomes much more
popular nowadays. Scientists believe that by engineering
material size into nanoscale, there will be an enhancement
on properties of the material. In many literatures, it can also
be learned that nano ZnO offers better performance
compared to that of in bulk size [3].
There have been many methods to synthesize nano ZnO.
Some of the widely used methods are, for instance,
Chemical vapor deposition (CVD), d ip coating, o r
mechanical alloy ing [4,5,6]. Those methods have their own
advantages and disadvantages. For example, CVD and dip
coating, they can produce nano ZnO with high purity,
however high growth temperature is needed in their system.
Also, the preparation scheme is quite co mplex and can be
very expensive [7]. Mechanical alloying is another
interesting method where it can synthesize nano Zn O in
relatively simple manner [8]. Nevertheless, to date, there has
been no reports on mechanical alloying method that can
yield pure nano ZnO. Another possible method is sol-gel
method. The good thing about this method is that, it is
relatively simple and cheap in process, and it does not need
to be treated in high growth temperature [9]. Ho wever, to
date, there is still a little knowledge on the effect of pH
variation on sol-gel wo rking solution, also whether high
purity of nano ZnO can be achieved by this method.
In this research, nano ZnO was synthesized by sol-gel
method, in an attempt to find the optimu m condition to
produce single crystal ZnO with relatively s mall size. The
pH condition would be varied for this optimization process.
II. EXPERIM ENTAL PROCEDURE
4.39 gram (CH3 COOH)2 Zn.2H2 0 (Merck) powder was
dissolved in 100 mL methanol. It was then sonicated at 750
Watt for 30 minutes to obtain homogenous solution of 0.2
M. Separately, 1.0 M NaOH was dissolved in 500 mL
distilled water. After that, optimizat ion for t itration was
conducted to find the optimu m condition of the time,
temperature, and stirring speed.
The optimized condition was used for titration of NaOH
solution dropped to (CH3 COOH)2 Zn.2H2 0 solution.
Titration was continued until 5 p H variations were obtained:
pH 7, pH 8, p H 9, pH 10, pH 11, and pH 12. After the colo r
of the solution become milky wh ite, the solution was
sonicated for another 30 minutes. It was then idled fo r
several days to observe the precipitation of nano ZnO in the
solution.
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 International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
After the precipitation could be clearly seen through,
solution was centrifuged at 3000 rp m for 30 minutes. The
supernatant was then removed, and the precip itation which
contains nano ZnO was obtained. Nano ZnO precipitates
was first treated in 800 C oven to remove the remaining
water. Finally, nano ZnO was grinded with mortar to be
shaped into powder.
To find out the particle size, Particle Size Analy zer ( DelsaTM
Nano C Beckman Coulter) was used. Briefly, nano ZnO was
dissolved in distilled water in 1:10 concentration. It was
then stirred until ZnO suspension in water was formed. 1
mL of the suspension was then tested to obtain the average
particle size.
The solution was then centrifuged, and the supernatant
was removed to obtain the nano ZnO. Finally, nano Zn O
powder was achieved after heat treatment at 800 C. The X-
ray diffract ion (XRD) pattern of the final Zn O nanoparticles
was obtained with Cu Kα radiation (Shimad zu, Japan). The
peak positions and relative intensities were characterized by
comparison with the Joint Co mmittee for Po wder
Diffraction Standards (JCPDS). Williamson-Hall plot was
used to analyze the crystal size at different pH.
The preparation scheme was shown in Fig. 1.
III. RESULTS AND DISCUSSIONS
The time for nano ZnO to precipitate fro m solution was
observed. It can be seen from Fig. 2 that time to precipitate
decreased over increasing pH. The range fro m p H 7
condition which needed 72 hours to pH 12 condition which
needed only 120 minutes to precipitate showed that pH
plays a very significant role in sol-gel experiment.
One of the pro minent charactristics of nanoparticles are
that they tend to float in solution and they need much longer
time to be precipitated inasmuch as the gravitation force
exerting them is very small, or even almost negligib le [10].
It was hypothesized that by varying the pH condition, the
size of the particle obtained would also be varied, and this
would affect the p recipitat ion profile of the Zn O
nanoparticles.
To test above hypotheses, size of the particles at lower
and upper pH (pH 7 and pH 12) were measured by PSA
mach ine. Results showed that the size of nanoparticles at pH
7 and pH 12 were 1,3 n m and 73,8 n m, respectively. It is in
agreement with hypotheses above that as pH of the solution
increased, the size of the nanoparticle increased as well.
Finally, XRD graph in Fig. 4 gave us information about
the elements of the particles fo rmed at p H 7, 8, 10 and 12.
Fro m the graph, it can be inferred that the purity of nano
ZnO produced increased as pH increased. On ly at p H 12 the
100% ZnO without any contamintants or mixture with other
compounds were obtained. The quantitative data of Zn O
purity at pH 7, 8, 10, and 12 was as follows: 42.9%, 62.2%,
64.7%, and 100%, respectively.
This phenomenon was well explained by Sunandan, et al.
that the growth of Zn O is normally enhanced in basic
med iu m. The final gro wth of ZnO depends upon the
competition between gro wth and etching [10]. The size
became significantly bigger at basic condition maybe
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because high purity ZnO nanoparticles tend to bind each
other and agglomaerate. In lower p H, although the particle
was much smaller in size, the ZnO obtained was still in
mixtu re with other co mpounds, such as CH3 COONa and
Zn(OH)2 , therefore they tend to be separated, hence each
has small size. Interestingly, at p H 7 there was almost no
ZnO part icles could be observed. It can be understood that
at pH 7, the growth of ZnO was suppressed. It can be
predicted that at pH lower than 7, there might be no ZnO
produced by sol-gel method using protocol implemented in
this research.
Another interesting finding was observed fro m
measurement of crystal size using Williamson-Hall plot
analysis as shown in Table I. Fro m those data, it can be seen
by comparing the particle size (before heat treatment) and
crystal size (after heat treat ment), there was a tendency for
the particle to grow in size. This might be due to
recrystallizat ion happened due to heat treatment effect.
Nevertheless, it can be deduced that the size increment was
not significant.
IV. CONCLUSIONS
Nano ZnO was synthesized succesfully fro m precursor
(CH 3 COOH) 2Zn.2H 2O and NaOH. pH of the working
solution was varied to see the different resulting nano ZnO
produced. Nano ZnO precipitation time increased over
increasing pH, wh ile the size of the nanoparticle also
increased over increasing pH. The XRD data showed that
fro m pH 7 to pH 12, there was significant imp rovement of
the nano ZnO purity. Interestingly, 100% purity of nano
ZnO could be obtained at pH 12. This research showed that
pH condition in sol-gel reaction plays a very significant ro le
to control the characteristics of nano ZnO produced. Further
modification and characterizat ion works are needed before
this nano ZnO used in several applicat ions, such as tooth
cements, or cosmetics.
REFERENCES
[1] Shen L., Bao N., Yanagisawa K., Do men K., Gupta A.,
Grimes C.A. “Direct synthesis of ZnO nanoparticles by a
solution-free mechanochemical reaction”, Nanotechnology
17 (2006) 5117-5123.
[2] Puckett S.D., Taylor E., Raimondo T., et al. “The
relationship between the nanostructure of titanium surfaces
and bacterial attachment”, Biomaterials 31 (2010) 706–713.
[3] Salah N., Habib S.S., Khan Z.H., Memic A., Azam A.,
Alarfaj E., Zahed N., Al-Hamedi S. “ High-energy ball
milling technique for ZnO nanoparticles as antibacterial
material”, Intl. J. Nanomed. 6 (2011) 863-869.
[4] Wang J.R., Ye Z.Z., Huang J.Y., et al. “ ZnMgO nanorod
arrays grown by metal-organic chemical vapor deposition”,
Mater. Lett. 62 (2008) 1263–1266.
[5] Sasani G.M., Vafaee M . “Sol–gel derived zinc oxide
buffer layer for use in random laser media”, Mater. Lett. 62
(2008) 1754–1756.
[6] Ye X.Y., Zhou Y.M., Chen J., Sun Y.Q., Wang Z.Q., et
al. “Coating of ZnO nanorods with nanosized silver
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particles by electroless plating process”, Mater. Lett. 62
(2008) 666–669.
[7] Damonte L.C., Mendoza Z.L.A., Mari S.B., Fenollosa
H.M.A. “Nanoparticles of ZnO obtained by mechanical
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[8] Yan J., Liu Y., Peng A., Lu Q. “Fabrication of nano-
crystalline W-Ni-Fe pre -alloyed powders by mechanical
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[9] Ansari A.A., Singh R., Su mana G., Malhotra B.D., “Sol-
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[10] Sunandan B., Joydeep D. “pH dependent growth oxide
nanorods”, J. Crystal Growth 318 (2009) 8 2549-2554

Fig. and Tables

1 M NaOH
dissolved in
Zn(CH3 COO)2 + CH3 OH distilled water
Sonicate 750 watt, 30
menit

Optimization of
Optimization of titration titration (time)
NaOH + water with
magnetic stirrer
Optimization of
titration
(temperature)
Optimization result of
titration for getting pH Optimization of
variation (7,8,9,10,11,12) titration (stirring
speed)

Observation of Particle size

precipitation time analysis by PSA

Centrifuge (3000 rpm)

Heat treatment (800 C)

Nano ZnO powder

XRD analysis (pH 7, 8, 10, 12)

Fig. 1. Experiment scheme

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80

70

Time to Precipitate (hours)

60

50

40

30

20

10

0
6 7 8 9 10 11 12 13
pH

Fig. 2. T he graph of precipitation time over pH of working solution

Fig. 3. Size distribution of ZnO nanoparticle at pH 7 (top) and pH 12 (bottom)

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Fig. 4. XRD graph of nano ZnO at pH 7, pH 8, pH 10, and pH 12

T ABLE I
CRYSTAL SIZE ANALYZED BY WILLIAMSON - HALL P LOT

pH Crystal size (nm)

7 10,94±0,99

8 17,44±5,36

10 38,27±2,14

12 74,04±41,77

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