Synthesis and characterizations of ZnO-Fe doped for
biodiesel production
Umar Kalmar Nizar1*, Sherly Kasuma W.N.1,
Eko Widodo1
Chemistry Department
Universitas Negeri Padang
Padang, Indonesia
1
*umarjati77@gmail.com
Abstract—This investigation is related to synthesized Fe
doped-ZnO catalyst made by co-precipitation method applied for
biodiesel production from palm oil, which has similar properties
to fossil fuel. The transesterification reaction between palm oil
and methanol (1:6) has been conditioned at 60 – 65 oC for 2h. A
centrifugal process has been used to separate biodiesel and solid
material. A rotary evaporator has been applied to remove excess
methanol. FTIR (Fourier Transformation Infra Red)
characterization of Fe doped-ZnO catalyst shows a wave number
shift of Zn-O (455.03 cm-1) to Zn-O-Fe (552.04 cm -1) for ZnO-Fe
4% and the data of XRD (X Ray Diffraction) show a reduction of
particle size after Fe doping in ZnO matrix at given
concentrations of Fe dopant (4%, 7%, and 10%). The physical
properties with respect to boiling point of biodiesel product has
observed lower than that of palm oil using either ZnO undoped
or Fe doped-ZnO. This study shows a good prospect for
alternative biodiesel production and may extend to industrial
scale after using some technical considerations since palm
plantation is abundantly available in Indonesia.
Keywords—biodiesel; Fe doped-ZnO; FTIR; palm oil;
transesterification; XRD.
I. INTRODUCTION
Generally vegetable oil may yield biodiesel. Palm
plantation may survive up to 25 years and resist towards any
climate change. Therefore, palm oil can be used as potential
alternative source for biodiesel production. The synthesis of
biodiesel generally needs a catalyst. Previous investigation
used homogeneous catalyst such as NaOH or KOH for
biodiesel production, however, the water product may
hydrolyze ester to form soap. The removal of soap from solid
material needs more complicated process. Reaction between
hydroxide and methanol yields water. On the other hand, an
enzyme catalyst is pretty expensive and easily damage to be
used in biodiesel production [1-2].
Heterogeneous catalysts such as metal oxides have broader
applications due to their safety, low cost, simple process, non
corrosive, and reusable [1,3]. In addition, the raw material of
heterogeneous catalyst is abundantly available particularly in
Indonesia. With respect to ZnO heterogeneous catalyst, it has
Sagir Alva2, Rita Sundari2*
Department of Mechanical Engineering
Universitas Mercu Buana
Jakarta, Indonesia
2
*sundaririta15@gmail.com
stable structure of hexagonal wurtzite at room temperature and
normal pressure. Moreover, ZnO can be used as catalyst in
biodiesel production that Zn+2 acts as Lewis acid and O -2 as
Lewis base. However, ZnO as a catalyst has a limitation
related to high particle size and large surface area.
Ba-Abbad [4] reported a doping method for ZnO reduced
its particle size and therefore, the method enhanced its surface
area. A doping method can be conducted by adding a small
amount of impurities to metal oxide, for instance by co-
precipitation method. Moreover, Fe(III) doping in ZnO
catalyst increases its active site [4]. The XRD data showed
the incorporation of Fe(III) ion into hexagonal wurtzite of
ZnO crystal lattice [4]. In other investigation, Gurunathan and
Ravi [5] reported Cu doped-ZnO nano composite used as
heterogeneous catalyst for biodiesel production from waste
cooking oil. The XRD data showed a substitution of Cu in
ZnO hexagonal crystal lattice [5].
This study investigates the ZnO catalyst doping by Fe that
uses co-precipitation method at room temperature with ZnCl 2
and FeCl2 precursors in aqueous solution of NaOH. The co-
precipitation method is selected on account of low operation
temperature and good control of precipitation process. The
synthesized Fe doped-ZnO will be applied as catalyst in
transesterification reaction of palm oil and methanol to yield
biodiesel. The separation of biodiesel will involve two
processes, i.e. (i) centrifugal process to separate biodiesel from
solid catalyst and (ii) rotary evaporation to remove excess
methanol. The Fe incorporation in ZnO crystal lattice will be
observed by FTIR, while the particle sizes of ZnO undoped
and Fe doped-ZnO (1%, 4%, 7%, and 10%) investigated by
XRD. The physical properties of biodiesel product with
respect to density, viscosity, and boiling point will be
examined.
II. EXPERIMENTAL
III. Synthesis of ZnO undoped and Fe doped-ZnO catalysts
The Fe doped-ZnO catalyst was made by mixing aqueous
solution of ZnCl2 0.25M, FeCl2 (1% w/w), and NaOH 1.0M
aqueous solution. Prior to mix the precursors, the aqueous
solution of ZnCl2 was prepared by dissolving a given weight flowed and observed the time until the burette empty was used
of ZnCl2 in 75 ml aquadest and stirring it by a magnetic stirrer to determine the viscosity of biodiesel, and a three-bottle neck
for 45 min. Afterwards, Fe dopant (1%) was added to ZnCl 2 Erlenmeyer filled with biodiesel was heated and connected to
solution, followed by addition of NaOH 1.0M slowly until pH a condenser was applied to determine the boiling point of
solution of 12 attained, and then continued by stirring for 90 biodiesel based on the first drop exit from the condenser. All
min. After 18h solution aging, the solution was centrifuged, the physical properties of biodiesel are compared to that of
filtered, and washed to obtain neutral solution. The precipitate palm oil.
was dried in an oven at 100-110oC for 2h. Furthermore, the
dried powder was calcinated in a furnace at 700oC for 2h. IV. RESULTS AND DISCUSSION
Then the sample stored in a desiccant. The procedure was
repeated for Fe dopant (4%, 7%, and 10%), respectively, as The results of FTIR characterizations show wave number
well as ZnO undoped. The above procedure was adopted from shifts from lower values (at level between 400 cm -1 and 500
Baskar and Soumiya [6] with some modifications. cm-1) attributed to vibrations of Zn-O bonding to higher values
(at level between 500 cm -1 and 600 cm-1) attributed to
vibrations of Zn-O-Fe bonding (Table I). This finding is a
2 FTIR and XRD characterizations justification that several Fe (II) ions replaced Zn(II) ions in
hexagonal crystal lattice, in other words, there is a
FTIR characterizations have been done to examine substitution of Zn(II) ion by Fe(II) ion.
chemical bondings between elements in a molecule related to
type of vibration at certain wave number, in this study the
chemical bondings between Zn-O, Zn-O-Fe, and Zn-O-Zn.
The FTIR spectra were scanned in the range of 400 – 4000 cm-
1
for ZnO undoped, ZnO-Fe-1%, ZnO-Fe-4%, ZnO-Fe-7%,
and ZnO-Fe-10%, respectively.
XRD characterizations have been conducted to examine
crystal structure and particle sizes. The peaks in XRD spectra
indicate types of crystal structure. In this case, the peaks of
ZnO undoped and Fe doped-ZnO attributed to hexagonal
wurtzite crystal structure. The XRD data could determine the
particle sizes of both ZnO undoped and Fe doped-ZnO.

1 Synthesis of biodiesel
The transesterification reaction of palm oil and methanol
(1:6) used ZnO undoped or Fe doped-ZnO catalyst of 2-5%
w/w of palm oil. The reaction was done in a 250ml three-
bottle neck Erlenmeyer provided by a thermometer, condenser,
heater, water bath and a magnetic stirrer. The reaction Fig.1. FTIR spectra of ZnO undoped (1),
condition was set at 60-65oC for 2h. ZnO-Fe-1% (2), ZnO-Fe-4% (3), ZnO-Fe-7% (4)
At first, methanol was mixed with catalyst using a and ZnO-Fe-10% (5).
magnetic stirrer of 100 rpm for 5 min. Then, 150 ml palm oil
added to the mixture slowly and heated at 60-65oC for 2h.
Afterwards, the mixture was cooled and followed by Fig. 1 shows the FTIR spectra of ZnO undoped and Fe
separation process between product, catalyst, and excess doped-ZnO at variation of Fe(II) (1%, 4%, 7%, and 10%). The
methanol. The separation included two processes. The first periodic table data show the ionic radii of Fe(II) and Zn(II) are
process related to centrifugation to separate between product 70 pm and 74 pm, respectively.
and solid catalyst. The glycerol deposited together with solid
catalyst due to its high density. The second process related to
evaporation of excess methanol applying a rotary evaporator TABLE I. FTIR data of wave number of Fe doped-ZnO.
at boiling point higher than that of methanol.
Sample Zn-O Zn-O-Fe Zn-O-Zn
ZnOundoped 467,61 cm-1 - 901,28 cm-1
2 Physical properties of biodiesel ZnO-Fe 1% 455,10 cm-1 539,44 cm-1 824,90 cm-1
ZnO-Fe 4% 455,03 cm-1 552,04 cm-1 885,69 cm-1
The physical properties of biodiesel product were
ZnO-Fe 7% 476,26 cm-1 541,91 cm-1 890,08 cm-1
determined with respect to density, viscosity, and boiling
point. A picnometer full with biodiesel compared to empty ZnO-Fe 10% 484,25 cm-1 551,16 cm-1 889,37 cm-1
picnometer was applied to determine the density of biodiesel,
while a burette filled with biodiesel with a given volume is
 The disparity of ionic radii between Fe (II) and Zn (II) is
not significant and therefore, ionic substitution between Fe (II)
and Zn (II) is possible. Since ionic radii of Fe (II) is slightly
lower than that of Zn (II), it is reasonable that Fe (II) doping in
ZnO catalyst may yield smaller particle size and larger surface
area expected causing larger active site.
Fig.2. XRD spectra of ZnO undoped (1),
ZnO-Fe-1% (2), ZnO-Fe-4% (3), ZnO-Fe-7% (4)
and ZnO-Fe-10% (5).
The results of XRD data are consistent with the FTIR
findings with regard to particle size decrease after Fe doping
in ZnO catalyst except for Fe-1% doping (TABLE II). This
finding is consistent with the investigation reported by Ba-
Abbad [4]. The XRD patterns of this investigation shown in
Fig. 2 have been compared with that of ZnO standard
(Inorganic Structure International Database Center for
Diffraction Data).
The XRD data in TABLE II justified that Fe doping at all
concentrations (1%, 4%, 7%, and 10%) in ZnO catalyst in
terms of diffraction peaks (Figure 2) not changed the single
phase hexagonal wurtzite structure. Kaur et al. [7] observed a
secondary phase formed in 10%Fe doped-ZnO showed by its
diffraction peaks of (2 2 0), (3 1 1), (4 0 0), (4 2 2), and (4 4 0)
at respected 2θ of 29.9o, 35.2o, 42.79o, 53.08o, and 62.12o. The
sol gel method used for 10%Fe doped-ZnO may yield
polycrystalline phase during calcinations process as reported
[7]. Further investigation reported a diffraction peak of (4 0
0) at 2θ = 42.79o was observed for 4%Fe doped-ZnO and a
diffraction peak of (3 1 1) at 2θ = 35.2 o for 7%Fe doped-ZnO
[7]. The later finding is expected to be corresponding with
diffraction peak of iron chloride.
With regard to the ionic radii of Fe(II) and Fe(III), i.e. 70
pm and 60 pm, respectively, which are smaller than that of
Zn(II), i.e. 74 pm, it is possible that either Fe(II) or Fe(III)
ions replaced Zn(II) positions in crystal lattice in Fe doped-
ZnO during any synthesis method of ZnO catalyst (co-
precipitation, sol gel, or solid state). This concept has already
proved by previous investigations [4 – 7]. The Fe doping in
ZnO catalyst may reduce its particle size due to smaller ionic
radii of Fe(II) ion as proved by this study except for 1%Fe
doped-ZnO (TABLE II). The particle size data of 1%Fe
doped-ZnO looks not consistent and this is still not clear,
probably it is corresponding with unstable transition condition
during aging or stirring process.
The transesterification reaction used methanol in this study
to form short chain alkyl ester, which is expected to reduce
physical properties of biodiesel product in terms of density,
viscosity, and boiling point. It is known that long chain alkyl
ester may generate problem in automotive engine and
therefore, methanol has been selected in this investigation.
Moreover, palm oil as vegetable oil cannot be used as fuel oil,
thus, palm oil has to be converted to biodiesel. In addition, the
free fatty acids in vegetable oil source has other limitations if
it is applied for fuel oil. The application of heterogeneous
catalyst such as Fe doped-ZnO may yield product that can be
easily separated from solid catalyst and free fatty acids by
centrifugation. In general, the free fatty acids in palm oil is
about 0.02% as reported [1].
TABLE III. Physical properties of palm oil and biodiesel
product
This investigation applied the molar ratio of palm oil
and methanol as 1:6. It is assumed that higher amount of
methanol may produce more glycerol disturbing the
purification process that more glycerol mixed with methanol.
Baskar and Soumiya [6] applied molar ratio of oil and
methanol as 1:12 for production of biodiesel from castor oil
and the yield of biodiesel about 91% (w/w). Kesic et al. [8]
applied molar ratio of oil and methanol as 1:10 for production
of biodiesel.
TABLE II XRD data of ZnO undoped and Fe doped-Zn in terms of diffraction plane and particle size.
Kesic et al. [8] used
sunflower oil with CaO.ZnO
catalyst made by balling
method, while Istadi and
Nugroho [9] used molar
ratio of oil and methanol as
1:15 for biodiesel
production from soybean oil
applying K2O/CaO-ZnO
catalyst made by co-
precipitation method. It
seems that the molar ratio of
vegetable oil and methanol
are varied on reasons of
many factors in relation to
type of catalyst, mode of
catalyst preparation, and
transesterification reaction
condition.
TABLE III shows the
physical properties results
for biodiesel product and
palm oil with respect to
heterogeneous catalyst
applied in terms of ZnO
undoped and Fe doped-ZnO
with variation of Fe(II)
concentrations (1%, 4%,
7%, and 10%). The data of
boiling points show
remarkable reduction
between palm oil and
biodiesel products using
heterogeneous catalyst. It
should be noted that the
effect of Fe doping in ZnO
slightly increased the
boiling points of biodiesel
product compared to that of
biodiesel applying ZnO
undoped. Moreover, the
higher concentration of Fe
doping slightly increased the
boiling points of biodiesel
product. In fact, the result
is beyond our expectation in
consistency with the
theoretical concept. The
concept is that the Fe doping
may increase active sites of
ZnO catalyst, however, the
Fe doping causing the ZnO-
Fe catalyst generating more
basic catalyst character.
According to previous
report [2 – 3, 5 – 6, 9],
vegetable oils with low FFA
are good using solid base
catalyst, on the other hand,
vegetable oils with high FFA
are recommended using as reactant. Alternative ble light photocatalytic
solid acid catalyst. reactant such as waste frying activity of Fe3+ doped
Therefore, the Fe doping in oil is expected to be more ZnO nanoparticle
ZnO catalyst is not significant in biodiesel prepared via sol-gel
significant to be applied for production applying more technique”,
fresh palm oil. It is expected basic catalyst character. Chemosphere, Elsevier,
that Fe doped-ZnO is vol. 91, pp. 1604-1611,
recommended to be applied 2013.
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[5] B.Gurunathan and
frying oil to biodiesel since
ACKNOWLEDGMENT A.Ravi, “Biodiesel
waste frying oil has lesser
free fatty acids due to production from waste
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of biodiesel from castor
production applying ZnO-Fe oil using iron (II) doped
catalyst. Similar findings
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