molecules
Article
Synthesis and Characterization of ZnO-SiO2 Composite Using
Oil Palm Empty Fruit Bunch as a Potential Silica Source
Fida’i Rahmat 1 , Yap Wing Fen 1,2, *, Muhammad Fahmi Anuar 2 , Nur Alia Sheh Omar 1 ,
Mohd Hafiz Mohd Zaid 2 , Khamirul Amin Matori 2 and Rahayu Emilia Mohamed Khaidir 1






Citation: Rahmat, F.; Fen, Y.W.;
Anuar, M.F.; Omar, N.A.S.;
Zaid, M.H.M.; Matori, K.A.;
Khaidir, R.E.M. Synthesis and
Characterization of ZnO-SiO2
Composite Using Oil Palm Empty
Fruit Bunch as a Potential Silica
Source. Molecules 2021, 26, 1061.
https://doi.org/10.3390/
molecules26041061
Academic Editor: Xin Min
Received: 9 January 2021
Accepted: 11 February 2021
Published: 18 February 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Molecules 2021, 26, 1061. https://doi.org/10.3390/molecules26041061
1 Institute of Advanced Technology, Universiti Putra Malaysia, UPM Serdang, Selangor 43400, Malaysia;
fidai.rahmat95@gmail.com (F.R.); nuralia.upm@gmail.com (N.A.S.O.);
rahayuemilia.upm@gmail.com (R.E.M.K.)
2 Department of Physics, Faculty of Science, Universiti Putra Malaysia, UPM Serdang,
Selangor 43400, Malaysia; fahmianuar6323@gmail.com (M.F.A.); mhmzaid@upm.edu.my (M.H.M.Z.);
khamirul@upm.edu.my (K.A.M.)
* Correspondence: yapwingfen@upm.edu.my
Abstract: In this paper, the structural and optical properties of ZnO-SiO2 -based ceramics fabricated
from oil palm empty fruit bunch (OPEFB) were investigated. The OPEFB waste was burned at 600,
700 and 800 ◦ C to form palm ash and was then treated with sulfuric acid to extract silica from the ash.
X-ray fluorescence (XRF) and X-ray diffraction (XRD) analyses confirmed the existence of SiO2 in the
sample. Field emission scanning electron microscopy (FESEM) showed that the particles displayed
an irregular shape and became finer after leaching. Then, the solid-state method was used to produce
the ZnO-SiO2 composite and the samples were sintered at 600, 800, 1000, 1200 and 1400 ◦ C. The XRD
peaks of the Zn2 SiO4 showed high intensity, which indicated high crystallinity of the composite.
FESEM images proved that the grain boundaries were larger as the temperature increased. Upon
obtaining the absorbance spectrum from ultraviolet–visible (UV–Vis) spectroscopy, the energy band
gaps obtained were 3.192, 3.202 and 3.214 eV at room temperature, 600 and 800 ◦ C, respectively, and
decreased to 3.127, 2.854 and 2.609 eV at 1000, 1200 and 1400 ◦ C, respectively. OPEFB shows high
potential as a silica source in producing promising optical materials.
Keywords: oil palm empty fruit bunch; ZnO-SiO2 nanocomposite; silica; structural; optical
1. Introduction
In recent years, environmental issues have been becoming increasingly more important
in Malaysia and all over the world. The palm oil industry is aware of the environmental
pollution being caused and is striving towards quality and environmental conservation
through sustainable development and cleaner technology approaches. The largest waste
materials from palm oil mills, namely oil palm empty fruit bunches (OPEFBs), are extremely
abundant, renewable and readily available lignocellulosic materials. Therefore, there is
a need for sustainable waste management and to convert the waste into useful materials.
Silica (SiO2 ) is a material with high porosity and a large surface area. It is widely used
in fillers, catalysts and pharmaceutical materials [1–3]. In industry, SiO2 can be produced
by using sodium silicate, where the production of sodium silicate requires a large amount
of energy to smelt quartz sand and sodium carbonate [4]. Consequently, efforts and ideas
have been developed to look for alternatives. Extensive studies have attempted to extract
silica from various agriculture waste products such as rice husk, corn cob ash and coconut
and palm waste [5–9]. To the best of our knowledge, a study on OPEFBs as a silica source
has yet to be explored.
There are a wide range of industrial applications where silica is associated with metals
and where the family of silicates is formed. For instance, zeolite clinoptilolite or alumino-
silicate (network of AlO4 and SiO4 ) have excellent detoxifying and anti-inflammatory
https://www.mdpi.com/journal/molecules
Molecules 2021, 26, 1061 2 of 11

properties that can be used in many industrial applications ranging from environmental
remediation to oral applications [10,11]. Another silica-metal-based material, ZnO-SiO2 ,
has been receiving growing attention from researchers owing to its interesting application
in glass ceramics, technical glasses and optical glasses [12,13]. It has excellent lumines-
cence properties in blue, green and red spectral regions [14]. On the other hand, when
heat treatment is applied, zinc silicate can be formed [15–17]. Zinc silicate has emerged
as a good host material in plasma display panels, cathode ray tubes, laser crystal and
electroluminescent devices [18–21].
Due to the large amount of energy needed to produce silica from quartz and sodium
carbonate, researchers are aiming to develop alternatives to fabricate ZnO-SiO2 by using
environmentally friendly silica sources [22–24]. OPEFB is envisaged as an alternative for
the extraction of silica to produce novel ZnO-SiO2 materials. This move will definitely
have a positive impact on our ecological system by reducing massive waste from palm oil
mill productions every year. In this study, the potential of OPEFB waste as a silica source is
investigated, and the structural and optical properties of the ZnO-SiO2 composite derived
from OPEFB waste are reported.

2. Results
2.1. Palm Waste Silica
2.1.1. XRF Analysis
The OPEFB was burned at three different temperatures, that is, 600, 700 and 800 ◦ C, to
produce palm ash samples. The chemical composition of palm ash samples was analyzed
using energy dispersive X-ray fluorescence (EDXRF). The chemical composition of the
samples is shown in Table 1.

Table 1. Chemical composition of palm ash derived from oil palm empty fruit bunch (OPEFB).

Percentage of Compositions
Compounds
600 ◦C 700 ◦ C 800 ◦ C
CaO 40.0 52.2 39.2
K2 O 40.2 29.8 35.2
SiO2 5.6 6.9 9.5
P2 O 5 2.9 4.2 4.2
Fe2 O3 2.4 1.5 2.6
Cl 5.9 3.0 2.5
SO3 1.7 1.3 2.1

The OPEFB that was burned at 800 ◦ C showed the highest percentage of SiO2 . There-
fore, it was selected for further processing to eliminate all impurities and increase the
percentage of SiO2 element in the sample using acid treatment. Table 2 shows the compari-
son of the sample’s chemical composition before and after leaching.

Table 2. Chemical composition of palm ash (before and after leaching).

Percentage of Compositions
Compounds
Before After
CaO 39.2 17.8
K2 O 35.2 16.4
SiO2 9.5 45.6
P2 O5 4.2 0.0
Fe2 O3 2.6 3.3
Cl 2.5 0.0
SO3 2.1 3.5
 and does not fully eliminate other metal impurities in the sample. This is because sulfuric
acid leaching can dissolve the metal elements in the sample. The mechanism involves the
existence of carboxyl groups in sulfuric acid that tend to donate protons, hence forming
the negatively charged carboxyl group. These negatively charged carboxyl groups can
Molecules 2021, 26, 1061 form stable complexes with positive charged ions, Ca+ and K+, that are present in the3palm
of 11
ash [25]. This is the reason why the impurities of the palm ash were reduced, as can be
observed in Table 2.
These results indicate that leaching can increase the percentage of SiO2 in palm ash
2.1.2.
and XRD
does notAnalysis
fully eliminate other metal impurities in the sample. This is because sulfuric
The results
acid leaching can of the X-ray
dissolve diffraction
the metal pattern
elements in theof sample.
the palm Theashmechanism
waste before and after
involves the
leaching are
existence shown ingroups
of carboxyl Figurein 1. sulfuric
From theacidgraph,
thatittend
can be seen that
to donate there was
protons, oneforming
hence obvious
strong
the peak before
negatively chargedthe leaching
carboxylprocess,
group. i.e.,
These CaO at 29.76°.charged
negatively Next, thecarboxyl
SiO2 element
groups can
canbe
found at 26.74° and 39.38° with a lower peak +
intensity, +
which
form stable complexes with positive charged ions, Ca and K , that are present in the palmhas a hexagonal crystal
structure.
ash Other
[25]. This elements
is the reasonthat
why can beimpurities
the found withoflower peakash
the palm intensities are K2O,asP2can
were reduced, O5 and
be
Fe2O3 with
observed peaks2.at 25.78°, 29.55° and 40.32°, respectively. These XRD results can be
in Table
proven by the XRF analysis results shown before.
2.1.2. The
XRDX-ray
Analysis
diffraction results after leaching show that more peaks appeared with a
higher
Theintensity.
results ofThe themajor
X-ray peaks belonged
diffraction pattern to SiO 2 which
of the palm has ash awaste
rhombohedral
before andcrystal
after
leaching are shown in Figure 1. From the graph, it can be seen that
structure at 20.93°, 29.18°, 31.10° and 32.87°. At 40.61°, K2O appeared with a hexagonal there was one obvious
strong ◦ . Next, the SiO element can
crystalpeak beforeAnother
structure. the leaching
element process, i.e.,was
detected CaOSO at329.76
which has an orthorhombic
2 crystal
be found at ◦ ◦
structure at26.74
peaks and 39.38
32.34°, with43.83°
40.36°, a lowerand peak intensity,
47.99°. which has
The presence of aSOhexagonal
3 was due crystal
to the
structure.
reaction ofOther
sulfuricelements
acid used thatforcan be found
leaching. Thesewith lower
results peak intensities
indicate that leachingare can
K2 O, P2 O5
increase
and Fe2 O3 with of peaks ◦ 29.55◦ and 40.32◦ , respectively. These XRD results can be
the percentage SiO2atin25.78
palm ,ash and remove part of the metal impurities in the sample
proven
[25]. by the XRF analysis results shown before.

Figure1.1. X-ray
Figure X-ray diffraction
diffraction(XRD)
(XRD)results
resultsfor
forpalm
palmash
ashbefore
beforeand
andafter
afterleaching.
leaching.

The X-ray diffraction results after leaching show that more peaks appeared with
a higher intensity. The major peaks belonged to SiO2 which has a rhombohedral crystal
structure at 20.93◦ , 29.18◦ , 31.10◦ and 32.87◦ . At 40.61◦ , K2 O appeared with a hexagonal
crystal structure. Another element detected was SO3 which has an orthorhombic crystal
structure at peaks 32.34◦ , 40.36◦ , 43.83◦ and 47.99◦ . The presence of SO3 was due to
the reaction of sulfuric acid used for leaching. These results indicate that leaching can
increase the percentage of SiO2 in palm ash and remove part of the metal impurities in the
sample [25].
 4 of 11

Molecules 2021, 26, 1061 4 of 11

2.1.3. FESEM Analysis

2.1.3. FESEM
The surface morphology ofAnalysis
the palm waste silica before and after the leaching process
The surface morphology
with sulfuric acid is presented in Figure of the
2. As shownpalm in
waste
thesilica before
figure, theand after the
results leaching
show thatprocess
with sulfuric acid is presented in Figure 2. As shown in the figure, the results show that
both of them have both
irregular medium-sized particles distributed with a crushed shape
of them have irregular medium-sized particles distributed with a crushed shape
structure. Figure 2bstructure.
shows particles in theparticles
Figure 2b shows sample thatsample
in the are finer compared
that are to Figure
finer compared 2a.
to Figure 2a. This
This is because the leaching
is becauseprocess eliminated
the leaching most of the
process eliminated metal
most of thecomposition in the
metal composition in sam-
the sample,
thus providing
ple, thus providing finer surface offiner surface of particles.
particles.

(a) (b)
Figure
Figure 2. Field
2. Field emission
emission scanning
scanning electronelectron microscopy
microscopy (FESEM)
(FESEM) images of palmimages of burned
waste ash at 800 ◦ash
palm waste C (a)burned
before and
(b)
at after
800 leaching.
°C (a) before and (b) after leaching.
2.2. ZnO-SiO2
2.2. ZnO-SiO2 2.2.1. XRD Analysis
2.2.1. XRD Analysis The results of the X-ray diffraction pattern of ZnO-SiO2 are shown in the Figure 3.
From the graph, it can be seen that the elements SiO2 and ZnO appeared in the sample
The results of the X-ray diffraction pattern of ZnO-SiO2 are shown in the Figure 3.
before it was sintered. At 21.09◦ , a very small peak appeared, indicating the presence of
From the graph, it canSiO2bewithseen that the elements
an orthorhombic SiO2 and
crystal structure. ZnO appeared
Another in theinsample
element presented the sample at
◦ , 34.55◦ and, for the highest peak,
before it was sintered. At 21.09°, a very small peak appeared, indicating the presence of
room temperature is ZnO, which was positioned at 31.85
36.36◦ . crystal structure. Another element presented in the sample at
SiO2 with an orthorhombic
At 600 ◦ C, the element of ZnO started to appear at 31.75◦ followed by 34.44◦ , and
room temperature is ZnO, which was positioned at 31.85°, 34.55° and, for the highest peak,
the highest peak of ZnO is at 36.25◦ . ZnO is hexagonal in structure. The diffraction peaks
36.36°. of single, well-crystallized ZnO phase are clearly obtained (found in excess compared to
At 600 °C, the element of ZnO started
the stoichiometric to appear
amount required foratthe31.75° followed
formation by 434.44°,
of Zn2 SiO , where and
2ZnOthe + SiO2 =
Zn SiO ). At a temperature of 800 ◦ C, the intensity of ZnO at peaks 31.82◦ , 34.47◦ and 36.19◦
highest peak of ZnO is2 at 436.25°. ZnO is hexagonal in structure. The diffraction peaks of
is higher compared to at the temperature of 600 ◦ C. As the temperature increases, the ZnO
single, well-crystallized ZnO phase are clearly obtained (found in excess compared to the
nanocrystals may grow to larger sizes but the process is hindered by the surrounding SiO2
stoichiometric amount matrixrequired
[17,26]. Thisforcauses
the formation
the SiO2 element of Zn
peak2SiO4, where 2ZnO + SiO2 =
to start to disappear from the graph. As
Zn2SiO4). At a temperature of 800 °C, the intensity ◦ of ZnO at peaks
the temperature increased to 1000 C, strong and high-intensity 31.82°, 34.47° and 36.19°
peaks appeared at 31.77◦ ,
◦ ◦
is higher compared to at the
34.42 and temperature of 600 °C.ofAs
36.25 . The formation Zn2the
SiOtemperature
4 has the highest increases, thetemperature
peak at this ZnO
compared to 600 and 800 ◦ C. It is believed that ZnO is the dominant diffusing species in
nanocrystals may grow to larger sizes but the process is hindered by the surrounding SiO2
ZnO/SiO2 at temperatures greater than 700 ◦ C. For the temperatures 1200 and 1400 ◦ C,
matrix [17,26]. This causes the SiO2 element peak to start to disappear from the graph. As
the intensity of peaks at 31.85◦ , 34.55◦ and 36.36◦ started to decrease after a temperature of
the temperature increased
1000 ◦ C.toThe 1000 °C, strong
decrease andintensity
in the peak high-intensity peaks to
can be attributed appeared at of
the collapse 31.77°,
the Zn2 SiO4
34.42° and 36.25°. The formation
tetragonal of ZnThis
structure. 2SiO has thethe
is4because highest
formationpeak at2 SiO
of Zn this4 started
temperature com-
at room temperature
pared to 600 and 800 800It◦ C,isand
until°C. this increases
believed that theZnO crystallinity of the samples,
is the dominant thus increasing
diffusing speciesthe in
intensity
ZnO/SiO2 at temperatures greater than 700 °C. For the temperatures 1200 and 1400 °C, the
intensity of peaks at 31.85°, 34.55° and 36.36° started to decrease after a temperature of
1000 °C. The decrease in the peak intensity can be attributed to the collapse of the Zn2SiO4
tetragonal structure. This is because the formation of Zn2SiO4 started at room temperature
Molecules 2021, 26, 1061 5 of 11

Molecules 2021, 26, x of peaks [19]. The collapse of Zn2 SiO4 formation with the remaining ZnO and SiO2 phase 5 of 11
at higher temperature causes the crystallinity to decrease and reduces the intensity of peaks
at temperatures of 1000 to 1400 ◦ C.

XRDanalysis
Figure3.3.XRD
Figure analysisof
ofZnO-SiO
ZnO-SiO22for
fordifferent
differentsintering
sinteringtemperatures.
temperatures.

2.2.2. FESEM Analysis

2.2.2. FESEM Analysis
The surface morphologies of ZnO-SiO2 that was sintered at various temperatures
The surface morphologies of ZnO-SiO2 that was sintered at various temperatures are
are shown in Figure 4. All of the SEM images are shown at 1000× magnification. It
shown in Figure 4. All of the SEM images are shown at 1000× magnification. It was ob-
was observed that the prepared sample at room temperature consisted of particles with
served that the prepared sample at room temperature consisted of particles with numer-
numerous little fragments on the surface, not uniform, and has irregular particle size
ous little fragments on the surface, not uniform, and has irregular particle size distribu-
distribution. Next, the microstructure shows that the crystal grains are still in irregular
tion. Next, the microstructure shows that the crystal grains are still in irregular shape at
shape at 600 ◦ C and started to aggregate among each other after being heated up to 800 and
600 °C and started to aggregate among each other after being heated up to 800 and 1000
1000 ◦ C. When the sintering temperature increased to 1000 ◦ C, the particles start to look like
°C. When the sintering
melted forms. However,temperature increased
the microstructure to 1000that
revealed °C, there
the particles start togrowth
is little crystal look like
on
melted
the sample surface, which indicates the crystals’ formation at the sintering temperatureson
forms. However, the microstructure revealed that there is little crystal growth of
the
1200sample surface,
and 1400 ◦ C. Atwhich indicates theZnO-SiO
high temperature, crystals’ formation
becomes at the sintering
granular and has atemperatures
homogenous
2
of 1200 and 1400
distribution, where°C.hexagonal
At high temperature, ZnO-SiO
and rectangular shapes2 becomes granular and has a homog-
can be observed. Overall, the shape
enous distribution, where hexagonal and rectangular shapes
of the grains structure is irregular and distributed homogenously can be observed. Overall,
for all samples. the
It can
shape of the grains structure is irregular and distributed homogenously
be observed that there is an increment in the grain size with the increase in sinteringfor all samples. It
can be observed that there is an increment in the grain
temperature, as seen from the crystal growth pattern [27,28]. size with the increase in sintering
temperature, as seen from the crystal growth pattern [27,28].
Molecules 2021, 26, 1061 6 of 11
Molecules 2021, 26, x 6 of 11

(a) (b)

(c) (d)

(e) (f)
Figure 4.
Figure 4. FESEM
FESEMimages
imagesofofZnO-SiO2 sintered
ZnO-SiO at (a) 27, (b) 600, (c) 800, (d) 1000, (e) 1200 and (f)
2 sintered at (a) 27, (b) 600, (c) 800, (d) 1000, (e) 1200 and
1400 °C.
◦
(f) 1400 C.

2.2.3. Optical Studies

2.2.3. Optical Studies
The
The opticalproperties
optical propertiesofofZnO-SiO
ZnO-SiO2 at different sintering temperatures were measured
2 at different sintering temperatures were meas-
using a UV–Visible
ured using spectrometer
a UV–Visible in theinrange
spectrometer of 200ofto200
the range 800tonm
800asnm
shown in Figure
as shown 5. It is
in Figure 5.
shown that intensive absorption occurs in the range of 250 to 370 nm for all
It is shown that intensive absorption occurs in the range of 250 to 370 nm for all tempera-temperatures.
However, when when
the sample was sintered at 1400 ◦ C, the absorption edge of the sample
tures. However, the sample was sintered at 1400 °C, the absorption edge of the sam-
shifted towards
ple shifted the the
towards longer wavelength
longer duedue
wavelength to the crystallization
to the of the
crystallization sample
of the enhancing
sample enhanc-
the absorption of redshift.
ing the absorption of redshift.
Molecules 2021,26,
Molecules2021, 26,1061
x 77ofof11
11

◦ C.
Figure5.5.Absorption
Figure Absorptionspectra
spectraof
ofZnO-SiO
ZnO-SiO22at
at27,
27,600,
600,800,
800,1000,
1000,1200
1200and
and1400
1400 °C.

Next,
Next,the
theabsorbance
absorbance coefficient
coefficient was
was calculated
calculated to
to determine
determine the
the energy
energy band
band gap.
gap.
The absorbance coefficient is given as:
The absorbance coefficient is given as:
αα = 2.303A
= 2.303A (1)
(1)
where the unit of α is m−1. The energy band gap of these composites can be calculated from
where the unit of α is m−1 . The energy band gap of these composites can be calculated
the Tauc relation [29,30]:
from the Tauc relation [29,30]:
k (hv − Eg )n n
α = k ( hv − E g ) (2)
α = hv (2)
where Eg is the energy band gap, k is proportional hvconstant, h is Planck’s constant, v is the
frequency of the incident photon and hv is the photon
where Eg is the energy band gap, k is proportional constant,energy. The
h is exponent
Planck’s n represents
constant, v is the
1
the type of transition,
frequency where
of the incident n = 2 for
photon anddirect
hv is transition
the photon while n = 2The
energy. for exponent
indirect transition. In
n represents
order to obtain the both direct and indirect energy band gaps, Equation (3) was rearranged
the type of transition, where n = ½ for direct transition while n = 2 for indirect transition.
to
Inyield:
order to obtain the both direct and indirect energy band gaps, Equation (3) was rear-
1
ranged to yield: (αhv) n = k(hv − Eg ) (3)
1
By substituting n = 12 and n = 2, both ngraphs of (αhv)2 versus hv and (αhv)1/2 versus
(α hv ) = k ( hv − E g ) (3)
hv for all sintering temperatures of the samples were plotted, as shown in Figures 6 and 7,
respectively. From the graphs, each best fit line was drawn until it reached the x-axis, where
By substituting n = ½ and n = 2, both graphs of (αhv)2 versus hv and (αhv)1/2 versus hv
the intersection gives the value of the direct band gap (Figure 6) and the indirect energy
for all sintering temperatures of the samples were plotted, as shown in Figures 6 and 7,
band gap (Figure 7). From Figure 6, the energy band gap of unsintered ZnO-SiO2 was
respectively. From the graphs, each best fit line was drawn until it reached the x-axis,
found to be 3.192 eV. At 600 and 800 ◦ C, the energy band gaps of the sample were 3.202 and
where the intersection gives the value of the direct band gap (Figure 6) and the indirect
3.214 eV, respectively. The energy band gap started to drop at temperatures of 1000, 1200
energy band gap (Figure 7). From Figure 6, the energy band gap of unsintered ZnO-SiO2
and 1400 ◦ C to 3.127, 2.854 and 2.609 eV, respectively. Meanwhile, for Figure 7, the energy
was found to be 3.192 eV. At 600 and 800 °C, the energy band gaps of the sample were
band gap of unsintered ZnO-SiO2 was 3.097 eV. At 600 and 800 ◦ C, the energy band gaps
3.202 and 3.214 eV, respectively. The energy band gap started to drop at temperatures of
of the sample were 3.120 and 3.141 eV, respectively. The energy band gap started to drop at
1000, 1200 and
temperatures of 1400
1000,°C
1200to 3.127, 2.854
and 1400 ◦ Cand 2.609 2.500
to 3.027, eV, respectively.
and 2.204 eV,Meanwhile, forThe
respectively. Figure
band7,
the energy band gap of unsintered ZnO-SiO 2 was 3.097
◦ eV. At 600 and 800 °C,
gap energy increased from room temperature until 800 C as the crystallinity of the samples the energy
band gapsThis
improved. of the
is insample
agreementwere 3.120
with and 3.141
previous eV,which
studies respectively.
revealed The energy
that the band gap
enhancement
started
of to dropcrystallinities
the samples’ at temperatures canof 1000,
cause the1200 and 1400
reduction °C to 3.027,states,
in delocalized 2.500 and
which2.204
led eV,
to
respectively. The band gap energy increased from room temperature until 800 °C as the
Molecules
Molecules2021,
2021,26,
26,xx 88of
of11
11

Molecules 2021, 26, 1061 8 of 11

crystallinity
crystallinityof ofthe
thesamples
samplesimproved.
improved.This Thisisisininagreement
agreementwith withprevious
previousstudies
studieswhich
which
revealed
revealed that
that the
the enhancement
enhancement of of the
the samples’
samples’ crystallinities
crystallinities can can cause
cause the
the reduction
reduction in in
delocalized states, which led to lesser defects, thereby promoting
delocalized states, which led to lesser defects, thereby promoting an increase in the band an increase in the band
gap
gap values
lesser values [31].
defects,[31]. ItIt started
thereby started to
to decrease
promoting decrease from
from 1000
an increase 1000
in the to 1400
1400 °C
toband °C because
gap because the
values [31].the formation
It started of
formation of
to
Zn
Zn22SiO
SiO44started
decrease to
from 1000
started tocollapse
to 1400
collapse at◦higher
at C because
higher temperatures
the formation
temperatures in
inthe
theZnO-SiO
of Zn2 SiO
ZnO-SiO 22composite.
started toThe
4composite. absorp-
collapse
The absorp-at
tion
tionedges
higher became
becamesmaller
temperatures
edges in the and,
smaller and,thus,
ZnO-SiO thus, decreased
decreasedthe
2 composite. Theoptical
the band
absorption
optical gap
gap[32–34].
bandedges becameOn
[32–34]. the
theother
smaller
On and,
other
hand,
thus, the
theobtained
hand,decreased
obtainedthe optical band
opticalband
bandgapgap value
valueisisOn
gap[32–34]. in
inagreement
the other hand,
agreement with aaprevious
withthe obtainedstudy
previous studywhere
optical band
where
pure
gap SiO
SiO22was
purevalue is inused
was [35],
agreement
used [35],which
with resulted
which aresulted
previous in
inthe
theband
study band gap
where being
gappure
being indirect.
SiO Therefore,
2 was used
indirect. ititcan
[35], which
Therefore, can
resulted
be
beconcludedin thethat
concluded band
that palmgapwaste
palm being has
waste indirect.
hashigh Therefore,
highpotential
potentialto toitbe
can
be anbealternative
an concludedthat
alternative thatcan
that palm
can wasteSiO
replace
replace has22
SiO
high
to potential
toproduce
produce theto
the be an alternative that can replace SiO2 to produce the composite.
composite.
composite.

Figure
Figure6.
Figure 6.Plot
6. Plotof
Plot of (αhv)222against
of(αhv)
(αhv) againsthv
hvof
ofZn-SiO
Zn-SiO222composite
compositesintered
sinteredatatvarious
varioustemperatures.
temperatures.

Figure 7. Plot of (αhv)1/2 against hv of Zn-SiO composite sintered at various temperatures.

Figure
Figure7.
7.Plot
Plotof
of(αhv)
(αhv)1/21/2against
againsthv
hvof
ofZn-SiO
Zn-SiO22composite
2compositesintered
sinteredat
atvarious
varioustemperatures.
temperatures.
3. Materials and Methods
3.3.Materials
Materialsand
andMethods
Methods
An empty fruit bunch was first cleaned using distilled water and then dried up
An empty fruit
◦ Cbunch was first
firstcleaned using distilled water and
andthen dried upupin an
in anAn empty
oven at 70fruit bunch
for 24 was
h. After cleaned
that, theusing
fruit distilled
bunch was water
crushedthen
anddried
burned in
inana
oven at 70
oven at 70 °C for
°C for 24 h.
24andAfter
h. Afterthat, the fruit bunch was crushed and burned in a furnace at
furnace at 600, 700 800 ◦that,
C forthe
2 h.fruit
Thebunch
palmwasash crushed
obtainedand
wasburned
cooledindown
a furnace
inside at
the furnace and collected for a preliminary quantitative analysis. Quantitative analysis
of the sample chemical compositions was carried out using an X-ray fluorescence (XRF)
XRF-EDX-720/7000 machine (Shimadzu, Kyoto, Japan).
Molecules 2021, 26, 1061 9 of 11

Next, the palm ash sample with the highest percentage of silica (800 ◦ C) was selected
for further experiments. The sample underwent acid treatment, where 20 mL of 5 N
(normality) sulfuric acid was added to the sample. The mixture was stirred using a hot
plate magnetic stirrer at 50 ◦ C for 30 min and then filtered using Whatmann No. 41 ashless
filter paper. Finally, the residue was dried in an oven at 60 ◦ C for 1 h to obtain the sample in
powder form. XRF analysis was conducted once again to confirm the chemical composition
of the sample after the acid leaching process. Phase identification of the samples was
conducted by using an X-ray diffraction (XRD) Phillips X’Pert High Pro PANanalytical
Diffractometer (Malvern Pananalytical, Almelo, (The Netherlands) and Malvern (UK)),
with a data range of 2θ from 20◦ to 80◦ . To analyze the morphological structure of the
samples, field emission scanning electron microscopy (FESEM) (Nova NanoSEM 30 (FEI,
Hillsboro, OR, USA)) was used.
To prepare the ZnO-SiO2 composite, a conventional solid-state method was used.
Acid-treated palm waste silica and ZnO nanopowders (US Research Nanomaterials, Inc.,
United State of America, 99%+, 10–30 nm ZnO) were mixed in the ratio 1:1 via milling
process using a ball milling jar for 24 h. After the milling process, the mixture was then
sintered in an alumina crucible at 600 to 1400 ◦ C at a heating rate of 10 ◦ C/min for 2 h in an
electrically heated furnace. One sample remained at room temperature, 27 ◦ C. Structural
characterization of the composite sintered at various temperatures was analyzed using
XRD and FESEM. For optical characterization, UV–Vis absorption analysis was carried out
using a UV-3600 Shimadzu spectrophotometer (Shimadzu, Kyoto, Japan). The absorption
spectrum obtained was used to calculate the optical band gap for the materials.

4. Conclusions
This study investigated oil palm empty fruit bunch (OPEFB) as an alternative resource
for silica. An OPEFB that was burned at 800 ◦ C was then leached to remove impurities
and increase the percentage of silica composition in the sample. The XRF result shows
that the percentage of silica increased from 9.5% to 45.6% after leaching. For ZnO-SiO2 ,
the XRD result showed that intensity was the highest at 1000 ◦ C as compared to other
sintering temperatures. Most of the diffraction peaks were indexed to the hexagonal
structure of ZnO. For the surface morphology of ZnO-SiO2 , the result showed that the
grain boundaries started to increase as the temperature raised, resulting from the crystal
growth. For UV–Vis analysis, the results showed that a sharp absorption edge was observed
at a wavelength of about 360 nm at room temperature. When the prepared sample was
sintered at temperatures from 600 to 1400 ◦ C, a broad absorption band appeared in the
range of 270 to 310 nm. Both direct and indirect energy band gaps of the composite
increased from room temperature to 800 ◦ C and started to decrease from 1000 to 1400 ◦ C
because the formation of Zn2 SiO4 started to collapse at higher temperatures for the ZnO-
SiO2 composite, with an indirect energy band gap close to the composite formed by pure
silica. In short, OPEFBs have high potential as a silica source to be used in optical materials.

Author Contributions: Conceptualization, methodology, and original draft preparation, F.R.; val-
idation, supervision, review and editing, and funding acquisition, Y.W.F.; visualization, M.F.A.;
investigation and formal analysis, N.A.S.O.; resources, M.H.M.Z. and K.A.M.; software, R.E.M.K. All
authors have read and agreed to the published version of the manuscript.
Funding: This work was funded by the Malaysian Ministry of Education (MOE) and the Universiti
Putra Malaysia (UPM) through the Putra Grant 9642800.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available within the article.
Molecules 2021, 26, 1061 10 of 11

Acknowledgments: The authors gratefully acknowledge the financial support for this study from
the Malaysian Ministry of Education (MOE) and the Universiti Putra Malaysia (UPM). The laboratory
facilities provided by the Institute of Advanced Technology and Faculty of Science, Universiti Putra
Malaysia, are also acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

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