nanomaterials

Article
Palm Kernel Shell Activated Carbon as an Inorganic
Framework for Shape-Stabilized Phase
Change Material
Ahmad Fariz Nicholas 1 , Mohd Zobir Hussein 1, * ID
, Zulkarnain Zainal 1 ID

and Tumirah Khadiran 2

1 Materials Synthesis and Characterization Laboratory, Institute of Advanced Technology (ITMA),
Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia; ahmadfariznicholas@yahoo.com (A.F.N.);
zulkar@upm.edu.my (Z.Z.)
2 Forest Product Division, Forest Research Institute Malaysia (FIRM), 52109 Kepong, Selangor, Malaysia;
tumirah@frim.gov.com
* Correspondence: mzobir@upm.edu.my; Tel.: +60-3-89468092




Received: 26 July 2018; Accepted: 30 August 2018; Published: 5 September 2018


Abstract: The preparation of activated carbon using palm kernel shells as the precursor (PKSAC)
was successfully accomplished after the parametric optimization of the carbonization temperature,
carbonization holding time, and the ratio of the activator (H3 PO4 ) to the precursor. Optimization at
500 ◦ C for 2 h of carbonization with 20% H3 PO4 resulted in the highest surface area of the activated
carbon (C20) of 1169 m2 g−1 and, with an average pore size of 27 Å. Subsequently, the preparation of
shape-stabilized phase change material (SSPCM-C20) was done by the encapsulation of n-octadecane
into the pores of the PKSAC, C20. The field emission scanning electron microscope images and the
nitrogen gas adsorption-desorption isotherms show that n-octadecane was successfully encapsulated
into the pores of C20. The resulting SSPCM-C20 nano-composite shows good thermal reliability which
is chemically and thermally stable and can stand up to 500 melting and freezing cycles. This research
work provided a new strategy for the preparation of SSPCM material for thermal energy storage
application generated from oil palm waste.

Keywords: activated carbon; palm kernel shell; phase change material; thermal energy storage; paraffin

1. Introduction
Malaysia, Indonesia, Thailand, African countries like Nigeria, Cameroon and several Southern
provinces of China are among the top producers of palm oil in the world [1]. As the leading producer
and supplier of the oil palm, Malaysia keeps on increasing the production of palm oil by developing
oil palm plantations beginning with only 54,000 hectares in the early 1960s, expected to increase to
5.1 million hectares by 2020 [2]. The oil palm industries in Malaysia are producing about 90 × 106 tons
of lignocellulosic biomass each year, of which empty fruit bunch (EFB), oil palm trunk (OPT) and oil
palm fronds (OPF) are about 40 × 106 tons [3]. It is an opportunity for oil palm industries to use these
wastes to turn them into valuable products instead of discarding them by open burning [4] which
resulted in bad consequences for the environment. The increasing number of waste material from
industrial development contributed to the deterioration of the earth through ozone depletion. Oil palm
solid waste (OPSW) like palm kernel shell is a good candidate for the production of activated carbon
as it contains a highly developed porosity and surface area because of its high carbon content and
relatively low price [5].
Palm kernel shell is a sustainable source of materials included in the economic sector
which is responsible for the breakdown of global greenhouse gas emissions and climate change.

Nanomaterials 2018, 8, 689; doi:10.3390/nano8090689 www.mdpi.com/journal/nanomaterials

Nanomaterials 2018, 8, 689 2 of 14

Many industries, academics, and governmental agencies are now focusing on the green chemistry
and engineering technologies to minimize the negative impacts towards the environment [6].
The manufacturing processes are now restructured by the application of green solvents and reagents,
energy conservations, waste minimization, and utilization of natural resources.
Consisting of about 87% to 97% of carbon and other elements such as hydrogen, oxygen, sulfur and
nitrogen, activated carbon has a very high adsorption capability by having the highest volume of
adsorbing porosity [7]. Activated carbon with highly developed porosity, has a large surface area, a high
micropore volume (Vmic ), a favourable pore size distribution, and thermal stability [8]. The surface
area of activated carbon is usually more than 1000 m2 /g. Activated carbon has a random imperfect
structure which consists of a broad range of pore sizes—micro, meso, and macro—that makes activated
carbon different from graphite [7] or other carbon materials. The surface of the activated carbon can be
used to accumulate contaminants as it contains the protonated (C–OH2 + ), neutral (COH), or ionized
(CO− ) groups [9].
Activated carbon can be prepared using three main methods: chemical, physical and
physicochemical activations. Researchers used the chemical method at the beginning of the activated
carbon production era, but recently the physical and physicochemical methods are more preferred for
the production of activated carbon, especially from oil palm solid waste. Chemical activation is the
most widely used for the production as it provides a superior quality, high surface area, high porosity,
and higher carbon yield [10]. Activating agents such as KOH, ZnCl2 , K2 CO3 , and H3 PO4 are usually
used as they help to develop the pore structure of the activated carbon [11]. The most popular chemical
activating agents that were used for the activation of activated carbon are ZnCl2 and H3 PO4 . It inhibits
the tar formation and widens the porous structure of the activated carbon by increasing the carbon
yield. The chemical activation by KOH and K2 CO3 show different mechanism as the reaction with
carbon causes carbon gasification and the formation of hydrogen, which will not contribute to the
increase in carbon yield [12].
Controlling the activation process by chemical treatment will enable one to enhance and provide
higher specific surface properties to the resulting activated carbon [13]. In chemical activation, an
acidic or basic solution is used as the activating agent to produce a higher surface area and porosity [8].
There are several activating agents which are usually used in treating the OPSW such as H3 PO4 ,
K2 CO3 , KOH, ZnCl2 , and H2 SO4. The synthesis method will determine the resulting physicochemical
characteristics of the activated carbon as it depends on the activating agent, the amount of the precursor,
the condition of the activation process, and the raw materials used [7]. Proper chemical management
is needed to discharge the activating agent after sample treatment in order to prevent pollutions.
There are several methods that can be adapted to dispose of this highly polluting effluent, such as
the treatment system based on membrane technology [14], in situ solvent and reagent recycle by
Nanofiltration [15], or by solvent recycle with imperfect membranes by the separation method [16].
Thermal energy storage is an energy storage device that functions to develop a new energy source
which is very important to help in conserving energy which, in turn, reduces the negative impact
towards the polluted environment [17]. Phase change material (PCM) is the medium for latent heat
thermal energy storage in which the energy stored will be used based on energy supply and demand
when there is a change of phase caused by the freezing or melting processes [18]. Solid-liquid PCM such
as n-octadecane is very useful as it can store a large quantity of energy with small changes of volume. In
addition, it also possesses desirable properties such as a high latent heat, chemical inertness, no phase
segregation, and it is commercially available [19]. In the preparation of the SSPCM nano-composite,
the PCM was encapsulated into the activated carbon pores or inorganic frameworks to prevent any
leakage during the solid-liquid phase transition.
In this work, the preparation of activated carbon from palm kernel shell will be studied and the
resulting activated carbon will be subsequently used as inorganic frameworks for the preparation of
shape-stabilized phase change material (SSPCM) for the thermal energy storage (TES) application.
Parametric optimization for the preparation of activated carbon was done in order to obtain the highest
Nanomaterials 2018, 8, 689 3 of 14

graphitic content with the highest surface area and porosity. Three different parameters, namely,
activation temperature, activation holding time, and concentration of H3 PO4 were optimized.

2. Materials and Methods

2.1. List of Materials

Palm kernel shell (PKS), deionized water, orthophosphoric acid (85%) (SystermChemAR, Shah
Alam, Malaysia), ethyl alcohol (99.7%) (R&M Chemicals, Semenyih, Malaysia), and octadecane (99%)
(Aldrich Chemistry, St. Louis, MO, USA) were used in this work.

2.2. Pre-Treatment of Palm Kernel Shell

The palm kernel shell (PKS) samples were collected from the Seri Ulu Langat Palm Oil Mill,
Dengkil, Selangor, to be used as the precursor for the activated carbon production. The PKS was
cleaned using water, followed by de-ionized water. The sample was crushed into powder using a
stable arm grinder before it was treated with H3 PO4 . About 20 g of the precursor was weighted and
treated with 100 mL of freshly prepared H3 PO4 at various concentrations of H3 PO4 : 0%, 5%, 10%, 20%,
30%, and 40% (v/v) using 85% H3 PO4 . Treatment was done in a conical flask with the ratio of 1:5 of
20 g of PKS and 100 mL of freshly prepared H3 PO4 . After 24 h of treatment, the liquid was filtered off
using a filter paper and the sample was dried in an oven at 70 ◦ C for 24 h before it was used as the
precursor for AC preparation.

2.3. Sample Activation

An electrical tubular furnace was used in this one step activation with a constant flow rate of
nitrogen gas at 150 cm3 min−1 . The sample was activated in three different conditions based on the
parameters to be optimized and this will be described in the following section.

2.3.1. Carbonization Temperature

The PKS samples of about 5 g were carbonized using a tubular furnace under a nitrogen gas
environment. The sample treated with 20% H3 PO4 was chosen to study the effect of the carbonization
temperature on the physicochemical properties of the activated carbons. The sample was carbonized at
different temperatures: 500 ◦ C, 600 ◦ C, 700 ◦ C, 800 ◦ C, and 900 ◦ C for 2 h with a holding time at a 10 ◦ C
min−1 heating rate. The resulting PKSACs prepared were crushed using a mortar and pestle before
they were cleaned. The cleaned samples were oven-dried at 110 ◦ C for 24 h to remove any remaining
internal moisture. The samples were weighted and recorded again before they were kept in vials and
labelled as T500, T600, T700, T800, and T900 for the sample prepared at carbonization temperatures of
500 ◦ C, 600 ◦ C, 700 ◦ C, 800 ◦ C, and 900 ◦ C, respectively, for further used and various analyses.

2.3.2. Carbonization Holding Time

For this experiment, the sample that was treated with 20% of H3 PO4 was subsequently chosen
and carbonized at 500 ◦ C at different holding times: 1 h, 2 h, 3 h, 4 h, and 5 h at a 10 ◦ C min−1 heating
rate. The as-produced activated carbons were crushed using a mortar and pestle before they were
further cleaned. The cleaned samples were oven dried at 110 ◦ C for 24 h to remove any internal
moisture left during the preparation. The samples were then weighted and recorded again before they
were kept into vials and labelled as H1, H2, H3, H4, and H5 for holding times of 1 h, 2 h, 3 h, 4 h, and
5 h, respectively, for further used and various analyses.

2.3.3. Concentration of the Activating Agent, H3 PO4

Each treated sample that was prepared at different concentrations of H3 PO4 was carbonized at
500 ◦ C for 2 h of a holding time and at a 10 ◦ C min−1 heating rate. The resulting PKSACs were crushed
using a mortar and pestle before it was cleaned. The cleaned samples were then oven-dried at 110 ◦ C
Nanomaterials 2018, 8, 689 4 of 14

for 24 h to remove any remaining internal moisture. The samples were then weighted and recorded
again before they were kept into vials and labelled as C0, C5, C10, C20, C30 and C40 for treatment
with H3 PO4 at 0%, 5%, 10%, 20%, 30%, and 40%, respectively for further used and various analyses.

2.4. Preparation of Shape-Stabilized Phase Change Materials

A shape-stabilized phase change material (SSPCM) nano-composite was prepared by a simple
impregnation method. About 30 mL of absolute ethanol was used to dissolve melted n-octadecane by
heating above the melting temperature of n-octadecane above 28–30 ◦ C. The prepared PKSAC, C20 was
added into the n-octadecane solution and the solution was then stirred at 600 rpm for 4 h. The mixture
was oven-dried at 80 ◦ C for 48 h or until all the excess ethanol was evaporated. The SSPCM-C20
prepared was stored in a sample bottle for further used and characterization.

2.5. Characterization Method

The chemical characterization of PKSAC was carried out using the Raman spectroscopic method
with a WiTec Raman spectrometer (WiTec, Ulm, Germany) using a 514 nm laser. The intensity ratio
between the D-line (~1350 cm−1 ) and the G-line (~1597 cm−1 ) of the Raman spectra was used to
evaluate the graphitic character of the PKSAC. In this study, characterizations were done for all the
PKSACs prepared from the three different parameters: carbonization temperature, carbonization
holding time, and concentration of the activating agent.
The surface area and porosity of PKSAC and SSPCM nano-composites were determined using
the BET nitrogen gas adsorption–desorption method at 77 K using a Micromeratics Tristar II plus
(Micromeratics, Norcross, GA, USA). The method was also conducted to identify whether the PCM,
n-octadecane, can be impregnated into the newly prepared PKSAC pores or only adsorbed on the
surface. The samples were degassed at 290 ◦ C for 9 h under vacuum before the measurements
and the specific surface area and pore size distribution of the samples was determined using the
Brunauer-Emmet-Teller (BET) and BJH (Barret-Joyner-Halenda) Equations, respectively.
The chemical properties of the PKSAC and SSPCM nano-composites were carried out using
the fourier-transform infrared spectroscopy (FTIR) on a Perkin Elmer BX FTIR spectrophotometer
(Waltham, MA, USA) with the KBr method at room temperature. The absorbance was recorded from
400–4000 cm−1 .
The powder X-ray diffraction (PXRD) patterns of PKSAC, n-octadecane, and SSPCM were
obtained using a Shimadzu XRD-6000 PXRD (Kyoto, Japan) at room temperature with a scanning
range of 10–35◦ (2θ) and a scanning rate of 4◦ min−1 for all samples.
TGA/DTG thermal analyses were obtained using a Q500 V20.13 Build 39 (TA Instruments,
Lukens Drive, New Castle, DE, USA) to investigate the thermal stability of the PKSAC, n-octadecane
and SSPCM. The experiment was conducted using 10 mg of samples and heated under the nitrogen
atmosphere at a 5 ◦ C min−1 heating rate from room temperature to 1000 ◦ C.
The thermal storage properties, such as the melting temperature, freezing temperature and
enthalpy (latent heat) of the pure n-octadecane and SSPCM nano-composite were measured by a
differential scanning calorimeter (DSC), 822e, Mettler Toledo equipped with a refrigerated cooling
system. About 6 ± 1 mg of sample was weighed into an aluminium pan. Under a constant flow of
nitrogen atmosphere with the flow rate of 60 mL/min, the measurements were performed at −20
to 70 ◦ C for the heating cycle stage and 70 to −20 ◦ C for the cooling cycle stage. The encapsulation
efficiency of n-octadecane in the nano-composite s was calculated based on the enthalpy of pure
n-octadecane using the following equation:

PCM content in nano − composite (wt %) = (∆Hm /∆HPCM ) × 100 (1)

where ∆Hm is the enthalpy of melting of the SSPCM nano-composite (Jg−1 ) and ∆HPCM is the enthalpy
of melting for the pure n-octadecane (Jg−1 ).
Nanomaterials 2018, 8, 689 5 of 14

The external surface morphology and microstructure of the PKS, PKSAC and SSPCM
nano-composites were obtained using a Nova Nanosem 230 field emission scanning electron
microscope (FESEM). The dried samples were dispersed on a conductive carbon adhesive tape surface
that was attached to a FESEM stub and then gold-coated prior to the analysis.
To measure the chemical and thermal stability of the SSPCM nano-composite s to be used as
a TES material, a thermal cycling test was conducted. This test is very important in determining
a material’s service lifetime. The test was performed at a relative humidity of 70% which was
maintained constant using a climatic chamber (Weiss Umwelt Technik, UK) equipped with a K-type
thermocouple in the middle [20]. About 5 g of the dried SSPCM nano-composite was placed in contact
with the thermocouple in a chamber. The accuracy of the temperature measurement was 0.1 ◦ C.
The nano-composite was subjected to 1000 thermal cycles at temperatures below and above the melting
point of n-octadecane. Sampling was performed at 100, 300, 500, 700, and 1000 cycles. Changes in
the samples’ thermal properties and chemical stability after the thermal cycling test were determined
using the DSC and FTIR technique, respectively.
The leakage study was performed by keeping the SSPCM nano-composite inside an oven at
80 ± 5 ◦ C for 3 days (72 h). Before that, about 1 g of the nano-composite was weighed on a filter paper
and exposed to 30 ◦ C for 8 h to study the ability of the C20 to hold n-octadecane during the melting
phase. Then the samples were directly placed into an oven at 80 ± 5 ◦ C for 3 days. The weight and the
latent heat of the sample after the exposure period were recorded.

3. Results and Discussion

3.1. Raman Spectroscopy

The PKSAC samples were analyzed using the Raman spectroscopy to identify the graphitic
character of the samples. The Raman spectra of all the PKSAC samples show two sharp peaks; a D
band at around 1350 cm−1 and a G band at around 1597 cm−1 (Refer Figure S1: Raman spectra of
PKSAC). The G band indicates the presence of a sp2 carbon network graphite-like structure which
composed of either C=C chains or aromatic ring structures. The D band in the Raman spectrum is due
to the disordered graphite structure which refers to defects of the graphitic characteristics that also
exists in all the PKSAC samples.
Figure 1a presents the plot of IG /ID versus temperature (◦ C) which shows that the graphitic
character in the resulting PKSAC sample decreased almost linearly with the increased of the activation
temperature. The highest graphitic content for the carbonization temperature is 500 ◦ C with an IG /ID
value of 1.166 followed by 600 ◦ C (1.106), 700 ◦ C (1.034), 800 ◦ C (0.963) and the lowest temperature of
900 ◦ C (0.933). The graphitic value was found to decrease as the carbonization temperature increased
and this is due to the reduction of amorphous carbon and the increase of the disorder aromatic carbon
during the carbonization process [21].
Figure 1b presents the plot of IG /ID against the holding time (h), which shows that no specific
trend was observed between the graphitic characters in the PKSAC samples to the holding time.
The highest value was obtained at 0.842 for the H2 sample followed by H4 (0.822), H5 (0.809), H1
(0.787), and H3 (0.754), the lowest. From the result, it is clear that the best holding time for the
preparation of PKSAC with a high graphitic character is 2 h.
Figure 1c shows a plot of the IG /ID value of PKSAC against a concentration of H3 PO4 (% w/w)
used for the activating agent for the PKSAC, indicating different graphitic contents of different samples
of PKSAC. The highest graphitic character was observed for the sample prepared without any H3 PO4
treatment, C0 (untreated sample) with a value of 1.5, followed by C5 (1.364), C10 (1.309), C20 (1.305),
C30 (1.272), and C40 with the value of 1.074. Generally, it shows that the graphitic content of the PKSAC
is indirectly proportional to the concentration of H3 PO4 . The higher the concentration, the lower the
graphitic content in the resulting PKSAC and the weaker the physical structure of the sample.
Nanomaterials 2018, 8, 689 6 of 14
Nanomaterials 2018, 8, x FOR PEER REVIEW 6 of 15

1.6
1.2 0.86 0.842 1.500
1.166 1.5
1.15 1.106 0.84 1.364
0.822 1.4
1.1 0.82 0.809 1.309 1.305 1.272
1.034

G D

IG/ID
1.05 1.3
IG/ID

I /I
0.963 0.8
1 0.787 0.754 1.2 1.074
0.95 0.933 0.78
0.9 0.76 1.1
500 600 700 800 900 0.74 1
1 2 3 4 5 0 10 20 30 40
Temperature (oC) Holding Time (h) Concentration of H3PO4 (%)

(a) (b) (c)

Figure 1. The plot of the IG/ID against (a) carbonization temperature, (b) holding time, and (c)
The plot of
Figure 1.concentration ofHthe I of/I
3PO4 G
against carbons.
D activated
the (a) carbonization temperature, (b) holding time, and (c)
concentration of H3 PO4 of the activated carbons.
3.2. Surface Area and Porosity
3.2. Surface Area and Porosity
3.2.1. Activated Carbon Framework
3.2.1. Activated Carbonadsorption-desorption
The nitrogen Framework isotherms of the three different parameters—carbonization
Thetemperature, holding time, and concentration
nitrogen adsorption-desorption isotherms of the three
of the activator—are
differentshown in Figure 2a–c,
parameters—carbonization
respectively (Refer Figure S2: Adsorption-desorption isotherms). This study was carried out in order
temperature, holding time, and concentration of the activator—are shown in Figure 2a–c, respectively
to get the highest surface area of the activated carbon for each of the parameters studied and finally
(Refer Figure
identifyS2:theAdsorption-desorption
optimum temperature, activation isotherms). Thistime,
holding studyand was thecarried out in order
concentration of H3PO to4get the
highest treatment,
surface area in theof preparation
the activated carbon
of the highestforspecific
each of the parameters
surface studied carbon.
area of the activated and finally
All theidentify
the optimum
samples temperature,
are dominated activation
by the Typeholding
1 isothermtime,(according
and the concentration of H3 PO4 treatment,
to the IUPAC classification) for all the in the
parameters used in this study. The isotherm indicates that the AC is dominated
preparation of the highest specific surface area of the activated carbon. All the samples are dominated by microporous-rich
texture mixed with some of the mesopores with the highest BET specific surface area of 1168 m2 g−1
by the Type 1 isotherm (according to the IUPAC classification) for all the parameters used in this study.
for the sample treated with 20% H3PO4 (C20).
The isothermFigure
indicates that the AC is dominated by microporous-rich texture mixed with some of the
2a shows the BET surface area of AC that was activated at 500 °C, which shows the
mesopores with the highest
highest value. The surface BETarea
specific
of the surface area offrom
ACs decreased 1168770 m2mg2 −g1−1 for themsample
to 464 2 g−1 andtreated
237 m2 g with
−1 20%
H3 PO4 (C20).
when it was carbonized at 600 and 700 °C. At 800 and 900 °C, the surface area increased to 572 m g 2 −1

and 2a
Figure 679shows
m2 g−1, the
respectively.
BET surfaceThis shows
area ofthatAC500 °C was
that was the at 500 ◦ C,towhich
best temperature
activated prepareshowsthe highest
the highest
value. The surface area of the ACs decreased from 770 m g to 464 m g and 237reduce
surface area of the AC. This relatively low temperature of
2 carbonization
− 1 is
2 also
− 1 good to m2 g−the 1 when it
use of energy which will reduce the cost of manufacturing.
was carbonized at 600 and 700 ◦ C. At 800 and 900 ◦ C, the surface area increased to 572 m2 g−1 and
Similar to the carbonization holding time as shown in Figure 2b, a carbonization holding time
−1 , respectively. This shows that 500 ◦ C was the best temperature to prepare the highest
679 m2 gless or more than 2 h results in a lower BET surface area value. It shows that a 1 h holding time is not
surface area
enough of the
timeAC. This relatively
to manufacture low temperature
more pores in the AC and of carbonization
when the samples were is also good
treated fortomore
reduce
thanthe use
of energy which
2 h, the BETwill reduce
surface areathe
andcost of manufacturing.
porosity value reduced with the increasing holding time. The sample
was overtreated,
Similar which destroyed
to the carbonization the pore
holding timeformation
as shownof the inAC. The overtreated
Figure samples extend
2b, a carbonization the time
holding
size of the pores from micro- to meso- and macro-pores sizes, which reduced
less or more than 2 h results in a lower BET surface area value. It shows that a 1 h holding time is not the surface area and
porosity of the AC. In other words, the porous structure development does not reach its optimum
enough time to manufacture more pores in the AC and when the samples were treated for more than
treatment when the H3PO4 concentration and activation holding time are lower or higher than the
2 h, the BET
valuessurface
of 20% H area and porosity value reduced with the increasing holding time. The sample
3PO4 and a 2 h holding time.

was overtreated, which

The same destroyed
result is shown thewithpore formation ofofthe
the concentration the AC.
H3POThe overtreated
4 parameter (Figure samples extend the
2c) in which
the pores
size of the BET surface
fromareamicro-of thetoAC treated
meso- with
and 20% H3PO4 resulted
macro-pores sizes, in the highest
which reduced surface
thearea and this
surface area and
porositywas subsequently
of the AC. In other used as the frameworks
words, the porous for structure
the encapsulation of the PCM,
development does n-octadecane,
not reach for its the
optimum
formation of a shape-stabilised PCM (SSPCM).
treatment when the H3 PO4 concentration and activation holding time are lower or higher than the
values of 20% H3 PO4 and a 2 h holding time.
The same result is shown with the concentration of the H3 PO4 parameter (Figure 2c) in which
the BET surface area of the AC treated with 20% H3 PO4 resulted in the highest surface area and this
was subsequently used as the frameworks for the encapsulation of the PCM, n-octadecane, for the
formation of a shape-stabilised PCM (SSPCM).
Nanomaterials 2018, 8, 689 7 of 14
Nanomaterials 2018, 8, x FOR PEER REVIEW 7 of 15

BET Surface area (m2g-1)

1200 1400

BET Surface area (m2g-1)

BET Surface area (m2g-1)
900 770 969 1169
800 679 1000 1200
700 5 800 605 1000
600 464 486 661
500 600 546 510 800
400 237 600 307 406
300 400 400 183 203
200 200 200
100
0 0 0
500 600 700 800 900 1h 2h 3h 4h 5h 0 5 10 20 30 40
Temperature (oC) Holding time (h) Concentration of H3PO4

(a) (b) (c)

Figure 2. The plot of the Brunauer-Emmett-Teller surface area against (a) the carbonization
The plot of
Figure 2.temperature,(b) the Brunauer-Emmett-Teller
holding time, and (c) the amount of Hsurface area against (a) the carbonization
3PO4 used as the chemical activator for the

temperature,(b) holding
preparation of Palmtime,
kerneland
shell(c) the amount
activated carbon. of H3 PO4 used as the chemical activator for the
preparation of Palm kernel shell activated carbon.
Based on the parametric optimization for the preparation of PKSAC to be used as a framework
for on
Based PCM,theit parametric
was found that activation at 500
optimization for°C,
thewith a 2 h activation
preparation holding time
of PKSAC to bewith
usedH3PO
as 4aofframework
20%
for PCM,treatment resulted
it was found in the
that highest surface
activation at 500 area and welldeveloped
◦ C, with porosity.
a 2 h activation holding time with H3 PO4 of 20%
treatment3.2.2.
resulted in the highest
Shape-Stabilized Phasesurface area and welldeveloped porosity.
Change Material
The preparation
3.2.2. Shape-Stabilized Phaseof SSPCM-C20 was done by the impregnation of n-octadecane into the pores of
Change Material
activated carbon, C20. The BET surface area and porosity analysis for SSPCM-C20 was conducted to
Theidentify
preparation of SSPCM-C20
the surface was done
properties changes beforebyand
theafter
impregnation of n-octadecane
the encapsulation into the pores of
process. The SSPCM-C20
activatednano-composite
carbon, C20. was Thedegassed
BET surfaceat 290area
°C for 9 h porosity
and under a vacuum
analysis before
for the specific surface
SSPCM-C20 wasarea and
conducted to
poresurface
identify the size distribution
properties by using
changesthe Brunauer-Emmet-Teller
before and after the (BET) and BJH (Barret-Joyner-Halenda)
encapsulation process. The SSPCM-C20
equations were measured. The result shows that the adsorption-desorption isotherms transformed
nano-composite was degassed at 290 ◦ C for 9 h under a vacuum before the specific surface area and
from the Type I in the AC-20 to the Type III in the SSPCM-C20 as shown in Figure 3a, indicating that
pore sizethe
distribution
nano-composite by using
is of a the Brunauer-Emmet-Teller
nonporous material. This material (BET) and BJH
is parallel with(Barret-Joyner-Halenda)
almost no pore size
equations were measured. The result shows that the adsorption-desorption
distribution that can be clearly observed for SSPCM-C20 compared to C20 as shown isotherms transformed
in Figure 3b.
from theThe
TypeBET I in the AC-20
surface to the
area, total poreType III in
volume, andthe SSPCM-C20
pore diameter of theas shown
former are in 2Figure
m g , 3a,
2 −1 0.012indicating
cm3 g−1, that
and 51 Å, respectively.
the nano-composite is of a nonporous material. This material is parallel with almost no pore size
This result
distribution that can be indicates
clearlythat there arefor
observed huge physical changes
SSPCM-C20 of the C20
compared to C20 (as the
as host)
shown before the
in Figure 3b.
encapsulation of the PCM for the formation of the SSPCM-C20, after the PCM (as2 the − 1guest) was 3 −1
The BET surface area, total pore volume, and pore diameter of the former are 2 m g , 0.012 cm g ,
encapsulated into the pores of AC. The encapsulation caused a reduction of the BET surface area and
and 51 Å,porosity,
respectively.
as well as the transformation from a microporous material to a nonporous material, as
Thisindicated
result indicates that there are huge
by the adsorption-desorption physical
isotherm changes
from Type of the
I to Type III. C20
These(as the host)
changes before the
happened
encapsulation
becauseof thethe PCM
pores for were
of C20 the formation
fully occupiedof by
thetheSSPCM-C20,
n-octadecane after theencapsulation
after the PCM (as the guest) was
process.
This result
encapsulated into clearly proves
the pores of that
AC.theTheSSPCM-C20 nano-composite
encapsulation caused awas successfully
reduction of fabricated by the area
the BET surface
impregnation of n-octadecane into the pores of C20 frameworks.
and porosity, as well as the transformation from a microporous material to a nonporous material, as
The size of a single n-octadecane molecule was estimated using the Pymol software. The 3D
indicatedmolecular
by the adsorption-desorption isotherm from Type I to Type III. These changes happened
structure of n-octadecane had a maximum energy of 44.4874 KJ mol−1 with a size of (20.7 ×
because 1.8
the×pores
1.8) Å.of C20
This sizewere
provesfully
thatoccupied
n-octadecaneby can
theben-octadecane
impregnated into after thethe encapsulation
pores of the activated process.
This result clearly
carbon proves that
that dominate withthe SSPCM-C20
a 12.85 nano-composite was successfully fabricated by the
Å pore diameter.
impregnation of n-octadecane into the pores of C20 frameworks.
The size of a single n-octadecane molecule was estimated using the Pymol software. The 3D
molecular structure of n-octadecane had a maximum energy of 44.4874 KJ mol−1 with a size of
(20.7 × 1.8 × 1.8) Å. This size proves that n-octadecane can be impregnated into the pores of the
activated carbon that dominate with a 12.85 Å pore diameter.
Nanomaterials 2018, 8, x FOR PEER REVIEW 8 of 15

Nanomaterials 2018, 8, 689 8 of 14

Nanomaterials 2018, 8, x FOR PEER REVIEW 8 of 15

(a) (b)
Figure 3. The (a) adsorption-desorption isotherm and (b) pore distribution of the activated carbon
(a)
(C20) and its Shape-stabilized phase change material (SSPCM-C20). The (b) insets show the expanded
y-axis.
Figure 3.
Figure 3. The
The(a)(a)adsorption-desorption
adsorption-desorption isotherm
isotherm and
and (b) (b) pore
pore distribution
distribution ofactivated
of the the activated carbon
carbon (C20)
(C20) and its Shape-stabilized
and its Shape-stabilized phase phase change material (SSPCM-C20). The insets show the expanded
change material (SSPCM-C20). The insets show the expanded y-axis.
3.3. Fourier-Transform Infrared Spectroscopy
y-axis.
The chemical characterization
3.3. Fourier-Transform of the C20, n-octadecane, and SSPCM-C20 was carried out using
Infrared Spectroscopy
3.3. Fourier-Transform Infrared Spectroscopy
the FTIR spectroscopy as shown in Figure 4. The main absorption band of C20 is observed in the
The chemical characterization of the C20, n-octadecane, and SSPCM-C20 was carried out using
region ofchemical
3650–2500 cm−1 due to the O–H stretching presumably due to H3POwas 4 treatment used and
the FTIR spectroscopy as shown inofFigure
The characterization the C20, n-octadecane,
4. The and SSPCM-C20
main−1absorption band of C20 iscarried observedout in
using
the
adsorbed
the FTIR moisture.
spectroscopy Theas
− 1 bands
shown at
in 1635
Figure and 4. 1537
The cm
main correspond
absorption to
band the
of C=C
C20 isstretching
observed of the
in the
region of 3650–2500 cm due to the O–H stretching presumably due to H3 PO4 treatment used and
aromatic
region ring carboncm
of moisture.
3650–2500 of−1the
duepolycyclic
to1635
the O–H aromatic hydrocarbons
stretching presumably thatdueforms
to Hthe PObasic structural
4 treatment
unit of
adsorbed The bands at and 1537 cm−1 correspond to the C=C 3stretching of theused and
aromatic
activated
adsorbed carbons. The absorption bands at 1463 cm −1 and 1385 cm−1 are due to the CH2 bending
carbonmoisture. The bands at 1635 and 1537 cm correspond to the C=C stretching of the
−1
ring of the polycyclic aromatic hydrocarbons that forms the basic structural unit of activated
vibrations.
carbons. The absorption bands at 1463 cm and 1385 cm are due to the CH2 bending vibrations.of−1
aromatic ring carbon of the polycyclic aromatic
− 1 hydrocarbons
− 1 that forms the basic structural unit
The carbons.
activated FTIR spectra The ofof n-octadecane
absorption exhibit
bandsexhibit
at 1463C–H C–H stretching
cm−1stretching
and 1385 in in −1the
cm region of 2975–2850 cm
The FTIR spectra n-octadecane theare due to
region of the CH2 bending
2975–2850 cm–1−1
corresponding
vibrations. to the main absorption band for the n-octadecane. The absorption band at 1470 cm is
corresponding to the main absorption band for the n-octadecane. The absorption band at 1470 cm–1
due Theto the CH 2 bending vibration in n-octadecane. The FTIR spectrum of the SSPCM-C20
is due to FTIR
the CH spectra of n-octadecane exhibit C–H stretching in the region of 2975–2850 cm−1
2 bending vibration in n-octadecane. The FTIR spectrum of the SSPCM-C20
nano-composite
corresponding toshows shows
the main the combination
absorption band of O–H
for and and C–H stretching
the n-octadecane. that corresponds to –1the
nano-composite the combination of O–H C–H stretchingThe thatabsorption
corresponds band at 1470
to the cm
absorption is
absorption
due to the band
CH in C20
bending and the n-octadecane.
vibration in Based
n-octadecane. on the
The FTIR
FTIR spectra,
spectrum no chemical
of the interaction
SSPCM-C20
band in C20 and the n-octadecane. Based on the FTIR spectra, no chemical interaction between
2
between the n-octadecane
nano-composite and C20 can be observed. The C–H
possible interaction is corresponds
due to capillary to and
the n-octadecane shows and C20 thecancombination
be observed.ofThe O–H and
possible stretching
interaction is duethatto capillary and surface the
surface
absorption tension
band forces
in C20between
and the the AC and
n-octadecane. the paraffin,
Based on where
the the
FTIR forces
spectra, prevent
no the
chemical liquid leakage
interaction
tension forces between the AC and the paraffin, where the forces prevent the liquid leakage of the
of the melted
between n-octadecane.
the n-octadecane and C20 can be observed. The possible interaction is due to capillary and
melted n-octadecane.
surface tension forces between the AC and the paraffin, where the forces prevent the liquid leakage
of the melted n-octadecane.

Figure4.4.The
Figure TheFTIR
FTIRspectra
spectraofofC20,
C20, n-octadecane,
n-octadecane, andand SSPCM-C20
SSPCM-C20 (the(the symbols
symbols on the
on the FTIRFTIR spectra
spectra are
are assigned
assigned to FTIR
to the the FTIR adsorption
adsorption peak;peak; (*) 3430
(?) 3430 cm−cm −1 , (#)
1 , (#) 2919
2919 cmcm−1 ,,(3)
−1 ( )2360
2360cm
cm−1,, ((♥)) 1635
−1
1635cmcm−. 1 ,
−1

(∆) 14704.cm −1
Figure The .FTIR spectra of C20, n-octadecane, and SSPCM-C20 (the symbols on the FTIR spectra
are assigned to the FTIR adsorption peak; (*) 3430 cm−1, (#) 2919 cm−1, ( ) 2360 cm−1, ( ) 1635 cm−1.
Nanomaterials 2018, 8, x FOR PEER REVIEW 9 of 15
Nanomaterials 2018, 8, 689 9 of 14
( ) 1470 cm-1).

3.4. X-ray Diffraction

3.4. X-ray Diffraction
The XRD patterns
The XRD patterns of of C20,
C20,n-octadecane,
n-octadecane,and
andthetheSSPCM-C20
SSPCM-C20 nano-composite
nano-composite areare displayed
displayed in
in Figure 5. The C20 was analyzed at room temperature while the n-octadecane
Figure 5. The C20 was analyzed at room temperature while the n-octadecane and SSPCM-C20 were and SSPCM-C20
were analyzed
analyzed ± 527°C±in
at 27 at 5 ◦order
C in order to maintain
to maintain the solid
the solid phasephase
of PCM of PCM
whilewhile we acquired
we acquired the data.
the data. The
The result shows that there were no XRD peaks for the C20, as the material used in
result shows that there were no XRD peaks for the C20, as the material used in this study is of an this study is of
an amorphous type. In contrast, an XRD pattern for the SSPCM-C20 nano-composite
amorphous type. In contrast, an XRD pattern for the SSPCM-C20 nano-composite is observed at 2θ = is observed
at
19°, = 19◦and
2θ 23°, , 23◦25°, 25◦ , which
, andwhich belongs
belongs to n-octadecane
to n-octadecane duedue
to to
its its crystallizationininthe
crystallization the solid
solid phase
phase
condition.
condition. It can be seen that the XRD pattern of the SSPCM-C20 resembles that of the C20 and the
It can be seen that the XRD pattern of the SSPCM-C20 resembles that of the C20 and the
n-octadecane. This infers
n-octadecane. This infers that
that the
the n-octadecane
n-octadecane was
was successfully
successfully impregnated
impregnated intointo the
the pores
pores ofof C20.
C20.

Figure 5. The X-Ray Diffraction patterns of C20, n-octadecane, and SSPCM-C20.

3.5. Thermal Properties

The TGA/DTG analysis was
TGA/DTG analysis was usedused to to study
study the thermal stability of the SSPCM-C20. For the TES
application, the thermal stability of of the
the material
material isis very
very important.
important. Figure
Figure 6a–c
6a–cshow
showthetheTGA/DTG
TGA/DTG
thermograms of C20, n-octadecane, and SSPCM-C20. C20 shows no thermal decomposition of the
sample below 512 ◦°C, C, however, a decomposition was observed from this temperature up to 861 861 ◦°C
C
due to ◦
to further
furtherpyrolysis.
pyrolysis.ThisThisis is
because
because thethe
carbonization
carbonization of C20 was was
of C20 donedoneat only
at 500
only C. This
500 °C.result
This
indicates that the ACthe produced is thermally stable stable
up to up513to ◦ C. The C20 is thermally stable until
result indicates that AC produced is thermally 513 °C. The C20 is thermally stable
500 ◦
until C500and
°Cable
andtoable
be used
to beasused
a supporting materialmaterial
as a supporting for PCM. forInPCM.
contrast, the n-octadecane
In contrast, shows a
the n-octadecane
weight ◦ C, which is due to the evaporation of n-octadecane. The SSPCM-C20
shows aloss between
weight loss94.00–253.7
between 94.00–253.7 °C, which is due to the evaporation of n-octadecane. The
nano-composite exhibits a similar
SSPCM-C20 nano-composite exhibits thermal
a similarstability
thermal tostability
that of C20.
to thatInofgeneral, the weight
C20. In general, loss of
the weight
the
loss SSPCM-C20
of the SSPCM-C20nano-composite
nano-composite agreesagrees
well with
well the
withonethe obtained
one obtainedfromfromthe DSC result
the DSC with
result an
with
encapsulation
an encapsulation efficiency of 32%.
efficiency of 32%.
Table 11 shows
shows the the percentage
percentage weightweight lossloss of
of C20,
C20, n-octadecane,
n-octadecane, and and SSPCM-C20
SSPCM-C20 upon being
subjected to ◦ C. The result shows that C20 exhibits
tothermal
thermaltreatment
treatment fromfrom roomroomtemperature
temperatureto 1000
to 1000 °C. The result shows that C20
aexhibits
25.08% weight
a 25.08% loss;weight
8.49% from
loss;the evaporation
8.49% from the of water and 16.59%
evaporation of from
watertheanddecomposition
16.59% from of C20
the
at temperatures of higher ◦
decomposition C20 than 500 C. It washigher
at temperatures foundthan
that 100%
500 °C. of pure
It wasn-octadecane
found thatwas evaporated,
100% of pure
while SSPCM-C20
n-octadecane was shows a total while
evaporated, weightSSPCM-C20
loss of 51.16%, witha3.22%
shows due to the
total weight lossevaporation
of 51.16%, of moisture,
with 3.22%
31.96% due to the evaporation of n-octadecane, and 15.98% due to the
due to the evaporation of moisture, 31.96% due to the evaporation of n-octadecane, and 15.98% due decomposition of C20 at
temperatures higher than
to the decomposition of C20 ◦
518at C in the SSPCM-C20.
temperatures higher than 518 °C in the SSPCM-C20.
Nanomaterials 2018, 8, 689 10 of 14
Nanomaterials 2018, 8, x FOR PEER REVIEW 10 of 15

(a) (b) (c)

Figure 6. The Thermogravimetric analysis thermograms of (a) C20, (b) n-octadecane and (c)
Figure 6. The Thermogravimetric analysis thermograms of (a) C20, (b) n-octadecane and
SSPCM-C20.
(c) SSPCM-C20.
Table 1. The thermal properties of n-octadecane, C20, and SSPCM-C20 derived from Thermogravimetric
Table 1.
analysis The thermal properties of n-octadecane, C20, and SSPCM-C20 derived from
thermograms.
Thermogravimetric analysis thermograms.
Sample Name T1–T2 (oC) Tm (°C) Δm (mg) Weight Loss (%) Total Weight Loss (%)
34–109 75 0.89 8.49
SampleC20 Name T1 –T2 (o C) Tm (◦ C) ∆m (mg) Weight Loss (%) Total 25.08
Weight Loss (%)
513–861 796 1.74 16.59
n-octadecane 34–109
94–273 26175 0.89
10.69 100.008.49 100.00
C20 25.08
513–861 796 1.74 16.59
47–87 58 0.34 3.22
n-octadecane
SSPCM-C20 94–273
115–263 261
193 10.69
3.38 100.00
31.96 100.00
51.16
518–853
47–87 761
58 1.69
0.34 15.983.22
SSPCM-C20 115–263 193 3.38 31.96 51.16
518–853
3.6. Differential Scanning Calorimetry 761 1.69 15.98

The melting and freezing activity of the PCM was characterized using the differential scanning
3.6. Differential
calorimeter Scanning Calorimetry
(DSC) method. Figure 7 shows the DSC curves of the C20, n-octadecane, and
SSPCM-C20. The DSC thermogram shows no activity of melting and freezing for C20 due to the
The melting and freezing activity of the PCM was characterized using the differential scanning
absence of n-octadecane. In contrast, the DSC thermograms for n-octadecane and SSPCM-C20 shows
calorimeter (DSC) method. Figure 7 shows the DSC curves of the C20, n-octadecane, and SSPCM-C20.
peaks of solid-liquid melting and liquid-solid freezing which indicate that heat was absorbed and
The released
DSC thermogram shows
for n-octadecane andno activity ofThe
SSPCM-C20. melting and freezing
pure n-octadecane for sharper
shows C20 due to the
peaks absence of
compared
n-octadecane.
to SSPCM-C20.In contrast, the DSC
This is because the thermograms
AC that acted asfor n-octadecane
a framework and
for the SSPCM-C20
n-octadecane shows peaks of
in SSPCM-C20
solid-liquid
exhibits melting
a higherand liquid-solid
adsorption freezing
capability which to
compared indicate that heat
n-octadecane, was increases
which absorbedthe andcapillary
released for
effect andand
n-octadecane surface tension forces
SSPCM-C20. Thebetween the n-octadecane
pure n-octadecane shows and the porous
sharper peaksnetwork of the
compared to AC and
SSPCM-C20.
This hinders
is becausethe the
molecular
AC that motion
actedofasn-octadecane
a framework during then-octadecane
for the melting and freezing processes.
in SSPCM-C20 exhibits a higher
adsorptionThecapability
supercooling effect of to
compared then-octadecane,
nano-compositewhich
was calculated
increasesbythethecapillary
differenceeffect
between
andthesurface
melting point and the freezing temperature of the sample. The SSPCM nano-composite shows the
tension forces between the n-octadecane and the porous network of the AC and hinders the molecular
melting and freezing temperatures of 28.8 °C and 26.8 °C, respectively, corresponding to the latent
motion of n-octadecane
Nanomaterials during
2018, 8, x FOR PEER the melting and freezing processes.
REVIEW 11 of 15
heat values of −87.42 Jg−1 and 84.31 Jg−1, respectively, indicating a very low supercooling effect. It also
shows that pure n-octadecane and SSPCM-C20 have similar thermal properties, which indicates that
there is no chemical reaction between them. This finding infers that n-octadecane was successfully
impregnated into the pores of C20.

Figure 7.
Figure 7. The
The Differential
Differential scanning
scanning calorimeter
calorimeter thermograms
thermograms of
of C20,
C20, n-octadecane
n-octadecane and
and SSPCM-C20.
SSPCM-C20.

3.7. Surface Morphology

Figure 8 shows the FESEM images of the PKS, C20, and SSPCM-C20 which show different
morphologies of the samples. Figure 8a shows the morphology of the PKS, which was used as the
precursor for the preparation of activated carbon. The resulting activated carbon prepared from
PKS, activated using H3PO4, and carbonized at 500 for 2 h shows a well-developed porous structure
Nanomaterials 2018, 8, 689 11 of 14

The supercooling effect of the nano-composite was calculated by the difference between the
melting point and the freezing temperature of the sample. The SSPCM nano-composite shows the
melting and freezing temperatures of 28.8 ◦ C and 26.8 ◦ C, respectively, corresponding to the latent heat
values of −87.42 Jg−1 and 84.31 Jg−1 , respectively, indicating a very low supercooling effect. It also
shows that pure n-octadecane and SSPCM-C20 have similar thermal properties, which indicates that
there is no chemical reaction between them. This finding infers that n-octadecane was successfully
impregnated into the pores of C20.
Figure 7. The Differential scanning calorimeter thermograms of C20, n-octadecane and SSPCM-C20.
3.7. Surface Morphology
3.7. Surface
Figure Morphology
8 shows the FESEM images of the PKS, C20, and SSPCM-C20 which show different
morphologies of the samples.
Figure 8 shows the FESEM Figure 8a shows
images of thethe morphology
PKS, of the PKS,which
C20, and SSPCM-C20 which wasdifferent
show used as the
precursor for the preparation
morphologies of the samples.ofFigure
activated carbon.
8a shows The resulting
the morphology activated
of the carbon
PKS, which was prepared
used as thefrom
precursor for
PKS, activated usingtheHpreparation
3 PO4 , and of activated carbon.
carbonized The2 h
at 500 for resulting
shows aactivated carbon prepared
well-developed porous from
structure
PKS, activated
with quite a similarusing
shape H3and
PO4, size
and carbonized
with variousat 500 forsizes
pore 2 h shows a well-developed
as shown porous
in Figure 8b. As astructure
result of the
with quite of
encapsulation a similar shape and
n-octadecane sizethe
into with various
pores pore sizes as
of activated shownn-octadecane
carbon, in Figure 8b. As a result
was of the into
absorbed
encapsulation of n-octadecane into the pores of activated carbon, n-octadecane was absorbed into
the porous networks of C20 and completely dispersed and occupied homogeneously into the pores,
the porous networks of C20 and completely dispersed and occupied homogeneously into the pores,
resulting in the absence of pores.
resulting in the absence of pores.

(a) (b) (c)

Figure 8. The Field Emission Scanning Electron Microscopy surface morphology images of (a) PKS
Figure 8. The Field Emission Scanning Electron Microscopy surface morphology images of (a) PKS
(50000× magnification), (b) C20 and (c) SSPCM-C20 (viewed under 10,000× magnification).
(50000× magnification), (b) C20 and (c) SSPCM-C20 (viewed under 10,000× magnification).
The n-octadecane was uniformly distributed into the pores of AC due to the capillary effect and
The n-octadecane
surface was
tension forces uniformly
between distributed
n-octadecane intopores
and the the pores
of AC.of
In AC due to
addition, thethe capillary
surface effect and
adsorption
surface tension forces between n-octadecane and the pores of AC. In addition, the surface adsorption
of n-octadecane on C20 cannot be ruled out. The porous structure of the C20 provides a mechanical
of n-octadecane on prevented
strength which C20 cannot thebe ruledofout.
escape The porous
the melted structure of the C20 provides a mechanical
n-octadecane.
strength which prevented the escape of the melted n-octadecane.
3.8. Leakage Study
3.8. Leakage Study
The purpose of this test is to see the ability of the C20 to hold n-octadecane at temperatures over
The purposetemperature
the melting of this test of
is n-octadecane. The of
to see the ability filter
thepaper
C20 toshows
holdno leakage, i.e., at
n-octadecane notemperatures
oily marks on over
the paper and the sample is still in a dry condition after being exposed to 30
the melting temperature of n-octadecane. The filter paper shows no leakage, i.e., no oily °C for 8 h.marks
Table on
2 the
summarizes the weight and latent heat of the SSPCM-C20 nano-composites before and after the
paper and the sample is still in a dry condition after being exposed to 30 ◦ C for 8 h. Table 2 summarizes
leakage study. The weight after it was exposed to 80 °C for 3 days shows a reduction of 0.0409 g from
the weight and latent heat of the SSPCM-C20 nano-composites before and after the leakage study.
The weight after it was exposed to 80 ◦ C for 3 days shows a reduction of 0.0409 g from 1 g of SSPCM-C20
used in this study. This insignificant difference of weight indicates that no leakage happened during
the study. The latent heat of SSPCM-C20 before and after the leakage study also shows no significant
difference. This is because the wall of the pores and n-octadecane provide strong adhesive forces
that are built from a strong covalent bond that prevents any seepage of liquefied n-octadecane.
Table 2 shows that the loading of n-octadecane is 34%, which is equivalent to the PCM that managed
to be loaded into the pores of the activated carbon. This loading percentage of n-octadecane is similar
to the weight loss percentage of n-octadecane in the TGA analysis. This result reconfirmed that the
Nanomaterials 2018, 8, 689 12 of 14

n-octadecane successfully penetrated and was encapsulated into the pores structure of PKSAC with a
34% loading value.

Table 2. The weight and latent heat of the SSPCM-C20 nano-composites before and after the
leakage study.

BET Surface Pore Volume Pore Diameter PCM Loading Latent Heat Before (J g−1 ) Latent Heat After (J g−1 )
Sample
Area (m2 g−1 ) (cm3 g−1 ) (Å) (%) ∆Hm a (J g−1 ) ∆Hc b (J g−1 ) ∆Hm c (J g−1 ) ∆Hc d (J g−1 )
SSPCM-20 2 0.012 51 33.62 −87.42 84.31 −85.31 84.13
a enthalpy on the DSC melting curve before the leaching test; b enthalpy on the DSC freezing curve before the
leaching test; c enthalpy on the DSC melting curve after the leaching test; and d enthalpy on the DSC freezing curve
after the leaching test.

3.9. Thermal Cycling Test

The thermal cycling test was performed to investigate the physical and chemical stability of the
SSPCM-C20 nano-composite when it was exposed to temperature changes. The repeated cycles of
the temperature change the thermal behaviour of the material. Changes in the thermal behaviour
of the nano-composite will affect its application as a TES. The number of cycles that the sample was
able to withstand imitates the life-spend of the materials. For example, if there are no changes in the
chemical or thermal properties of the nano-composite after 1000 cycles, the composite can be used
in the building material to reduce and maintain the internal temperature for a minimum of 3 years.
The higher cycle the SSPCM-C20 nano-composite can withstand, the better its application as a TES for
building applications.
Figure 9 shows the DSC thermograms (a) and FTIR spectra (b) of SSPCM-C20 after 100–500 cycles.
The DSC thermograms show peaks of solid-liquid melting and liquid-solid freezing for 100–500 cycles.
After 300 cycles, the melting and freezing peaks of the nano-composite were reduced, compared to
100 cycles. No melting and freezing activity for SSPCM-C20 was observed after 500 cycles. The peak
keeps reducing until it disappeared at 500 cycles, which indicated that there are changes in the thermal
properties of the SSPCM-C20 nano-composite. The FTIR spectra of the SSPCM-C20 nano-composite
after 100, 300, and 500 cycles show similar FTIR features, indicating a similar chemical structure and
that no chemical
Nanomaterials 2018, 8,reaction between
x FOR PEER the C-20 and n-octadecane can be clearly observed.
REVIEW 13 of 15

(a) (b)
Figure 9.9. The
Figure The (a)
(a)DSC
DSCthermograms
thermograms and
and (b)
(b) FTIR
FTIR spectra
spectra of
ofSSPCM-C20
SSPCM-C20 after
after 500
500 cycles
cycles of
of thermal
thermal
cycling test.
cycling test.

4. Conclusions
The activated carbon prepared using PKS (PKSAC) as the precursor shows a good graphitic
characteristic at the following optimum conditions: 20% H3PO4 (w/w) at 2 h holding time and 500 °C
carbonization temperature. The nitrogen adsorption-desorption isotherm shows that the resulting
PKSAC is micropore-rich as indicated by the Type I adsorption-desorption isotherm with the
highest BET surface area of 1169 m2 g−1 and IG/ID ratio of 1.305. When the resulting PKSAC was used
as the frameworks for the encapsulation of the PCM material, n-octadecane, for the formation of a
Nanomaterials 2018, 8, 689 13 of 14

4. Conclusions
The activated carbon prepared using PKS (PKSAC) as the precursor shows a good graphitic
characteristic at the following optimum conditions: 20% H3 PO4 (w/w) at 2 h holding time and 500 ◦ C
carbonization temperature. The nitrogen adsorption-desorption isotherm shows that the resulting
PKSAC is micropore-rich as indicated by the Type I adsorption-desorption isotherm with the highest
BET surface area of 1169 m2 g−1 and IG /ID ratio of 1.305. When the resulting PKSAC was used
as the frameworks for the encapsulation of the PCM material, n-octadecane, for the formation of a
shape-stabilised PCM, the nitrogen adsorption-desorption isotherm changed to a non-porous material
of Type III with the BET surface area reduced to only 2 m2 g−1 . The change of the type of isotherm
and the reduction of the BET surface area proves that the pores of the AC were fully occupied by the
n-octadecane after the impregnation processes. The FESEM studies also show that the pores of the
activated carbon were fully occupied by the PCM materials.
The interaction between the wall of the pores and the n-octadecane due to the strong covalent
bond provides strong adhesive forces that prevent any seepage of the liquefied n-octadecane.
The SSPCM-C20 is chemically and thermally stable, capable of standing up to 500 cycles. This result
shows that the SSPCM-C20 nano-composite is thermally and chemically reliable to be used as a TES
application. Due to the fact that the PKS was obtained from bio-wastes of the palm oil industry,
the reproducibility is expected to be low. It is difficult to repeat and have exactly the same result for
the experiment due to several aspects. The raw material used, processing methods and productions
conditions will directly affect the physicochemical properties of the AC [22]. However, this experiment
could be improved using other raw materials because the properties of the resulting AC produced are
very much dependent on the precursor used. In addition, the further optimization on the preparation
of AC framework can be accomplished using other precursors, activating agents, and different
carbonization temperatures and holding times, so that a higher loading percentage of PCM and
better thermal energy storage materials can be obtained.

Supplementary Materials: The following are available online at http://www.mdpi.com/2079-4991/8/9/689/s1,

Figure S1: Raman spectra of PKSAC, Figure S2: Adsorption-desorption isotherms.
Author Contributions: A.F.N. conducted the preparation and characterization of Activated carbon and SSPCM
and wrote the manuscript. M.Z.H., Z.Z. and T.K. supervised the project and edited the manuscript. All authors
discussed the results and commented on the manuscript at all stages.
Acknowledgments: We would like to thank Universiti Putra Malaysia and the Ministry of Higher Education of
Malaysia (UPM-MOHE) for funding this project under NANOMITE grant, vote No. 5526300 and 9443100.
Conflicts of Interest: The authors declare no conflict of interest.

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