Renewable and Sustainable Energy Reviews 137 (2021) 110638

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Renewable and Sustainable Energy Reviews

journal homepage: http://www.elsevier.com/locate/rser

Bifunctional nano-catalyst produced from palm kernel shell via

hydrothermal-assisted carbonization for biodiesel production from waste
cooking oil
Rose Fadzilah Abdullah a, Umer Rashid a, *, Mohd Lokman Ibrahim b, c, Balkis Hazmi a, Fahad
A. Alharthi d, Imededdine Arbi Nehdi d, e
a
Institute of Advanced Technology, Universiti Putra Malaysia, 43400, UPM Serdang, Selangor, Malaysia
b
School of Chemistry and Environment, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450, Shah Alam, Selangor, Malaysia
c
Centre of Nanomaterials Research, Institute of Sciences, Universiti Teknologi MARA, 40450, Shah Alam, Selangor, Malaysia
d
Chemistry Department, College of Science, King Saud University, Riyadh, 1145, Saudi Arabia
e
Chemistry Department, El Manar Preparatory Institute for Engineering Studies, Tunis El Manar University, P.O. Box. 244, Tunis, 2092, Tunisia

A R T I C L E I N F O A B S T R A C T

Keywords: A highly mesoporous activated carbon derived from palm kernel shell was successfully prepared by
Biodiesel hydrothermal-assisted carbonization (HTC) by improving the degradation of lignocellulosic composition and
Hydrothermal-assisted carbonization increase the porous texture of carbon structure. Additional NaOH treatment increased the surface area of the
Activated carbon
catalyst which enhanced the loading of the active site. Further impregnation of HTC based activated carbon with
Bifunctional nanocatalyst
Waste cooking oil
K2CO3 and CuO via wet impregnation provided bifunctional characteristics suitable for simultaneous esterifi­
cation and transesterification processes. The physicochemical properties of the prepared catalysts were con­
ducted through the state-of-the-art techniques including N2 adsorption-desorption analysis, functional group
determination, surface morphology study, electron dispersive x-ray mapping, elemental distribution analysis,
amount of basicity and acidity strength and thermal degradation behavior analysis. The investigation found that
the chemical treatment with NaOH significantly increased the surface area from 3.57 to 3368.60 m2/g and
impregnation with K2CO3 and CuO offered higher amount of basicity of 5.73 mmol/g and acidity of 1.48 mmol/
g, respectively. These properties enhanced the simultaneous esterification-transesterification of waste cooking oil
to biodiesel. The catalytic study produced 95.36 ± 1.4% of biodiesel over 4 wt% of PKSHAC-K2CO3(20%)CuO(5%)
catalyst, 12:1 of methanol to oil molar ratio, reaction temperature of 70 ◦ C for duration of 2 h. Meanwhile, the
catalyst can be employed for five subsequent reaction cycles with FAME yield of 82.5 ± 2.5%. Thus, the syn­
thesized bifunctional nanocatalyst supported on the HTC based activated carbon has been validated as an effi­
cient catalyst for biodiesel production.

quality activated carbon such as pyrolysis, gasification, dry Torrefaction

1. Introduction
Recently, the usage of activated carbon in the catalysis field received
significant attention. The activated carbon can be defined by carbona­
ceous material with a high surface area which generally in the range of
less than 2 nm as micropores, 2–50 nm as mesopores and larger than 50
nm as macropores. Because of its high porosity, the activated carbon
gaining significant interest in various applications such as carbon
sequestration [1], wastewater treatment [1,2], bio-refinery as well as
energy production [3].
Nowadays, several techniques are introduced to produce a high
and hydrothermal carbonization (HTC) [4]. The pyrolysis and gasifica­
tion involves carbonization of materials to produce an activated carbon
at elevated temperature at high temperature of 300–650 ◦ C and
600–1200 ◦ C in an inert atmosphere, respectively [5]. On the contrary,
the dry Torrefaction and HTC process requires a lower temperature on
the range of 200–300 ◦ C. However, the HTC process involves sub­
merging materials in water and is heated in a sealed system under
auto-generous inner pressure [6]. Nonetheless, the most preferred
techniques in producing activated carbon were pyrolysis and HTC.
Most of the studies reported that activated carbon with a high surface
area could be obtained by pyrolysis technique. According to

* Corresponding author.
E-mail addresses: umer.rashid@upm.edu.my, umer.rashid@yahoo.com (U. Rashid).

https://doi.org/10.1016/j.rser.2020.110638
Received 31 May 2020; Received in revised form 5 November 2020; Accepted 26 November 2020
Available online 5 December 2020
1364-0321/© 2020 Elsevier Ltd. All rights reserved.
R.F. Abdullah et al.
List of abbreviations
BET Brunauer-Emmet-Teller
BJH Barret-Joyner-Halenda
CH4 Methane
CO Carbon monoxide
CO2 Carbon dioxide
Cu(NO3)2 Copper nitrate
EDX Energy dispersive X-ray
FAME Fatty acid methyl ester
FESEM Field emission scanning electron microscope
FTIR Fourier transform infrared
GC-FID Gas chromatography – flame ionization detector
H2 Hydrogen
Januszewicz et al. [7], they produced pyrolyzed wood char and straw
pellets at 850 ◦ C for 1 h exhibited a high surface area of 1194.4 m2/g and
1340.6 m2/g by additional of chemical activation of KOH, respectively.
On the contrary, another study reported by Ayoob and Fadhil [8] pro­
duced activated carbon from a waste tire with physical treatment via the
steam activation method demonstrated a lower surface area of 590.2
m2/g after being pyrolyzed at 500 ◦ C for 5 h. From the examples given,
the chemical activation method also plays a vital role in creating
porosity of the activated carbon and increase the surface area compared
to physical treatment [9,10]. However, the high energy consumption in
the pyrolysis technique and the need for fully dried materials are among
the disadvantages. To overcome these problems, HTC has been identi­
fied as one of the main methods to produce carbon material, especially
from wet biomass for energy purposes [11].
The HTC process involves a series of reactions such as decarboxyl­
ation, dehydration, condensation and aromatization [12]. In the range
of 200 ◦ C–280 ◦ C, subcritical water could cause degradation of organic
compounds such as lignin, hemicellulose and cellulose to produce a solid
material known as hydrothermal-assisted carbonization (HTC) char [5].
Other than that, the auto-generated inner pressure facilitates hydrolysis
of organic compounds and fabricating a high degree of aromatization
that contains roughly 40–90% of the mass with more than 80% of the
fuel value compare to the original biomass feed [13]. Besides, HTC is an
environmental-friendly method that has a lot of advantages, especially
when dealing with wet materials. There is no pre-drying step involved
and water as the solvent gives a significant economic impact especially
the cost of production [14]. Unfortunately, the produced HTC char will
have a very low surface area that limited its wider application. The HTC
char were mostly applied as adsorbent in water and wastewater treat­
ment plant as well as air purification due to the presence of functional
groups on its surfaces such as quinine and carboxyl groups to adsorbed
heavy metals and refractory organics compounds in wastewater treat­
ment plant, respectively [15,16].
Recently, researchers now considered a combination of HTC and
pyrolysis techniques to produce a better quality of activated carbon. The
study by Unur et al. [17] and Liu et al. [18], reported that biomass-based
electrode for supercapacitors and anode lithium for lithium batteries
exhibited a highly porous graphitic activated carbon owing excellent
capacitances, better rate capability and excellent stability compared to
the traditional chemical activation. Besides, this study also highlights
the green approach in producing a high quality of activated carbon by
using lower energy and hazardous chemicals [17,18]. Other than that,
Jain et al. [19] reported that the overall production cost was reduced as
only 50% of the activating agent was required to produce the high
mesoporous texture of activated carbon by employing the HTC-assisted
technique followed by pyrolysis of coconut shell.
Additionally, suitable biomass selection also plays an important
factor for commercialization, especially referring to cost and
2
Renewable and Sustainable Energy Reviews 137 (2021) 110638
HTC Hydrothermal-assisted carbonization
JCPDS Joint Committee on Powder Diffraction Standards
K2CO3 Potassium carbonate
NH3 Ammonia
PKSHC Palm kernel shell hydro-char
PKSHAC Palm kernel shell hydro-activated-char
PKS Palm kernel shell
TCD Thermal conductivity detector
TGA/DTG Thermogravimetric analysis/Differential
thermogravimetric analysis
TPD-CO2 Thermal programmed desorption – carbon dioxide
TPD-NH3 Thermal programmed desorption – ammonia
WCO Waste cooking oil
XRD X-ray diffraction
availability. In 2015, Malaysia had processed a total of 95.38 Mt of palm
fruit to produce palm oil products in Malaysia [20]. Unfortunately, only
10% of the total palm oil is required to extract palm oil while 4.46 Mt
palm kernel shell (PKS) and 7.34 Mt empty fruit bunch (EFB) were
generated as waste [21]. At present, these huge amounts of waste are
sent to landfill for burning in an open atmosphere, which creates an
additional unnecessary cost for waste management facilities and creates
other environmental issues [22].
Nowadays, utilization of palm oil waste biomass, especially the palm
kernel shell (PKS) in the biodiesel field as catalyst support has been
extensively reported. Apart from its availability, the ability for fabrica­
tion on its physical and chemical properties shows impressive advan­
tages to the construction industry, water purification and renewable
energy production, including bioenergy production and as a primary
feedstock for biochar, bio-oil, biogas and biodiesel production [23–25].
Aforetime, biodiesel production was using homogeneous catalysts such
as sodium hydroxide [26] and concentrated sulfuric acid [27] as it
promises high production efficiency with shorter reaction time [28].
However, after facing many drawbacks with homogeneous catalysts
such as catalyst recovery, wastewater generation through neutralization
process and equipment destruction by corrosion, researchers are now
actively studying the potential usage of a heterogeneous catalyst derived
from PKS for biodiesel production for lab-scale and industrial scale [29].
As an alternative for environmental consideration, biomass such as PKS
has been used to fulfil the future energy demand [30].
Considering all its advantages, the main objective of this study was to
produce hydrothermal-assisted carbonization (HTC) based activated
carbon support derived from palm kernel shell (PKS) for efficient cata­
lyst synthesis and its application for esters production from waste
cooking oil. The best in our knowledge, this is the first report on the
synthesis of bifunctional catalyst based on HTC activated carbon support
for biodiesel production. The physicochemical properties of the HTC
activated carbon support based bifunctional catalysts were character­
ized using state-of-the-art analytical techniques. The produced bifunc­
tional nano-catalyst was implemented first time to convert both
triglycerides and free fatty acids to biodiesel. The detailed study on its
performance was monitored by reaction optimization variables such as
the amount of catalyst loading, methanol to oil molar ratio, temperature
and reaction duration by conventional reflux method using one-
variable-at-a-time (OVAT) approach. Furthermore, the reusability of
the synthesized catalyst was evaluated, and the spent catalyst was
characterized to identify the factors which contributed the loss of cat­
alytic performance after the reaction process.
R.F. Abdullah et al.
2. Materials and methods
2.1. Chemicals and materials
Palm kernel shell (PKS) were collected from FELDA Mempaga,
Bentong, Pahang, Malaysia. The PKS was washed with hot water to
remove dirt and impurities and was dried at 105 ◦ C for 24 h for the
removal of any surface moisture. Dried samples were crushed and sieved
to a particle size of less than 250 μm. Meanwhile, the WCO was collected
from food stalls located in Bandar Baru Bangi, Selangor, Malaysia. The
molecular weight of the WCO sample was 914.05 g/mol. The oil was
filtered to separate food debris and preheated to eliminate moisture
prior used in the reaction. Methanol (CH3OH, 99.8%), n-hexane (99.0%)
and potassium carbonate (K2CO3; 99.5%), copper nitrate (Cu(NO3)2;
99.5%) and sodium hydroxide (NaOH; 98.0%) were purchased from
R&M Chemicals (Subang, SGR, MY). Pure FAME standards such as
methyl heptadecanoate, methyl oleate, methyl linoleate, methyl
palmitate, methyl myristate and methyl stearate were purchased from
Merck (Darmstadt, DE). All of the chemicals obtained in this work were
used directly without any purification process.
2.2. Preparation of HTC based activated carbon derived catalyst from
PKS
The schematic diagram of the autoclave batch reactor is presented in
Fig. 1. The HTC of the PKS was carried out at a fixed PKS/water ratio at
1:10 (w/v). Typically, 10 g of PKS powder was mixed with 100 mL of
distilled water in a 250 mL Teflon cup. After that, the autoclave was
closed tightly to ensure zero leakage. The stirring rate was kept
continuously at 400 rpm throughout the reaction. The autoclave was
heated to 240 ◦ C for 24 h. End of the reaction, the heater was auto­
matically off and started to cool down to room temperature. After that,
the slurry was filtered and washed with hot distilled water to separate
the solid (activated carbon) and liquid (bio-oil). The cleaned biochar
was dried at 105 ◦ C for 24 h and labelled as PKSHC. Chemical activation
of the produced HTC activated carbon was carried out using NaOH/
activated carbon ratio (w/w) of 0.5:1 b y physical mixing overnight at
room temperature. After that, the mixture was carbonized at 600 ◦ C for
3 h with nitrogen flow. The cooled activated carbon was neutralized
with 1 M HCl followed by washing with hot distilled water until pH 7.
Finally, the samples were dried at 105 ◦ C for 24 h designated as
PKSHAC. In comparison, an activated carbon without HTC-assisted
pretreatment was produced and given the name of PKSAC. The
PKSHAC were functionalized with different weight percentages of
Fig. 1. Schematic diagram of the autoclave batch reactor.
3
Renewable and Sustainable Energy Reviews 137 (2021) 110638
potassium carbonate (K2CO3) and copper nitrate (Cu(NO3)2). Typically,
5 g of PKSHAC were mix with 10 wt%, 20 wt%, 30 wt% and 40 wt% of
K2CO3 and 1 wt%, 3 wt%, 5 wt%, 8 wt% and 10 wt% of Cu(NO3)2 so­
lution with continuous stirring at room temperature for 6 h. Then, the
mixture was dried for 24 h at 105 ◦ C. The synthesized catalyst was given
a name as PKSHAC-K2CO3(x%)CuO(y%), where x and y refer to wt.% of
K2CO3 and Cu(NO3)2 with subjected to the weight of the PKSHAC,
respectively.
2.3. Catalyst characterization
The physical and chemical properties of the raw PKS and prepared
catalysts were studied by various analytical techniques. A preliminary
analysis was done on the raw material and activated carbon to deter­
mine carbon, hydrogen, sulfur (CHNS) and oxygen (O) content. The
CHNS analysis was analyzed using LECO: CHNS-628 analyzer. Deter­
mination of oxygen content was calculated by equation (1).
O% = 100% - (C% + H% + N% + S% + ash%) (1)
Where the ash content was determined by calculating the sample left
after being calcined in a muffle furnace at 650 ◦ C for 16 h (ASTM
D2866-94).
The nitrogen physisorption analysis was carried out using Micro­
meritics ASAP-2020 (Micromeritics Instrument, Norcross, GA, USA) to
determine the total surface area, pore volume and pore diameter of the
raw PKS, PKSHC, PKSHAC and PKSHAC derived catalysts by using the
Brunauer–Emmett-Teller (BET) and Barrett–Joyner–Halenda (BJH)
techniques, respectively. Prior analysis, approximately 0.5 g of sample
was outgassed for 12 h at 150 ◦ C under vacuum condition of pressure
<10− 2 Pa.
The morphological study, elemental composition and dispersion of
the catalysts were carried out using Novananosem-2300, field emission
scanning electron microscope (FESEM) equipped with the EX-230BU,
JOEL energy dispersive X-ray (EDX) spectrometer with an emission
current at 15 kV. All the samples were coated with gold using a JFT-
1600, JEQL sputter coater at 20 mA magnetron-type sputtering cur­
rent per minute.
The phase composition of the catalysts was recorded on a Shimadzu,
6000 diffractometer, X-ray diffraction (XRD) with Cu Ka radiation (λ =
1.5406 Å) at 30 kV and 30 mA, generated by Philips glass diffraction X-
ray tube broad-focused on 2.7 kW. The sample was finely grounded and
was placed in an aluminum sample holder. The continuous scan was set
over a range of 5◦ –80◦ with a scan rate of 2◦ /min.
The types of the functional group available on the catalyst surface
R.F. Abdullah et al.
were ascertained by using the Thermo Fisher Scientific, Thermo Nicolet
7000, Fourier Transform Infrared (FTIR) Waltham, MA, USA. About
0.01 g of the sample was grounded into a fine powder using a ceramic
mortar and pestle and was spread on a diamond ATR crystal. The
spectrum was recorded over a wavenumber ranging from 400 to 4000
cm− 1.
Meanwhile, the amount of basicity and acidity was determined using
the Thermo Finnigan, TPDRO 1100, temperature-programmed desorp­
tion of carbon dioxide and ammonia (TPD-CO2 & TPD-NH3) (Kyoto,
JPN), and it was equipped with a thermal conductivity detector (TCD).
The analysis was carried out by placing approximately 50 mg of the
sample into a quartz tube prior series of pretreatment with nitrogen gas
flow of 20 mL/min heating from 50 ◦ C to 150 ◦ C with a heating rate of
10 ◦ C/min and hold for 30 min to remove moisture. The pretreatment
for TPD-CO2 was continued by passing CO2 gas (30 mL/min) for 60 min.
After that, the nitrogen gas (20 mL/min) was again flowed for 30 min to
remove the excess CO2 from the sample. On the other hand, the pre­
treatment for TPD-NH3 was continued by treating the cleaned catalyst
with NH3 gas for 1 h at room temperature and later the excess of NH3 gas
was purged out with nitrogen gas (30 mL/min) for 15 min. Finally, both
analyses were started by flowing helium gas (30 mL/min) with heating
from 50 ◦ C to 900 ◦ C with a 10 ◦ C/min of heating rate.
The degradation behavior and thermal characteristics of the PKSHAC
and optimized PKSHAC derived catalyst through TG analysis were
analyzed using the Mettler Toledo, TG-50 Mettler instrument (Shah
Alam, SGR, MY). The sample was heated from 25 ◦ C to 1000 ◦ C at a
heating rate of 10 ◦ C/min with a 200 mL/min of nitrogen flow.
2.4. The catalytic activity of the catalyst
Series of experiments were conducted in a single-necked 100 mL
round bottom flask accommodated with a magnetic stirrer, a condenser
and hotplate with stirring function as shown in Fig. 2. Typically, 10 g of
WCO was mixed with 6:1 to 18:1 of methanol to oil molar ratio and 1 to
6 wt% of catalyst loading and the reaction mixture was heated at
60–100 ◦ C for 1–4 h with continuous stirring at 500 rpm. After that, the
catalyst was separated from the resultant through centrifugation at
5000 rpm for 15 min and the excess methanol was recovered by rotary
evaporator. Finally, the biodiesel or namely FAME layer (top layer) was
collected and washed with hot distilled water and the remaining mois­
ture was absorbed by sodium sulfate. The same procedure was repeated
Fig. 2. Schematic diagram of the conventional reflux system for esterification/
transesterification reaction.
4
Renewable and Sustainable Energy Reviews 137 (2021) 110638
3 times to ensure the reproducibility of the reaction.
2.5. Waste cooking oil (WCO) methyl ester analysis
The collected biodiesel was analyzed by using Agilent 7890 A, Gas
chromatography with flame ionization detector (GC-FID) equipped with
highly polar BPX 70 capillary column (length: 60 m, ID: 0.25 mm and
capillary: 0.25 μm). Technically, 0.02 mL of sample was makeup to 1 mL
(50 dilution factor) with 500 ppm of the methyl heptadecanoate as in­
ternal standard. The GC port was set at 230 ◦ C and the oven was pro­
grammed to heat from 100 ◦ C to 250 ◦ C with 10 ◦ C/min of heating rate.
About 1 μL of the mixture was injected into the GC port and detected by
FID at 270 ◦ C. Finally, the FAME yield was calculated by equation (2)
adapted from EN14103 standard.
∑
FAME yield, % = ( A – Ameh)/Ameh x (Cmeh x Vmeh)/Wt x 100 (2)
∑
Where A is the total area for free fatty acid peaks, Ameh is the peak area
of the hepta decanoate, Cmeh is the concentration of the methyl hepta­
decanoate, Vmeh is the volume of the methyl heptadecanoate, and Wt is
the mass of the produced methyl ester.
2.6. Reusability and characterization of spent catalyst
In this work, the reusability study was done to determine the life
spent activity of the catalyst. The reaction was kept constant at optimum
condition of 4 wt% of catalyst, 12:1 methanol to oil molar ratio at 70 ◦ C
for 2 h. The product mixture was centrifuged at 5000 rpm for 15min and
the recovered catalyst was rinsed with methanol and hexane to remove
the polar and non-polar compounds from the surface of the catalyst. The
cleaned catalyst was dried at 105 ◦ C for 4 h followed by re-calcination at
600 ◦ C for 3 h before it was used for the next reaction cycle. Finally, the
spent catalyst was analyzed to investigate the deactivation process.
3. Results and discussion
3.1. Preliminary analysis
Preliminary analysis was carried out to investigate the effect of the
HTC technique and chemical activation on the physical characteristics of
the produced PKS HTC activated carbon. The ultimate analysis of the
raw PKS, PKSHC and PKSHAC were presented in Table 1. From the re­
sults, a significant increment of the carbon content after being hydro­
thermalized and treated with NaOH resulting from dehydration and
decarboxylation reaction during each process was observed [31]. During
the HTC process, the nitrogen content in the raw PKS was removed due
to dissolution in hot water, thus lowering the nitrogen content in the
PKSHC [32]. Further treatment of PKSHC with NaOH and calcination at
600 ◦ C had increased the amount of nitrogen on the structure through
the amination process of hydroxyl groups [33]. These results are also
reflected in the reduction of O/C and H/C atomic ratio for each sample.
The N/C atomic ratio determined the quality of the samples where a
higher N/C atomic ratio rendered a higher stabilization degree, as re­
ported by Nizamuddin et al. [34]; Ma et al. [35] and Diaz et al. [36].
3.2. Catalyst characterization
3.2.1. N2 adsorption and desorption analysis
The BET surface area, pore volume and pore diameter of PKS raw,
PKSHC, PKSAC, PKSHAC and PKSHAC derived catalysts were presented
in Table 2. The results show that the PKS after being hydrothermalized
rendered a low BET surface, which was in line with the previous study
that proposed additional pretreatment steps to improve the value [37,
38]. Thus, after considering chemical treatment with NaOH, the BET
surface area was further increased to 3368.60 m2/g and the proposed
chemical equations are presented in equations (3)–(5) [4]. This reaction
R.F. Abdullah et al. Renewable and Sustainable Energy Reviews 137 (2021) 110638

Table 1
Ultimate analysis of raw PKS, PKSHC and PKSHAC.
Sample Ultimate analysis (%)

C H N S O O/C H/C N/C Ash

Raw PKS 45.86 6.095 0.117 0.043 44.26 0.965 0.132 0.00255 3.73
PKSHC 52.25 5.702 0.115 0.129 39.22 0.750 0.109 0.00225 2.58
PKSHAC 72.80 2.732 0.446 0.143 22.58 0.310 0.037 0.00616 1.30

3.2.2. Surface morphology analysis

Table 2
The microscopic images of the PKSHC, PKSHAC and PKSHAC
Physicochemical properties of raw PKS, PKSAC, PKSHC, PKSHAC and PKSHAC
derived catalysts were examined by FESEM spectroscopy with 50,000
derived catalysts.
magnification, as captured in Fig. 5. The HTC process produced droplet-
Catalyst BET surface area BJH pore volume BJH pore shaped carbonaceous nanoparticles on the PKSHC and irregular porous
(m2/g) (mm3/g) diameter (nm)
carbon framework was found after being pyrolyzed at 600 ◦ C as depicted
Raw PKS 3.57 0.04 5.10 in Fig. 5(a) and (b), respectively [5,29]. The accumulation of irregular
PKSAC 91.37 0.06 4.52
shaped nanoparticles proved that the active components of K2CO3 and
PKSHC 103.19 0.29 6.56
PKSHAC 3368.60 2.36 5.17 CuO were successfully impregnated on the PKSHAC, as presented in
PKSHAC-K2CO3 116.57 0.36 5.17 Fig. 5(c–f).
(10%)CuO(5%)
PKSHAC-K2CO3 69.62 0.22 5.08 3.2.3. Elemental composition analysis
(20%)CuO(5%)
PKSHAC-K2CO3 62.43 0.21 5.18
The elemental compositions of the PKSHAC-K2CO3(20%)CuO(5%)
(30%)CuO(5%)
catalyst was carried out by using an electron dispersive x-ray (EDX)
PKSHAC K2CO3 29.06 0.13 5.19 analyzer and the particle distribution of elements was characterized
(40%)CuO(5%) through the EDX-mapping technique. The elemental composition
revealed that 20% of carbon, 55% of oxygen, 1% of silica, 19% of po­
introduced Na metal into the carbon structure and released H2, CO2 and tassium and 5% of copper elements were evenly distributed on the
CO. In addition, it simultaneously increases the porosity of the carbon surface of the catalyst, as presented in Fig. 6.
resulting from the evaporation of NaOH by-products and other volatile
compounds [39]. 3.2.4. X-ray diffraction analysis
XRD diffractogram profiles of PKSHAC and PKSHAC derived cata­
6 NaOH +2 C → 2 Na + 2 Na2CO3 +3H2 (3) lysts were illustrated in Fig. 7. The diffractogram shows a broad peak
centered at 2θ = 22◦ attributed to the disordered and amorphous carbon
Na2CO3 → Na2O + CO2 (4)
structure and the peak was disappeared after impregnation of K2CO3 and
2 Na + CO2 → Na2O + CO (5) Cu(NO3)2 onto the surface of the PKSHAC [47]. The cellulose peak at 2θ
= 18.3◦ , 26.6◦ and 44.1◦ (JCPDS File No: 00-050-2241) exhibited
Basically, the high surface area of the HTC activated carbon gives microcrystalline structure and aromatic layers in a planar direction [48,
advantages in providing extra surface for the deposition of active sites. 49]. Other than that, the presence of silicon dioxide also has been
The BET surface area results obtained in this study were relatively discovered at 2θ = 64.5◦ and 33.7◦ (JCPDS File No: 01-085-0457) and
higher than the direct activation of PKS with NaOH without the HTC- K2O was detected at 2θ = 13.0◦ (JCPDS File No: 00-039-1380) and 30.9◦
assisted process [40]. Other than that, another study reported by (JCPDS File No: 01-018-0994) [50]. The diffraction peaks at 2θ = 26.0◦ ,
Cazetta et al. [41] and Tseng [42] required a higher NaOH to carbon 29.6◦ , 32.1◦ , 34.4◦ and 38.0◦ (JCPDS File No: 00-035-0313) proved the
ratio to produce activated carbon to achieve a surface area of 2825 m2/g appearance of the bimetallic phase of K–Cu–Si–O thus verified the
and 2318 m2/g, respectively, which was still lower than the current interaction between K+ and Cu2+ and distribution of K+ in the copper
study. Thus, instead of generating a higher surface area, the lattice. The result also shows the formation of monometallic Cu at 2θ =
HTC-assisted process before carbon activation reduces the chemical 43.5◦ and 50.8◦ in all the synthesized catalysts (JCPDS File No:
used as this study only required a 0.5:1 NaOH to char ratio to achieve a 01-001-1241).
surface area of 3368.60 m2/g. This finding is parallel to the results ob­
tained by Mbarki et al. [43] and Jain et al. [44], who agreed that the 3.2.5. FTIR analysis
surface area could be increased by 33% with the HTC technique. Besides The FTIR analysis was conducted to determine the functional groups
that, the BET surface area was decreased after surface modification by that existed on the surface of PKSHAC and PKSHAC derived catalysts, as
K2CO3 and CuO due to partial obstruction by the active components displayed in Fig. 8. A broad absorption band at 3321 cm− 1 to 3108 cm− 1
[45]. However, the pore diameter was not significantly affected, as the showed hydroxyl group (v-OH) due to moisture adsorption on the
deposition of metals compound only blocks some of the entry and the catalyst surface [51]. The stretching and bending vibration of the
channel pores [46]. The results also show that the average pore diameter aliphatic group (v-C-H) showed at 2904 cm− 1 and 1314 cm− 1, respec­
in the range of 5.08–5.19 nm demonstrated that the derived catalysts tively [52]. The vibration of aromatic ring groups (v-C–– C) appeared at
rendered mesoporous structure, supported with the N2 adsorption/de­ absorption bands of 1599 cm− 1 to 1418 cm− 1 and the (v-C-H) bending
sorption isotherms as presented in Fig. 3. vibration bands of the meta and ortho-substituted benzene rings
The mesoporous structure was indicated by the existence of a hys­ appeared at 996 cm− 1 to 767 cm− 1 [53]. The absorption band at 1712
teresis loop in the isotherm curves was similar to type IV isotherms ac­ cm− 1, 1103 cm− 1 and 1024 cm− 1 could be assigned to the stretching
cording to the International Union of Pure and Applied Chemistry vibration of v-C–– O, v-C-O-C and v-C-O on the surface of the PKSHAC,
(IUPAC) classification, as depicted in Fig. 3 (a)–(h). Also, a high pore respectively [54]. After impregnation of K2CO3 and CuO, a broad and
volume with a diameter in the range of 2–17 nm was discovered, as intense absorption band of carbonate ion (v-CO2-3 ) occurred in the range
shown in Fig. 4. Thus, these properties facilitate the infusion of tri­ of 1366 cm− 1 and 1346 cm− 1 [55]. The formation of a new functional
glycerides molecules through the available pores. group of v-C-O-M+ was detected at 875 cm− 1 and 689 cm− 1, where M+
was associated with Cu and K [56,57]. The absorption bands of the

5
R.F. Abdullah et al.
Fig. 3. N2 adsorption and desorption isotherm curves of (a) raw PKS, (b) PKSAC, (c) PKSHC, (d) PKSHAC, (e) PKSHAC-K2CO3(10%)CuO(5%), (f) PKSHAC-K2CO3
(20%)CuO(5%), (g) PKSHAC-K2CO3(30%)CuO(5%) and (h) PKSHAC-K2CO3(40%)CuO(5%).
v-M+-O functional group respectively assigned to Cu–O and K–O located
at 552 cm− 1 and 464 cm− 1 [58]. The absorption spectra of v-K+-O
became more intense with the increasing amount of K2CO3 on the
PKSHAC. Besides, the reduction of electron density after metal
impregnation had caused the absorption bands of v-C– – O and v-C-O
shifted to the lower frequency [59].
3.2.6. Temperature programmed desorption of CO2 and NH3 analysis
Thermal programmed desorption (TPD) analyses was used to deter­
mine the strength and amount of basicity and acidity of the catalysts,
which were classified into weak, medium and strong where the weak
strength refers to the desorption peaks appeared at below 400 ◦ C,
400◦ C–600 ◦ C for medium and over 600 ◦ C for strong strength and was
associated with the interaction between CO2 and NH3 with active basic
and acidic active components available on the catalyst, respectively
[60]. On the other hand, the amount of basicity and acidity was calcu­
lated by integrating the CO2 and NH3 desorption curves [61]. The result
demonstrated that the basicity of PKSHAC was distributed at weak and
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Renewable and Sustainable Energy Reviews 137 (2021) 110638
medium strength with basicity amount of 0.49 mmol/g and 1.24
mmol/g, respectively. However, the impregnation of K2CO3 on the
PKSHAC exhibited a lower amount of basicity at weak strength (Tmax =
126–135 ◦ C) and a new CO2 desorption peak with a high amount of
basicity was appeared at strong strength (Tmax = 790–845 ◦ C), as sum­
marized in Table 3. Other than that, the amount of basicity was
increased with an increasing amount of K2CO3 from 10 wt% to 20 wt%,
from 2.77 mmol/g to 4.66 mmol/g, respectively. However, the amount
of basicity was decreased to 3.65 mmol/g after adding 40 wt%. Of
K2CO3. The low desorption at weak strength was related to CO2
desorption by hydroxyl group on the surface of the catalyst, and strong
strength was associated with greater CO2 uptake by the oxide ion, O2−
[62,63]. Moreover, the decreasing amount of basicity with higher
loading of K2CO3 might be due to the limited accessibility and bulky
effect which hindered the CO2 uptake by the active sites [64,65].
The TPD-NH3 results of PKSHAC exhibited desorption peak at weak
and medium strength and strong acidity strength with a high amount of
NH3 uptake by the copper species [66]. The PKSHAC-K2CO3
R.F. Abdullah et al.
Fig. 4. Pore volume distribution of raw PKS, PKSAC, PKSHC, PKSHAC and PKSHAC derived catalysts.
Fig. 5. FESEM images of (a) PKSHC, (b) PKSHAC, (c) PKSHAC-K2CO3
(10%)CuO(5%), (d) PKSHAC-K2CO3(20%)CuO(5%), (e) PKSHAC-K2CO3(30%)CuO(5%)
and (f) PKSHAC-K2CO3(40%)CuO(5%) at 50,000 magnification.
(20%)CuO(5%) exhibited the highest amount of NH3 desorption of 1.48
mmol/g, as presented in Table 3. Unfortunately, the same trend also
happened for TPD-NH3 where the higher loading of K2CO3 decreased the
amount of acidity as there were unreachable acidic components for NH3
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Renewable and Sustainable Energy Reviews 137 (2021) 110638
uptake [67].
Overall, the impregnation of K2CO3 and CuO increased the amount of
basic and acidic on the surface of the catalyst. This study also found that
the high amount of basicity and acidity was strongly related to the BET
surface area. It provides extra space for the deposition of active sites,
thus enhancing the biodiesel yield by promoting the esterification
transesterification reaction.
3.2.7. Thermal analysis
The degradation behavior and thermal characteristics were per­
formed by TGA/DTG analysis, as shown in Fig. 9(a) and (b). The same
trend of decomposition behavior was obtained from PKSHAC derived
catalyst thus the PKSHAC-K2CO3(20%)CuO(5%) catalyst has been chosen
as representative. It should be mentioned that all the samples were dried
overnight before the TGA/DTG test. The TGA/DTG curve in Fig. 9(a) and
(b) exhibited a small weight loss of 4.1% and 6.0% in the range of
50 ◦ C–130 ◦ C, respectively, associated with the loss of absorbed mois­
ture from the environment. The TGA/DTG curves in Fig. 9(a) show a
significant loss of 47.7 wt% starting from 250 ◦ C to 600 ◦ C at Tmax =
424 ◦ C due to the decomposition of organic matters such as hemicellu­
lose, cellulose and lignin.
The addition of K2CO3 and Cu(NO3)2 exhibited a sharp and intense
degradation peak at Tmax = 202 ◦ C, possibly due to the decomposition of
intermediate products of Cu2(OH)3⋅NO3 and nitric acid before it become
CuO [68]. The appearance of a twin peak at Tmax = 746 ◦ C and 842 ◦ C
was associated with the decomposition of K2CO3 [69]. Eventually, a
small peak was discovered at the end of the analysis was attributed to
residual products of CO2, CO and tar originated by the decomposition of
lignin [68,70].
4. Application of catalyst for biodiesel production
4.1. Screening experiment
The performance of the synthesized catalysts was determined in
biodiesel production. The screening experiment was done to identify the
best percentages of K2CO3 and CuO loading to produce the highest
biodiesel. The experiments were performed by varying the weight per­
centage of K2CO3 of 10 wt%, 20 wt%, 30 wt% and 40 wt% at fixed
weight percentages of CuO of 5 wt%. The reaction condition was set at a
catalyst loading of 5 wt%, methanol to oil molar ratio of 15:1, reaction
temperature of 70 ◦ C for a duration 4 h. Fig. 10(a) shows that the re­
action over PKSHAC-K2CO3(20%)CuO(5%) exhibited the highest biodiesel
yield of 90.88 ± 1.4%. Thus, the PKSHAC-K2CO3(20%)CuO(5%) was
R.F. Abdullah et al.
Fig. 6. EDX-mapping of PKSHAC-K2CO3(20%)CuO(5).
Fig. 7. XRD diffractogram profiles of PKSHAC and PKSHAC derived catalysts.
chosen to determine the best weight percentages of CuO afterward by
variation of 1 wt%, 3 wt%, 5 wt%, 8 wt% and 10 wt%. At the same
reaction condition, PKSHAC-K2CO3(20%)CuO(5%) resulted in the highest
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Renewable and Sustainable Energy Reviews 137 (2021) 110638
biodiesel yield, as shown in Fig. 10(b). Thus, it was found that too low
and too high amount of K2CO3 and CuO weight percentage produced a
lower biodiesel yield due to insufficient amount of basicity and acidity
for esterification-transesterification and thick soap emulsion caused
difficulties to separate the biodiesel layer, respectively. Therefore, the
PKSHAC-K2CO3(20%)CuO(5%) was chosen as the best catalyst for further
investigation.
4.1.1. Optimization of esterification-transesterification reaction parameters
The optimization of the reaction parameter is important for the in­
dustry to maximize production efficiency while minimizing production
costs. The optimization included catalyst loading, methanol to oil molar
ratio, reaction temperature and duration.
4.1.1.1. Effect of different catalyst loading on biodiesel yield. The effect of
catalyst loading on the biodiesel yield over PKSHAC-K2CO3(20%)CuO(5%)
was determined in the range of 1 to 6 wt% while the other parameters
was set at methanol to oil molar ratio of 15:1, reaction temperature of
70 ◦ C for 4 h. As depicted in Fig. 11(a), the biodiesel yield was
R.F. Abdullah et al. Renewable and Sustainable Energy Reviews 137 (2021) 110638

Fig. 8. FTIR spectrum of PKSHAC and PKSHAC derived catalysts.

Table 3
Amount of desorbed CO2 and NH3 of PKSHAC and PKSHAC derived catalysts.
Catalyst Amount of desorbed CO2 Amount of desorbed NH3
(mmol/g) (mmol/g)

Weak Medium Strong Weak Medium Strong

a
PKSHAC 0.49 1.24 n.d 0.24 0.81 n.d
PKSHAC-K2CO3 0.21 n.d 2.77 n.d n.d 1.25 Fig. 9. TGA/DTG thermogram of (a) PKSHAC and (b) PKSHAC-
(10%)CuO(5%) K2CO3(20%)CuO(5%).
PKSHAC-K2CO3 0.01 n.d 4.66 n.d n.d 1.48
(20%)CuO(5%)
PKSHAC-K2CO3 0.17 n.d 3.47 n.d n.d 1.10
parameter.
(30%)CuO(5%)
PKSHAC-K2CO3 0.01 n.d 3.69 n.d n.d 0.97 4.1.1.3. Effect of reaction temperature on biodiesel yield. The optimiza­
(40%)CuO(5%)
tion of the reaction temperature is crucial as it involves energy con­
a
n.d = not detected. sumption. The collision theory plays an important role in pushing the
reaction process to produce the maximum biodiesel yield. The effect of
significantly increased from 56.70 ± 2.5% to 93.72 ± 0.8% by adding 4 reaction temperature was done in the range of 60 ◦ C–100 ◦ C and the
wt% of catalyst and further addition of the catalyst up to 6 wt% did not biodiesel yield was presented in Fig. 11(c). At the reaction temperature
show any significant enhancement biodiesel yield as the higher amount of 70 ◦ C, it was believed that the molecules of the reactant had gained
of catalyst loading had disturbed the mixing process between oil, maximum energy to move faster and collide more frequently thus raising
methanol and catalyst [71]. Thus 4 wt% of catalyst loading was iden­ the rate of reaction [73]. A lower biodiesel yield was obtained above
tified for the next optimization parameter to ensure maximum contact 80 ◦ C as the methanol had excessive energy and transformed to the
between the reactant and the active sites on the catalyst surface for the gaseous state. Therefore, the temperature of 70 ◦ C was identified as the
esterification-transesterification of WCO over PKSHAC-K2CO3 optimum reaction temperature for biodiesel production for the next
(20%)CuO(5%).
optimization parameter.

4.1.1.2. Effect of methanol to oil molar ratio on biodiesel yield. The
methanol to oil molar ratio is one of the critical parameters to be opti­
mized in biodiesel production. According to the stoichiometry, the
transesterification reaction requires 3 mol of methanol to react with 1
mol of triglycerides. However, the actual process needs an excess
amount of methanol to avoid a reversible reaction, as shown in Fig. 11
(b). Despite that, too much methanol will cause flooding in the reaction
system, thus diluting the active sites. Moreover, it also increases the
production cost since the flooded methanol had caused soap emulsion
between layers that complicated the separation process [72]. This
statement was supported by experimental results that show the biodiesel
yield was decreased starting from 15:1 of methanol to oil molar ratio.
Thus, since the 12:1 methanol to oil molar ratio produced the highest
biodiesel yield of 94.51 ± 1.2%, it was chosen for the next optimization
4.1.1.4. Effect of reaction duration on biodiesel yield. The effect of reac­
tion duration on biodiesel yield was investigated from 1 h to 4 h using
the optimized parameter of 4 wt% of catalyst loading, 12:1 of methanol
to oil molar ratio at 70 ◦ C. The results show that the biodiesel yield was
significantly increased from 1 h to 2 h reaction duration as presented in
Fig. 11(d). However, the extended duration up to 4 h shows no signifi­
cant changes to the biodiesel yield as the reaction had achieved the
equilibrium [74]. In conclusion, the esterification-transesterification
requires 4 wt% of catalyst loading, 12:1 of methanol to oil molar
ratio, 70 ◦ C of reaction duration for 2 h reaction duration to produce the
maximum biodiesel yield of 95.36 ± 1.4%.

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R.F. Abdullah et al. Renewable and Sustainable Energy Reviews 137 (2021) 110638

Fig. 10. (a) Effect of K2CO3 loading (wt.%) on the catalyst surface for biodiesel production, (b) Effect of CuO from Cu(NO3)2 loading (wt.%) on the catalyst surface
for biodiesel production. Reaction condition: 5 wt% catalyst loading, 15:1 methanol to oil molar ratio at 70 ◦ C for 4 h.

Fig. 11. (a) The effect of catalyst loading on the biodiesel yield (methanol to oil molar ratio of 15:1 at 70 ◦ C for 4 h), (b) The effect of methanol to oil molar ratio on
the biodiesel yield (catalyst loading of 4 wt% at 70 ◦ C for 4 h), (c) The effect of reaction temperature on the biodiesel yield (catalyst loading of 4 wt%, methanol to oil
molar ratio of 12:1 for 4 h) and (d) The effect of reaction duration on the biodiesel yield (catalyst loading of 4 wt%, methanol to oil molar ratio of 12:1 at 70 ◦ C).

5. Reusability and spent catalyst characterization
The reusability study was conducted at the optimum condition of 4
wt% of catalyst loading, 12:1 of methanol to oil molar ratio, 70 ◦ C of
reaction temperature for 2 h. The results show that the high biodiesel
yield with slightly reduced up to the fifth reaction cycle and the
remarkable reduction was only detected at the sixth reaction cycle, as
shown in Fig. 12(a). The decrement was probably due to the deposition
of the unreacted oil and glycerol hence covered the active components.
The spent catalyst was washed with 1 mL of methanol and n-hexane to
remove the organic and inorganic substances to overcome this situation.
After that, the cleaned catalyst was re-calcined at 600 ◦ C for 3 h to re-
instate its catalytic activity. This step is crucial for the base catalyst as
it was sensitive to CO2 and moisture in the air [75].

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R.F. Abdullah et al. Renewable and Sustainable Energy Reviews 137 (2021) 110638

Fig. 12. (a) Reusability study on biodiesel production by using PKSHAC-K2CO3(20%)CuO(5%) (Reaction condition: catalyst loading of 4 wt%, methanol to oil molar
ratio of 12:1 at 70 ◦ C for 2 h), (b) FTIR of fresh PKSHAC-K2CO3(20%)CuO(5%) and spent PKSHAC-K2CO3(20%)CuO(5%).

The BET surface area, amount of basicity and acidity including FTIR 6. Comparison studies
analysis of the spent catalyst after the sixth reaction cycle was deter­
mined to investigate the deactivation effect. The BET surface area was The comparison of the produced activated carbon with previously
slightly reduced by the attachment of large molecules such as glycerol reported were presented in Table 5. The results show that the activation
and unreacted oil on the catalyst surface [76]. Furthermore, the by chemicals such as NaOH and KOH promotes a higher surface area
repeated calcination caused the carbon structure to collapse due to than the physical treatment of CO2. The listed activated carbon exhibi­
sintering, thus blocking the available pores [77]. Consequently, the ted a higher BET surface area than 1000 m2/g with respective process
amount of basicity and acidity was decreased to 1.20 mmol/g and 0.63 techniques and conditions. However, activated carbon produced by the
mmol/g, respectively, as presented in Table 4. These results were sup­ current study shows the highest BET surface area of 3368 m2/g with a
ported by the FTIR analysis where the broad and intense peak of the lower amount of activating agent. However, future work could focus on
carbonate group at 1353 cm− 1 was significantly reduced, as illustrated optimizing the HTC process to save more energy to support green
in Fig. 12(b). Thus, the future work will focus on the re-activation step technology and further reduce the overall production cost.
by avoiding or replacing the re-calcination step at high temperature with Table 6 compares the catalyst in the current study with other cata­
other methods. lysts used in the transesterification reaction for biodiesel production.
The list revealed that most of the catalysts only focused on high basicity
to promote transesterification of triglycerides from the respective feed­
Table 4
stock. However, the synthesized catalyst in the current study provides
Amount of basicity and acidity of fresh and spent PKSHAC-K2CO3(20%)CuO(5%)
catalyst. acidity to support simultaneous esterification-transesterification to fully
utilize the triglycerides and free fatty acid in the WCO. The most com­
Catalyst BET surface Amount of Amount of
parable catalysts in the list were SrO-carbon, ACLa20Ca15 and
area (m2/g) basicity (mmol/ acidity (mmol/g)
g) Fe2O3–MnO–SO2- 4 /ZrO2. Even though the SrO-carbon possesses a higher
amount of basicity and acidity than that in the current study, the bio­
Fresh PKSHAC-K2CO3 69.62 4.67 1.48
diesel yield resulting in the esterification-transesterification over
(20%)CuO(5%)
a
Spent PKSHAC-K2CO3 52.88 1.20 0.63 PKSHAC-K2CO3(20%)CuO(5%) produced a higher biodiesel yield of
(20%)CuO(5%) 95.36%. It is worth noting that esterification-transesterification over
a
Spent catalyst after the 6th reaction cycle. ACLa20Ca15 and Fe2O3–MnO–SO2- 4 /ZrO2 shows better performance

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R.F. Abdullah et al. Renewable and Sustainable Energy Reviews 137 (2021) 110638

Table 5
Comparison study for process technique and condition for the production of activated carbon.
Catalyst Process technique and condition BET surface area Application Ref.
(m2/g)

Activated carbon-3 1. Treatment with NaOH (3:1) and 2. Pyrolysis at 2825 Wastewater treatment for adsorption of Methylene [41]
500 ◦ C, 2 h. Blue
Corncorb-NaOH-6:1 1. Treatment with NaOH (6:1) and 2. Pyrolysis at 2362 Wastewater treatment for adsorption of Methylene [42]
500 ◦ C, 2 h. Blue
HydroThermal-ZnHydroThermal- 1. HTC with H2O2 (10%) at 200 ◦ C, 20min, 2050 Wastewater treatment for adsorption of Rhodamine [44]
3:1-Pyrolysis 2. HTC with ZnCl2 (3:1) at 200 ◦ C, 20min and 3. B
Pyrolysis at 800 ◦ C, 2 h.
Carbon-HTC300 1. HTC at 300 ◦ C,1 h, 1945 Electrode for capacitors [18]
2. Treatment with NaOH (4:1) and 3. Pyrolysis at
900 ◦ C, 4 h
(a) Char-straw pellet 1. Treatment with KOH (2:1) and 2. Pyrolysis at (a) 1340 Wastewater treatment for adsorption of Rhodamine [7]
(b) Char-wood 850 ◦ C, 1 h (b) 1194 B
Act_CHCS 1. HTC at 180 ◦ C, 6 h and 2. Pyrolysis at 900 ◦ C,1 1111 Wastewater treatment for adsorption of Methylene [43]
h, with CO2 treatment. Blue
Waste tire activated carbon 1. Pyrolysis at 500 ◦ C, 5 h and 2. Steam activation 590 Impregnation with Li for transesterification of the [8]
at 800–900 ◦ C,2 h non-edible oil mixture
PKSHAC 1. HTC at 200 ◦ C, 24 h, 3368 Biodiesel production from WCO Current
2. Treatment with NaOH (0.5:1) and 3. Pyrolysis study
at 600 ◦ C, 3 h.

Table 6
Comparison study for esterification-transesterification of high free fatty acid feedstock.
Catalyst Amount of basicity (mmol/ Amount of acidity (mmol/ Feedstock and optimum reaction Biodiesel yield Ref.
g) g) conditionb (%)

SrO-carbon 8.321 1.591 Date seed oil 94.27 [78]

4 wt%, 15:1, 65 ◦ C, 90min
ACLa20Ca15 1.993 11.880 WCO 98.60 [79]
3 wt%,16:1, 100 ◦ C,4 h
Fe2O3–MnO–SO2-
4 /ZrO2 1.519 1.784 WCO 96.50 [80]
3 wt%, 20:1, 180 ◦ C, 4 h
CaO-800 ◦ C 12.4 n.aa Soybean oil, 98.00 [81]
3 wt%, 6:1, 65 ◦ C, 2 h
Na2O(20 wt%)Carbon nanotubes 11.05 n.a WCO 97.00 [61]
3 wt%,20:1,65 ◦ C,3 h
20Fe:80Ba/Al2O3 2.585 n.a Refined used cooking oil 84.00 [82]
6 wt%, 18:1, 65 ◦ C, 3 h
CaO/activated carbon 2 0.884 n.a Soybean oil 98.60 [83]
5 wt%, 12:1, 65 ◦ C, 5 h
Citrus Sinensis peel 0.170 n.a WCO 98.00 [84]
ash@Fe3O4 6 wt%, 6:1, 65 ◦ C, 3 h
Dual-Stage-Char-SO4 n.a n.a WCO 97.00 [85]
4 wt%, 12:1, 65 ◦ C, 90min
Activated-eg-char-10 n.a n.a WCO 96.90 [86]
10 wt%, 12:1, 65 ◦ C, 3 h
PKSHAC-K2CO3(20%)CuO(5%) 5.73 1.48 WCO 95.36 Current
4 wt%, 12:1, 70 ◦ C,2 h study
a
n.a = information not available.
b
Sequence by amount of catalyst loading, methanol to oil molar ratio, reaction temperature and reaction duration.

than that in the current study but higher reaction temperature was
required to achieve 98.6% and 96.5% of biodiesel yield, respectively.
7. Conclusion
In this work, an efficient bifunctional impregnated with K2CO3 and
Cu(NO3)2 on porous HTC activated carbon support based nanocatalyst
was successfully prepared by the hydrothermal technique. It is revealed
that the activated carbon produced through HTC technique has
increased the performance of the raw PKS as a support of the synthesized
heterogeneous nanocatalyst, such as increment of surface area was from
3.57 m2/g up to 3368 m2/g, increased the quantity of base and acid
active sites of 5.73 mmol/g and 1.48 mmol/g, respectively. Because of
that, the reaction assisted by bifunctional PKSHAC-K2CO3(20%)CuO(5%)
nanocatalyst produced biodiesel yield up to 95.36 ± 1.4% from WCO via
single-step reaction process with 4 wt% of catalyst loading, 12:1 of
methanol to oil molar ratio at 70 ◦ C within 2 h. Furthermore, the
prepared catalyst also showed a remarkable reusability profile of up to
the fifth reaction cycles with 57.5 ± 2.3% biodiesel yield at the sixth
reaction cycle due to the poisoning by unreacted oil and glycerol as a by-
product of the reaction. It can be concluded that this bifunctional
catalyst prepared from the HTC-assisted technique has great potential
for the conversion of high FFA feedstock especially WCO to biodiesel.
CRediT authorship contribution statement
Umer Rashid: Conceptualization, Methodology, Data curation, Su­
pervision, Writing - review & editing, Validation, Funding acquisition,
Project administration. Balkis Hazmi: Writing - review & editing,
Validation. Fahad A. Alharthi: Data curation, Writing - original draft,
Methodology, Investigation, Validation, Writing - review & editing, Data
curation, Methodology, Writing - original draft. Imededdine Arbi
Nehdi: Resources, Writing - review & editing.

12
R.F. Abdullah et al.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This research work received financial support from Universiti Putra
Malaysia (Project No: GP-IPS/2016/9580300). The authors would like
to extend their gratitude to the King Saud University (Riyadh, Saudi
Arabia) for the funding of this research through Researchers Supporting
Project number (RSP-2020/160).
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