Renewable and Sustainable Energy Reviews 67 (2017) 257276

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Renewable and Sustainable Energy Reviews

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

Synthesis of magnetic biochar from agricultural waste biomass to

enhancing route for waste water and polymer application: A review
K.R. Thines a, E.C. Abdullah a,n, N.M. Mubarak b,n, M. Ruthiraan a
a
b

Malaysia-Japan International Institute of Technology (MJIIT), Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur, Malaysia
Department of Chemical Engineering, Faculty of Engineering and Science, Curtin University, 98009 Sarawak, Malaysia

art ic l e i nf o

a b s t r a c t

Article history:
Received 7 January 2016
Received in revised form
17 August 2016
Accepted 9 September 2016

The development of magnetic biochar from biomass and the prospect of developing magnetic nanomaterials have attracted many researchers worldwide. The conversion of this biomass into something
more prospective has reduced the waste management issue without any hassle. Magnetic biochar which
is derived from various types of biomass exhibits a good magnetic property with high surface area and
signicant morphology through various production methods. These magnetic biochar showed a remarkable application as an adsorbent for various wastewater treatments and were cooperated in certain
selected polymer composites for application in supercapacitor. This study provides an extensive summary of various production methods of magnetic biochar along with its application in wastewater
treatment and selected polymer cooperation.
& 2016 Elsevier Ltd. All rights reserved.

Keywords:
Magnetic biochar
Polymer
Waste water
Vacuum pyrolysis
Adsorption

Contents
1.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
1.1.
History and development of biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
1.2.
Development of magnetic biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
1.3.
Production of magnetic biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
1.3.1.
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
1.3.2.
Co-precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
1.3.3.
Calcination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
2. Application of magnetic biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
3. Future challenges of magnetic biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

1. Introduction
The continuous growth in various industries in this modernization era requires a continuous improvement in every aspect
with a manageable cost to increase the prot margin of these industries. Agricultural waste has always been given extra attention

Corresponding authors.
E-mail addresses: thinesraj27@gmail.com (K.R. Thines), ezzatc@utm.my,
ezzatchan@gmail.com (E.C. Abdullah), mubarak.mujawar@curtin.edu.my,
mubarak.yaseen@gmail.com (N.M. Mubarak).
http://dx.doi.org/10.1016/j.rser.2016.09.057
1364-0321/& 2016 Elsevier Ltd. All rights reserved.

due to its extensively and abundantly availability throughout the

world. On that note, countries like Malaysia which has its one part
of major economy turnover solely based on the agricultural sector;
produces more than 2 million tons of agricultural waste annually
which are either dumped or burned in an open landll which
leads to extensive environmental related issues such as groundwater contamination or air pollution [1]. Materials such as empty
fruit bunch, rice husk and coconut shell were found to be one of
the abundantly available agricultural waste which contains high
amount of mineral such as silica, magnesium and potassium along
with a high porosity as well [25]. These agricultural waste were

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K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

further developed into biochar by a common pyrolysis process

which is well-known for its successful application in various sectors such as enhancing the soil fertility for a higher crop production by increasing the fertilizers retention time [6,7], as a dopant
to increase the capacitance value of a supercapacitor [8] and as an
adsorbent in the removal of various wastewaters contaminants
such as lead [9], copper, zinc [10] and natural organic matter [11].
An additional centrifugation process is required for the separation
of biochar from aqueous solution [12] or a further activation process by the oxygen plasma method with a strong base prior is
required prior to its application in supercapacitor [13,14]. This
difculty is overcome by the development of magnetic biochar
with the attachment of various metallic ions on the surface of
biochar to enhance its magnetic effect and application in various
elds. Common production methods such as conventional heating
in an electrical furnace [1517], microwave heating in a modied
furnace or oven [2,18,19], co-precipitation [2022] and calcination
[23,24] were employed for the production of magnetic biochar in
laboratory scale. These produced magnetic biochar showed an
extensive application as an adsorbent in wastewater treatment for
the removal of contaminants such as cadmium [25,26], arsenic
[16,27], lead [28,29], methylene blue [2,17,30] and phosphate [31].
Besides that, certain selected magnetic biochar showed an excellent capability to be used as electrode for supercapacitor to
increase the capacitance and electrical conductivity value as well
[32].
In this study, a brief summary of different production methods
of magnetic biochar is presented along with the characterization
of the magnetic biochar produced. Further applications of these
magnetic biochar in wastewater treatment, supercapacitor and
polymer composite are also discussed.
1.1. History and development of biochar
Biochar, generally dened as the solid carbon-rich residue obtained from the thermal decomposition of plant derived biomass
in the absence of oxygen or in a partial oxygen condition [33],
faced a series of development originating from char throughout
these many years to attain its current position in the market. Although the production and application of biochar reached its peak
level only in this modernization era, its history goes all the way
back to the early stages of human life. Biochar were believed to be
initially discovered after activities such as forest res and burning
activities in pits which are solely reserved for open-air combustion
of trash. These char were then added to the soil for improving its
nutrient intake and growth rate. Although the pits where the
burning process done is solely reserved and far away from
humanity, the release of toxic gases into the surrounding environment does lead to harmful effects [34].
Certain research suggests that biochar was initially found at the
Amazon Basin of South America where the Native Indians began to
produce biochar by pilling up wood stock in pits and slowly
burning them without the presence of air during the early stage of
civilization [35]. These types of dark and fertile soil, known as terra
preta soil were scattered patchily all over the locations of historic
living place, approximately 20 hectares in area in which the high
content of biochar being the main cause of the dark colour of the
soil [36,37]. On the same note, these black soils were found to
provide a high quantity of enhanced calcium, nitrogen, phosphorus and potassium along with organic matter which eventually
be the main reason behind the increase of crops production rate.
Apart from that, matching soils as the terra preta soil were
found in few other locations such as Ecuador, Peru and West Africa
in the agricultural application as well [38]. Besides the American
continent, biochar were found to be widely used in Asian continents as well for the agricultural processes since ancient times.

At that moment, Japan led the carbon productions market by

producing charcoal for commercial purposes with a trading rate of
15,000 tones yearly [39]. On the other hand, the very rst batch of
activated carbon was industrially produced in the twentieth century where agricultural products were used as the raw material for
the synthesis of activated carbon in the sugar rening industry
[40]. Prior to the usage in sugar rening industry, powder activated carbon was generated from wood in Europe in the early 19th
century for commercial purpose. As for the United States, activated
carbon was produced from black ash which was discovered from
its capability in decolorizing liquids [41]. Besides that, activated
carbon was also widely used in the 19th century in England for
water treatment to eliminate any unwanted and undesirable tastes
and odours from drinking water [40].
1.2. Development of magnetic biochar
The continuous growth in technology has always been a key
factor for further improvement in any current product or technology in the world market. The development of magnetic biochar
rose after the difculty faced in the application of biochar in a vast
area of interest.
Recently, magnetic materials are being offered a great interest
of research in many sectors such as catalysis [42], magnetic resonance imaging [43], data storage [44] and environmental remediation [2]. Magnetic materials were found to provide optimum
performance when it has a particle size in a range of 1020 nm.
Magnetic materials were generally produced by utilizing metallic
salt which are able to provide the magnetic medium such as iron
chloride hexahydrate [45], iron sulfate heptahydrate [46], manganese oxide tetrahydrate [28] and manganese sulfate hydrate
[47]. The production of magnetic materials was then focused on
the utilization of agricultural waste material as the raw material
and the produced magnetic materials were known as magnetic
biochar. A wide range of waste material such as pine wood [48],
corn cob [49], cottonwood [30] and chitosan [47] has already been
roped into the production of magnetic biochar which exceled in
various applications. The next section focuses on the various
synthesis methods of magnetic biochar by the employment of
different magnetic material and agricultural waste material.
1.3. Production of magnetic biochar
Generally, there are three common techniques employed to
produce magnetic material such as pyrolysis, co-precipitation and
calcination method. These methods are utilized by many researches to produce high quality and high yield of magnetic materials. Every method has its own advantage and pullback in which
a set of innovative skills is required to utilize the advantage of
single production method to produce novel magnetic biochar with
a signicant production method.
1.3.1. Pyrolysis
Generally, pyrolysis is dened as the chemical and thermal
decomposition of an organic material to temperature greater than
400C in the absence of oxygen [50,51] which leads to the production of three main substances which consist of a residual solid
char (biochar), a liquid product commonly known as bio-oil, pyrolysis oil or bio-crude and a non condensable gas known as syngas
which consist of carbon monoxide (CO), carbon dioxide (CO2),
hydrogen (H2), and methane (CH4) [52]. An additional understanding of the nature of the biomass and the reactor conditions
provides an extra knowledge of the complex physics and chemistry that occur during a pyrolysis reaction [53,54]. Biomass is
generally dened as the susbtance of a mixture of lignin, cellulose,
hemicellulose and minor amounts of other organics in which each

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

of the them is pyrolysed or degraded at different rates and mechanisms depending on the pyrolysis temperature, biomass heating rate and pressure.
A general pyrolysis process is classied into primary and secondary stages. The primary stage began by the transfer of heat to
the particle surface through radiation or convection, and then into
the particle. The continuous increase of temperature leads to the
removal of moisture from the biomass particle during the prepyrolysis and main pyrolysis process. The volatiles and syngas
produced during this process ow through the pores of the particles and engage in heat transfer process which acts as a function
of time [54]. The second stage of pyrolysis process begins with the
enlargement of the pores of the solid due to the conversion of
biomass into gases [55]. The extensive enlargement of pores provides additional sites to the reactions of volatile and syngas produced during the pyrolysis process within the hot biomass [56].
The heat is transferred in the pores material by three main mechanisms such as the conduction inside the biomass particle,
convection inside the pores of the biomass particle, and the
convection and radiation from the surface of the nal product.
Similarly, a typical pyrolysis process can be divided into three
types such as conventional pyrolysis, fast pyrolysis and ash pyrolysis depending the operating conditions as listed in Table 2.1.
From Table 2.1, the conventional pyrolysis process takes place
under a slow heating rate which allows the production of solid,
liquid, and gaseous product in compelling portions [57]. Conventional pyrolysis process consists of either a batch or continuous
system in which the particle size and moisture content are only
given importance for the continuous system. A pre-pyrolysis process that takes place between 395 and 475 K permits the rst stage
of decomposition of biomass, in which few internal rearrangement
such as breakage of bond, free radicals appearance, elimination of
water and formation of carboxyl, carbonyl and hydroperoxide occur [58]. The main pyrolysis process occurs during the high rate of
second stage biomass decomposition. The third stage comprises of
the decomposition of char at slow rate leading to formation of a
solid residual rich with carbon, which is generally known as biochar. The overall yield of conventional pyrolysis would be approximately 35% biochar, 30% bio-oil and 35% syngas by mass [59].
The bio-oil which is present in the form of vapors and aerosols
cannot be separated from the syngas, and the emission of this gas
into the atmosphere causes a serious pollution emission. On the
contrary, fast pyrolysis is opted when the production is focused
mainly on liquid or gaseous products. Conditions such as high
operating temperatures, very short contact time and ne particles
are required to achieve the fast heating rates condition in fast
pyrolysis [54]. The overall yield of fast pyrolysis would be approximately 5070% bio-oil, 1030% biochar and 1520% syngas by
mass [59]. The feedstock is required to be dried and ground to a
size of less than 2 mm before entering the main system of the
pyrolysis reactor. However, ash pyrolysis is generally chosen for
producing gaseous products due to the high heating rate and very
small particle size [60]. The overall yield of ash pyrolysis would
be approximately 60% biochar and 40% volatiles by mass. This
process consists of a gasier which allows small, limited amount of
oxygen to enter the reaction chamber which causes partial combustion of biomass, producing 515% of char and traces of bio-oil
which are referred to as tar [59]. As for laboratory scale, the
pyrolysis process is generally done either through conventional
heating or microwave heating.
1.3.1.1. Conventional heating. The conventional pyrolysis process
through modied furnace has been successfully roped into the
production of magnetic biochars based on different biomass and it
has been applied in various industries. On that note, Zhang et al.
[61] employed ve different biomass such as sugar beet tailings

259

Table 2.1
Operating conditions for different type of pyrolysis processes.
Parameters

Fast
pyrolysis

Flash
pyrolysis

Conventional
pyrolysis

Particle size (mm)

Biomass residence time
(s)
Pyrolysis temperature
(K)
Heating rate (K/s)

Less than 1
0.51.0

Less than 0.2

Less than 0.5

550
450550

8501250

10501300

550950

10200

Less than
1000

0.11.0

(SBTs), sugarcane baggase (SB), cottonwoods (CWs), pine woods

(PWs) and peanut shells (PSs) to produce MgO/biochar magnetic
composite by utilizing magnesium chloride hexahydrate
(MgCl2
6H2O) as the metallic solution to provide the magnetic
behaviour for the composite being pyrolysed in an electrical furnace at 10C/min upto 600 C with nitrogen, N2 gas ow for 1 h. In
general, an inert gas ow such as nitrogen or argon will be
equipped along with the furnace during a pyrolysis process to
remove all the contaminants to facilate the formation of MgO
particles in the biochar matrix. This pyrolysis process under a zero
oxygen condition successfully produced MgO/biochar magnetic
composite with a highly crystalline strucutre and a BET surface
area of 2.8, 18.9, 122.5 50.1 and 70.0 m2/g with respect of PWs, PSs,
SBs, CWs, and SBTs. Furthermore, the MgO/biochar magnetic
composite was found to have a rough and porous morphology due
to the intrinsic nature of biochar while the MgO akes was deposited uniformly across the entire susbtrates with a length of 1.2
1 mm. This study concluded that a simple pyrolysis process with
the ow of an inert gas can be employed to convert various biochar precursors to a magnetic composite with a signicant morphology and surface area.
Furthermore, Chen et al. [31] employed orange peel, the abudantly available agricultural biomass waste to produce three novel
magnetic biochars (MOP250, MOP400, MOP700) by employing the
orange peel as the raw material in the presence of FeCl3
6H2O and
FeCl3 in which the biomass mixture were pyrolysed under different temperatures (250 C, 400 C and 700 C) at 5C/min for
6 continuous hours. This pyrolysis method was done successfully
without the ow of any inert gas. The magnetic biochar produced
exhibited signicant crystal lattice planes for the iron oxide and an
amorphous morphology for the biochar. The lower carbon contents and higher ash contents of the magnetic biochar produced
acknowledge the introduction of iron oxide, Fe2O3 as the magnetic
source for the biochar. The surface areas of the magnetic biochar
produced were found to be 41.2. 23.4 and 19.4 m2/g with respect
of MOP250, MOP400, MOP700 where higher temperature leads to
a reduction in the surface area due to the destruction of pores.
Furthermore, Liu et al. [62] employed this remarkable pyrolysis
process to reduce the pinewood sawdust which is found abudantly
from the wood processing factory in Beijing by developing a
Fe3O4-loaded magnetic biochar in the presence of FeCl3 as the
metallic solution to provide the magnetic effect on the magnetic
biochar produced. The pyrolysis process was carried out in the
horizontal pyrolysis reactor in an electrical furnace with the ow
of nitrogen, N2 gas at 600C for almost 3 h. This pyrolysis process
successfully synthesized Fe3O4-loaded magnetic biochar with a
spinel strucutre (magnetite, Fe3O4 or maghemite, -Fe2O3) which
acknowledges the reduction of -Fe2O3 to Fe3O4. Likewise, the
Fe3O4-loaded magnetic biochar was found to have more coarse
surface due to the deposition of Fe3O4 particles with a specic
surface area value of 349 m2/g and total pore volume of 0.20 cm3/
g. Furthermore, the Fe3O4-loaded magnetic biochars particles
were distributed in the range from 0.30 to 5.48 mm and a mean

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K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

particle size of 1.98 mm exhibited a good saturation magnetization

value, MS of 47.67 emu/g as well. The signicant advantages of this
study would be the capability of conversion of waste biomass into
something more useful and the low-cost production method of
Fe3O4-loaded magnetic biochar.
On the other hand, Wang et al. [16] focused on the production
of magnetic biochar by utilizing a mixture of naturally-occurring
hematite mineral and pinewood biomass in a tube furnace under
the ow of inert gas nitrogen, N2 at the peak temperature of
600 C for an hour. This magnetic biochar was produced with a
specic surface area of 193.1 m2/g which showed a slightly more
stability compared to the normal biochar. This pyrolysis process
also successfully soldered and stabilized the hematite particles on
carbon surfaces and activated the magnetic property of hematite
to produce a magnetic biochar with a high magnetic property. The
magnetic biochar produced in this study can be used as an alternative remediation agent in various environmental applications
due to the availability and low cost of biomass and hematite material. Additionaly, Khan et al. [63] also performed a study on the
difference of magnetic biochar produced using pine needle as the
raw material in the presence of Fe3O4 and Cu-Cu2O. The Fe3O4 and
Cu-Cu2O magnetized biochar were produced with a well-crystallined structure with the most dominant peak of calcite, CaCO3
present in both samples. Additionaly, both of the Fe3O4 and CuCu2O magnetized biochar exhibited an irregular and macro-porous
surface structure with a wide range of different pore shapes.
However, the Fe3O4 magnetized biochar had some pores which are
covered with volatile matters or tar agglomerrates along with the
presence of some partly split cells with rough surface while the
Cu-Cu2O magnetized biochar demonstrated a formation of tubes
of carbonaceous material on its surface. The presence of tar agglomerrates were attributed to the fast volatile release during
pyrolysis. Table 2.2 summarises the conventional heating process
on the production of magnetic biochar employing different types
of biomass.
1.3.1.2. Microwave heating. Another common and growing heating
technique would be the microwave heating which was originally
conceived about 40 years ago. The extensive application of microwave synthesized magnetic biochar was brought into different
disciplines through Ramasahayam et al. [64] who employed the
abundant daily waste of spent coffee grounds to produce P,N codoped C (PNDC) material by a novel microwave-assisted method
with the utilization of ammonium polyphosphate (APS) as the only
reactant. The produced magnetic materials were attempted to be
used as electrocatalyst for the supercapacitor application. The
synthesized P,N co-doped C (PNDC) magnetic particles were found
to contain spherically shaped particles with the highest surface
area of 999.64 m2/g consisting of micropores, mesopores and
macropores. Consequently, the presence of micropores, mesopores
and macropores was found to be critical for the performance of
supercapacitor, in which the macropores and mesopores play a
role in decreasing the ion transportation distance and resistance
facilitating ion transport, whereas micropores plays a role in the
energy storage. On that note, the highest capacitance value of
PNDC magnetic particles obtained was 286 F/g at a scan rate of
5 mV/s and this high specic capacitance value was attributed to
its high surface area, good pore volume, presence of micropores,
mesopores and macropores and the presence of the highest concentration of N,P and O dopants. Apart from that, the PNDC
magnetic particles also exhibited good electrochemical stability
over the duration of continuous 200 cycles in both acidic and alkaline electrolytes. This step proved that an abundant wastes life
does not end when it is dumped, but it can be further modied to
be applied in a growing industry as a cost reduction step. On the
other hand, Meng et al. [47] employed chitosan as the raw material

for the production of MnFe2O4-loaded magnetic biochar by a novel

one step microwave-assisted hydrothermal at a microwave heating temperature of 120 C for 10 min. This study exhibits that the
additional chitosan did not generate any phase change of the
spinel structure of Mn ferrites. Meanwhile, the application of microwave heating provided a shorter time and reduced temperature
for the production of Mn ferrite magnetic particles. Furthermore,
the chitosan-modied MnFe2O4 composite produced were present
in homodisperse without any aggregation with a cubic structure.
Although the magnetic biochar exhibited a ferromagnetic behaviour, the saturation magnetization, MS of chitosan-modied
MnFe2O4 magnetic biochar was found to be lower than MnFe2O4
particles without chitosan modied due to the existence of the
nonmagnetic chitosan on the surface on the MnFe2O4 particles.
Furthermore, Mubarak et al. [2] employed a single stage microwave heating technique to produce magnetic biochar utilizing
empty fruit bunch as the raw material in the presence of ferric
chloride hexahydrate (FeCl3
6H2O). The single stage microwave
heating was done in a microwave mufe oven with a constant ow
of nitrogen, N2 gas at 200 cm3/min to produce a magnetic biochar
with a remarkable BET surface area of 890 m2/g. The magnetic
biochar were found to be developed with large pores of different
sizes and shapes with microporosity being broadened with a shift
to meso and micropore. The ow of inert gas during the microwave heating process assisted in the development of pores on the
surfaces of the precursor. This magnetic biochar produced were
found as a suitable substituent for activated carbon due to its high
porosity and high surface area. On the contrary, Zhang et al. [65]
focused on the conversion of bamboo charcoal into magnetic
biochar by ultrasonicating the raw material with iron chloride,
FeCl3 and heated in a microwave with an output of 640 W and a
frequency of 2.45Ghz for 6 min under a nitrogen ow of 10 mL/
min. The iron bamboo magnetic biochar produced were found to
have rougher surfaces compared to the normal biochar in which
the increase in concentration of FeCl3 generated better agglomeration of iron oxide on the surface of magnetic biochar. An increase in the concentration of FeCl3 provided the highest BET
surface area value of 298.732 m2/g and a total pore volume of
0.273 cm3/g which indicated that the pores were well widened
and not blocked by the presence of Fe2O3. Similarly, Wang et al.
[66] employed the bamboo charcoal as the raw material for the
production of bamboo based-iron coated magnetic biochar (Fe-BC)
by using Fe2(SO4)3 as the precursor of iron oxide incorporation
into the pores of granular sized porous biochar prior to heating the
mixture in a modied microwave with an output of 640 W and a
frequency of 2.45 Ghz for 6 min under a nitrogen ow of 10 mL/
min. The Fe-BC was found to be well-crystallized with a BET surface area of 49 m2/g which is found to be lower than biochar
(64 m2/g) due to the blockage of pores by iron oxide. Similarly,
Wang et al. [67] employed the same bamboo charcoal for the
production of bamboo based-cobalt coated magnetic biochar (CoMBC) by utilizing Co(NO3)
6H2O as the precursor of cobalt oxide
incorporation into the pores of granular sized porous biochar prior
heating the mixture in a modied microwave with an output of
640 W and a frequency of 2.45 Ghz for 6 min under a nitrogen ow
of 10 mL/min. On the contrary, the Co-MBC produced through this
study was to have a higher BET surface area of 263 m2/g compared
to the biochar (15 m2/g) due to successful pore development done
by the microwave heating. This Co-MBC was also found to have a
regeneration and reuse capability through the desorption study.
Likewise, Zhu et al. [68] obtained cotton fabric from a commercially available T-shirt to be used as raw material for the
production magnetic biochar in the presence of Fe(NO)3
9H2O.
Both conventional heating (heated to 850 C with heating rate of
10 C/min in a N2 atmosphere with 5% H2-Ar mixture as the purging gas in a tube furnace) and microwave heating (heated to

Table 2.2
Summary of conventional heating process on production of magnetic biochar with different biomass.
Raw material

Reagent

Magnetic biochar

Operating condition

Cottonwood

Aluminum chloride hexahydrate, AlCl3
6H2O

Cottonwood biochar/
AlOOH

Biomass were dried at 80C for 24 h prior pyrolyzing at

600 C under N2 ow for 1 h

Cottonwood

Ferric chloride hexahydrate, FeCl3
6H2O

Cottonwood biochar/Fe2O3

Biomass were immersed into FeCl3 solution for 2 h and

dried at 80 C for 2 h followed by pyrolyzing the biomass
mixture in a furnace at 600 C with the ow of N2 for 1 h

Characteristic of magnetic biochar

 Magnetic biochar had a rough and porous morphology due to [30]

the intrinsic nature of the biochar matrix

 Well-crystallined of biochar/AlOOH composite were produced

 AlOOH akes were found to be homogenously and densely




-Fe2O3, natural hematite

material

Hematite modied
biochar

Pyrolysed in a tube furnace under N2 at a peak temperatures

of 600C for one hour






Date pits

Pine wood char

FeCl3

FeCl3

Date pits magnetic

biochar

Pyrolysed in a stainless steel furnace at constant rate of

10 C/min of pyrolysis temperature of 700 C for 1 h

Carbon encapsulated Fe
particles

Pyrolysed at 1000 C at a ramping rate of 20 C/min under

argon stream with a ow rate of 1 L/min in an electrical
furnace








Pine bark

Pinewood saw dust

Co(NO3)2
6H2O and Fe

(NO3)3
9H2O

Pine bark/ magnetic biochar composite (MBC)

Pyrolysed at 950 C for 2 h with a heating rate of 30 C/min

under N2 atmosphere

FeCl3

Fe3O4-loaded saw dust

magnetic biochar

Pyrolysed in a horizontal pyrolysis reactor heated by electrical furnace at 873 K within 115 min under 30 mL/min N2
ow and held at 873 K for 60 min.




Baggase

FeCl3
6H2O

Fe3O4-loaded baggase
magnetic biochar

Pyrolysed in an modied electrical furnace with the presence of N2 gas





Mn oxide-modied pine
biochar (MPB)

Pyrolysed in a tube furnace under owing N2 by a heating

rate of 10 C/min and holding at a peak temperature of

[110]

[16]

[17]

[48]

[25]

[62]

[45]

[28]
261

Loblolly pine (Pinus taeda) MnCl2
4H2O

wood

grown across the entire substances and separated from each

other
Well-crystallined of biochar/-Fe2O3 composite were produced
Magnetic biochar had a rough and porous morphology due to
the intrinsic nature of the biochar matrix
Formation of -Fe2O3 particles in the shape of cubic and octahedral on the surface of biochar
Magnetic biochar exhibited ferromagnetic properties with MS
value of 69.2 emu/g and HC value of 34.1 Oe
Magnetic biochar had a BET surface area value of 193.1 m2/g
while non-magnetic biochar exhibited BET surface area value
of 209.6 m2/g.
Small decrease in BET surface area after magnetization proves
that the hematite did not block the opening of biochar
Small aggregates/particles stabilized on the surface of magnetic biochar
Magnetic biochar were found to be more crystallined and
exhibited a strong magnetic properties
Magnetic biochar were produced with 780.06 m2/g of BET
surface area
Magnetic biochar had a rough and porous surface
Pores are basically consists of micropores with micropore volume of 0.468 cm3/g and mesopore volume of 0.105 cm3/g.
Yield of magnetic biochar and non magnetic biochar were
found to be 56.3% and 43.7% respectively
Non-magnetic biochar had an amorphous morphology which
were further reduced in magnetic biochar
Fe particles were encapsulated by well-alligned and multilayered graphitic shells
Long and tangled multi layered graphitic carbon structures
were observed around these Fe particles.
Magnetic biochar were well crystallined with spinel-type lattice of cobalt ferrite
Magnetic biochar had a well agglomerated surface with attachement of small particles of cobalt ferrate on the surface of
biochar
Iron oxide in magnetic biochar exhibit a spinel strucutre
(magnetite, Fe3O4 or maghemite, Fe2O3) while the sawdust
pyrolysis creates a reduction atmosphere of -Fe2O3 to Fe3O4
Magnetic biochar had a smooth and porous surface due to the
attachement of Fe3O4 on the surface of biochar
Fe3O4-loaded magnetic biochar exhibited a good MS value of
47.67 emu/g
Magnetic biochar were produced with BET surface area of
97.07 m2/g and total pore volume of 1.71 cm3/g
Fe3O4 attached on the surface of biochar present in a cubical
shape
Well-crystallined magnetic biochar were found to be more
thermally stable
MPB has a higher thermal stability compared with pristine
biochar

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276


Pine wood

Reference

with the attachment of spherical -Fe3O4 on the surface

were 6.4014.98 emu/g, as the temperature increases

 Highly porous surface of magnetic biochar were produced

0.632 cm3/g of magnetic biochar were obtained

 The saturation magnetization values of the magnetic biochar

and total pore volume of 0.022 cc/g

Pyrolysed under N2 ow of 1 L/min for 30 min at a temperature range of 500C to 800C

FeCl3
6H2O and ZnCl2
Hydrochar of salix psammophila (SP)

Fe3O4-loaded hydrochar
magnetic biochar

 MPB were produced with a high BET surface area of 463.1 m /g

600 C for 1 h.

Characteristic of magnetic biochar

Operating condition
Magnetic biochar
Reagent
Raw material

Table 2.2 (continued )

 Highest BET surface area of 1110 m2/g and total pore volume of [140]

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

Reference

262

850C in a microwave heated system with 5% H2-Ar and high

purity N2 atmosphere for 2 h) were opted for the production of
magnetic biochar and the results obtained were compared. Conventional heating was found to produce large magnetic particles
(CN) which are not in uniformed size while the microwave heating
was found to produce magnetic particles with controlled size and
dispersion without any agglomeration. Furthermore, the application of N2 gas as the purging gas produced magnetic biochar with
a more rough surface and highly porous structure. On the same
note, magnetic biochar produced by the application of microwave
heating employing N2 gas (MN) and H2-Ar gas (MH) as the purging
gas were found to have a core-shell structure. The BET surface
areas of CN, MN and MH were found to be 190.1 m2/g, 91.1 m2/g
and 73.7 m2/g respectively where by the decrease in the surface
area is attributed to the blockage of iron oxide particle within the
porous carbon. Table 2.3 demonstrates the overall summary of the
microwave heating process on the production of magnetic biochar
based on different biomass.
1.3.2. Co-precipitation
Coprecipitation is a process in which a solute precipitates out
from a solution through a carrier that forces the solute to bind it
together with it rather than staying dissolved in the solution.
Solutes are also sometimes referred to as impurities as well.
This method is commonly applied for sampling, purifying solutions and cleaning hazardous efuent from industry to the surrounding environment. A solute can be co-precipitated out from a
solution through three common methods such as inclusion, occlusion and surface adsorption [69]. Inclusion or also known as the
formation of mixed crystals is a process which consists of the incorporation of solute in the crystal lattice of the carrier through a
hole in which the regular structure of the carrier remains unchanged. This combination forms a mixed crystal in which the
amount depends on the adsorption phenomena during the precipitation process. Apart from that, during the occlusion process,
the solute remains incorporated into the crystal lattice of carrier,
instead of the carrier being completely surrounded by the solute
during the formation of the crystal matrix, entraping the solute
from returning to the solution. The surface adsorption process on
the other describes about the solute which is attached to the
surface of the carrier and moves out from the solution only when
the crystal matrix forms a large surface area and behaves like a
occulated colloid.
This method is generally known as the simplest step on the
production of magnetic particles. Generally, magnetite, Fe3O4 and
maghemite, -Fe2O3 are prepared by a mixture of ferrous and
ferric salts in an aqueous medium according to Eq. (1), in which
the complete precipitation of Fe3O4 occurs at pH between 8 and 14
in a non oxidizing oxygen environment [70]

Fe2 + + 2Fe 3 +8OH Fe3O4 + 4H2O

(1)

Magnetite, a susbtance which is not stable and sensitive to

oxidation is transformed into maghemite in the presence oxygen
according to Eq. (2), in which high range of electrons and ions are
transferred depending upon the pH of the suspension.

Fe3O4 + 2H +

Fe2O3 + Fe2 +H2O

2

(2)

Referring to Eq. (2), surface of Fe

ions are desorbed as hexaaqua complexes in an acidic and anaerobic condition of solution
while the oxidation-reduction of the surface of magnetite occurs
under basic conditions. In maghemite, the Fe3 ions are distributed in octahedral (Oh) and tetrahedral (Td) sites of the spinel
structure as in Eq. (3) while magnetite differs by the presence of
cationic vacancies within the octahedral site as showed in Eq. (4).
On par with this statement, the X-ray diffraction and IR

Table 2.3
Summary of microwave heating process on production of magnetic biochar with different biomass.
Reagent

Magnetic biochar

Operating Condition

Bamboo charcoal

FeCl3 and Co(NO3)2

Fe-MBC and Co-Fe-MBC

Microwave heating were done in a modied microwave heating

system with continuous output power of 640 W and a frequency
of 2.45 GHz for 6 min under N2 ow of 10 mL/min

Characteristic of magnetic biochar

Reference

 Both Fe-MBC and Co-Fe-MBC were well crystallined

[19]
 The surface of Fe-MBC is covered with botryoidal clusters while the
surface of Co-Fe-MBC is well covered with small botryoidal clusters

 The specic surface area of Co-Fe-MBC and Fe-MBC were 331 and
247 m2/g respectively

 Introduction of cobalt promoted pore formation and prevented the

pores from being blocked by the presence of CoFe2O4

Empty fruit bunch FeCl3

(EFB)

Bamboo charcoal

NiCl2

Empty fruit bunch FeCl3

(EFB)

FeCl3-loaded magnetic
biochar

Ni-doped magnetized
bamboo charcoal

FeCl3-loaded magnetic
biochar

Microwave heating were done in a quartz tube in microwave

mufe system with process conditions such as radiation time of
30 min, microwave power of 800 W and impregnated ratio of 0.5

 The ow of N2 gas assisted on the removal of impurity and con- [113]

Microwave heating were done in a modied microwave heating

system with continuous output power of 640 W and a frequency
of 2.45 GHz for 6 min under N2 ow of 10 mL/min

Microwave heating were done in a quartz tube in microwave

mufe system with process conditions such as radiation time of
30 min and microwave power of 800 W


Chitosan

FeCl3
6H2O and

MnSO4
H2O

Chitosan-modied
MnFe2O4 magnetic
biochar

Microwave heating were done in Teon-lined agitated reactors in

a modied microwave oven at 120 C for 10 min






sumption of carbon to create porosity. This helps on the opening and

widening of microporosity with a shift to meso and macroporosity
Magnetic biochar were created with a large surface area (765 m2/g)
and porous structure
Magnetic biochar were produced with a high BET surface area and [141]
total pore volume of 263 m2/g and 0.27 cm3/g respectively compared
with biochar
Magnetic biochar had a more smooth and porous surface due to the
Ni dispersion on the surface
The ow of N2 gas trigger the diffusion of oxidizing agent to create [18]
porosity on magnetic biochar while removing the impurities as well.
This helps on the opening and widening of microporosity with a shift
to mesopores and macropores
Magnetic biochar were produced with a high BET surface area of
890 m2/g
Additional of chitosan did not generate any phase change of the [47]
spinel structure of Mn ferrites
Application of microwave heating provided a shorter time and reduced temperature for the production of Mn ferrite magnetic
particles
Chitosan-modied MnFe2O4 composite present in homodisperse
without any aggregation with a cubic structure
The MS of chitosan-modied MnFe2O4 particles found to be lower
than MnFe2O4 particles without chitosan modied due to the existence of the nonmagnetic chitosan on the surface on the MnFe2O4
particles.

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

Raw material

263

264

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

spectroscopy show that the vacancies can be completely random,

or partially or totally ordered for particles exceeding 5 nm [71]. A
large amount of magnetic materials can be produced through this
method, but the control over the particle size distribution is limited.
3+
Fe2O3: 0. 75[Fe 3 +]Td [Fe5/3
V1/3]Oh O4

(3)

Fe3O4 : Fe 3 + Fe 3 +Fe2 + O4
Td +
Oh

(4)

In general, the precipitation process is initiated by a short burst

of nucleation when the concentration of the species reaches critical supersaturation and followed by the slow growth of the nuclei by diffusion of the solutes to the surface of crystal [72,73].
However, the shape and size of the magnetic material produced by
this method can vary by manipulating certain parameters such as
the ionic strength, pH, temperature, nature of the salts (perchlorates, chlorides, sulfates and nitrates) or the concentration
ratio of Fe2 /Fe3 [74,75]. In addition, the particle size of magnetic nanomaterials can be controlled by the addition of chelating
organic anions (carboxylate or hydroxyl carboxylate ions such as
citric, gluconic or oleic acid) or polymer surface complexing agents
(dextran, carboxydextran, starch or polyvinyl alcohol) [76]. Many
researchers have employed this coprecipitation method on the
production of magnetic materials due to its simplicity and brought
in a wide range of manipulated parameters to obtain the required
dimension and characteristics of magnetic particles obtained.
Massart [77] was among the rst researchers to perform a controlled preparation of superparamagnetic iron oxide particles utilizing the alkaline precipitation of FeCl3 and FeCl2 which manages
to produce spherical magnetite particles with a diameter in the
nanometer scale. Furthermore, Massart [77] also performed another study to demonstrate the inuence of base (ammonia,
CH3NH2 and NaOH), the pH value of added cations (N(CH3)4 ,
CH3NH3 , Na , Li , K , and NH4 ) and the ratio of Fe2 /Fe3 on
the yield of the coprecipitation reaction along with the size of
magnetic material obtained [78]. Additionally, Jolivet et al. [79]
also performed a research on studying the inuence of the ratio of
Fe2 /Fe3 on the composition, size, morphology and magnetic
properties of the magnetic materials produced. The ratio value of
Fe2 /Fe3 which is represented by x demonstrates the phase that
exists between the particles produced. When the value of x obtained is 0.3, there were two distinct phases present; one is oxyhydroxyde and made of particle size of 4 nm with a low Fe2
content while the other phase is the nonstochiometric magnetite
consisting of variable size of larger particles. On the other hand,
the value of x 0.5 represents the magnetite stoichiometry phase
in which the particles are found to be homogenous in size and
composition [80]. Besides that, another study conducted by Babes
et al. [81] indicates that as the ratio of Fe2 /Fe3 increases, the
mean size of particle increases as well while the yield of magnetic
material obtained decreases.
The extensive growth of this simple yet signicant method
which has the control over the particle size of magnetic particles
being produced provided space for researchers to perform studies
on the production of magnetic biochar based on various biomasses. On that note, Saravanan et al. [20] employed gum kondagogu (GK) which were abundantly found in Hyderabad, India for
the production of GK-modied magnetic iron oxide particles by
coprecipitating Fe2 and Fe3 ions in the ratio of 2:1 using ammonia solution in the presence of GK biomacromolecules. This
well crystallined magnetic biochar were found to be thermally
stable compared to the raw GK with spherical aggregates structure
containing iron oxide particles. The magnetic biochar also exhibited a ferromagnetic behaviour with MS value of 60 emu/g

where by a 65.2% of Fe3O4 is able to provide a MS value of 92 emu/

g. This magnetic behaviour provides an additional room for the
application of this magnetic biochar in various industries. Moreover, Jiang et al. [21] synthesized magnetic chitosangraphene
oxide (MCGO) through the chemical precipitation of Fe2 and
Fe3 ions (obtained from the mixture of NH4Fe(SO4)2
12H2O and
NH4Fe(SO4)2
6H2O) over the chitosan-graphene oxide (CGO)
suspension which were synthesized earlier. This study produced
MCGO with a quite rough surface and spherical iron oxide particles were well-dispersed on the surface of CGO layers with a high
density. The good magnetic properties of MCGO composite were
attributed to the presence of maghemite and magnetite particles
in the magnetic biochar composite. This signicant characteristic
of magnetic biochar led to further application in waste water
treatment.
Similarly, Yu et al. [22] employed sugarcane bagasse as the raw
material for the production of magnetic modied sugarcane bagasse (MSCB) through the chemical precipitation of Fe2 and
Fe3 (obtained from FeCl3 and FeSO4) over the sugarcane bagasse
particles in an ammonia solution to go through an ultrasound irradiation at 60C. A large amount of carboxyl groups was found on
the surface of sugarcane bagasse which made the surface more
negatively charged. In addition, Devi et al. [82] synthesized zerovalent iron magnetic biochar composites (ZVI-MBC) from the paper mill sludge biochar in which the NaBH4 solution was used as
the reducing agent for the reduction of FeSO4 to Fe(0) as in Eqs. (5)
and (6)

FeSO4 + H2O FeOHSO4 + H +

(5)

4Fe 3 + + 3BH4 + 9H2O 4Fe( 0) + 3H2BO4 + 12H + + 6H2

(6)

The BET surface area and micropore volume of ZVI-MBC were

found to be 101.23 m2/g and 0.029 cm3/g while the BET surface
area and micropore volume of paper mill based biochar was
67 m2/g and 0.026 cm3/g respectively. This study suggests that the
immobilization of the ZVI on the biochar surface provided additional surface area for adsorption. However, the total pore volume
of the ZVI-MBC (0.079 cm3/g) was found to be lower than biochar
(0.083 cm3/g) due to the introduction of NaBH4 in some of the
mesopores. The micropores of the biochar were still found to be
unaltered after the magnetization process, which indicates that
the ZVI-MBC retained its adsorptive capability. The magnetic biochar also exhibited well-crystalline morphology.
Similarly, Mohan et al. [83] employed abundant almond shells
through the chemical precipitation of Fe2 and Fe3 (through the
usage of FeCl3 and FeSO4) over the almond shell based biochar. The
total pore volume of the magnetic biochar (0.97 cm3/g) and nonmagnetic biochar (0.95 cm3/g) indicated that both products are
more mesoporous than macroporous. Moreover, the BET surface
area of magnetic biochar and non-magnetic biochar were found to
be 527 m2/g and 733 m2/g respectively, in which the reduction in
the BET surface area after magnetization is attributed to the
smaller fraction of carbon present in the magnetic biochar or the
same amount of pore blockage by dispersed iron oxide particles.
Besides that, magnetic biochar were found to exhibit a spongy
porous texture while the non-magnetic biochar exhibited a porous
texture with small canals. This change acknowledges the formation of well-dispersed iron particles covering the biochar. In addition, the magnetic biochar also demonstrated a ferromagnetic
behaviour with MS value of 4.47 and 6.54 emu/g at 27 C and
227 C. These remarkable characteristics provided an extra source
of information regarding the application of magnetic biochar as a
good adsorbent in waste water treatment. On par with this
statement, Yuwei et al. [84] synthesized a novel chitosan based
magnetic biochar through one-step coprecipitation method in the

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

presence of FeSO4
6H2O and FeCl3
6H2O with a molar ratio of 1:2
with respect of Fe2 :Fe3 . This magnetic biochar exhibited no
remanence and coercivity, which suggests that the well-crystallined magnetic biochar produced are superparamagnetic with a
saturation magnetization, MS value of 36 emu/g [85]. Table 2.4
summarizes the co-precipitation process on the production of
magnetic biochar with different biomass.
1.3.3. Calcination
In brief, calcination is dened as a thermal process in which a
material is subjected such as ores or carbon material to heat in the
absence of fusion to remove water, drive off CO2, SO2 and other
volatile constituent and to bring upon thermal decomposition
[86]. Generally, as for the laboratory scale, calcination is done in a
pressurized autoclave or while the pyrolysis process is done in
different types of furnace with the ow of inert gas such as nitrogen or argon. The simplicity of this process was the main reason
behind the wide application of this process in the production of
magnetic nanomaterial.
On that note, Ma et al. [23] employed the abundantly available
agricultural waste, corncob to produce magnetic biochar in the
presence of FeCl3
6H2O in sealed Teon autoclave at 180 C for
6 h. The magnetic biochar produced through this method exhibited successful immobilization of iron oxide particles on the
surface of the corncob biochar despite their uneven distribution.
The calcination process on the corncob along with a metallic solution led to the removal of impurities without destroying the
core structure of corncob. Besides that, the attachment of Zn2
on the corncob biochar yields a carbonaceous structure composed
of polycyclic aromatic carbon sheets under a low calcination
temperature. Similarly, the magnetic biochar produced exhibited a
combination of macropores and mesopores in its morphology
upon the activation of Fe3 through the heating process in the
autoclave. The BET surface area of the magnetic biochar was calculated to be 153.89 m2/g and found to be higher than biochar
(69.45 m2/g) in which the drastic increase in the surface area is
attributed to the presence of Fe3 species which increased the
formation of pores on the surface of magnetic biochar. Furthermore, the magnetic biochar produced showed a good reusability
and easy separation property in regeneration studies. Similarly,
Gao et al. [24] synthesized magnetic biochar in the presence of
FeCl3
6H2O as the metallic salt solution and pine cone as the raw
material. These mixtures were calcined in a Teon-lined high
pressure reaction autoclave at a constant temperature for a given
time period. The Fe3O4/P magnetic biochar produced showed wellcrystallined morphology with a porous structure of pinecone
biochar which were adhered tightly by the Fe3O4 particles. On the
other hand, the increase in the specic surface area from 23.85 m2/
g (Fe3O4) to 27.86 m2/g (Fe3O4/P) and the pore size value from
9.26 m2/g (Fe3O4) to 21.02 (Fe3O4/P) indicates that the combination of calcined porous pinecone increased the pore size of Fe3O4
leading to a higher specic surface area and pore size. In addition,
Peng et al. [87] employed this calcination process to an extensive
level by converting the blue-green microalgae to magnetic biochar
in the presence of FeSO4
6H2O in a stainless steel reactor at different heating temperatures for a duration of 6 h. This study exhibited a different morphology of magnetic biochar being produced during the loading of different amount of FeSO4
6H2O. A
lower amount of FeSO4
6H2O exhibited magnetic biochar with
sheet morphology while a higher amount of FeSO4
6H2O produced magnetic biochar in the form of particles. This development
of different morphology at different loading of iron salt may be
attributed to the Fe3 conjugation effect which induces the carbon
structure aggregation. Additionally, the highest content of iron salt
found to produce magnetic biochar with the highest BET surface
area value of 128.3 m2/g and pore volume value of 0.029 cm3/g.

265

The saturation magnetization, MS value of magnetic biochar was

measured to be 39.8 emu/g, in which it exhibits a ferromagnetic
behaviour and its ability to be attracted by a strong magnet for
easy separation from an aqueous solution. Besides that, the magnetic biochar showed a good 96% recovery after a three consecutive adsorption-desorption cycles, indicating its ability to be
reused. Similarly, Lian et al. [88] developed magnetic biochar from
a well-known clay, bentonite in the presence of FeCl3
6H2O by the
performing the calcination process on these mixtures in an autoclave at a temperature of 190C for 8 h. An advantage of the calcination process would be the tendency of generating materials
with controlled size and high magnetism. Hence, this study exhibited the well-developed Fe3O4 particles with controlled size on
the surface of the bentonite homogenously due to the vigorous
boiling solvent. The Fe3O4 produced through this method also
exhibited a smoother surface and narrower size distribution.
Consequently, the loading of Fe3O4 particles on the surface of
bentonite produced magnetic biochar which are more stripped,
loose and curly slice layers on the bentonite surface along with the
high amount of Fe3O4 on its surface. Similarly, the well-crystallined magnetic biochar produced exhibited high magnetization
saturation, MS value of 36.18 emu/g with no remanence, indicating
superparamagnetism behaviour due to the attachment of Fe3O4
microspheres. This magnetization property indicates its ability to
be easily removed from the aqueous solution by an external
magnet. Table 2.5 summarises the calcination process on the
production of magnetic biochar based on the availability of different biomass.
All of these three synthesis methods of magnetic biochar exhibits a good future of the utilization of agricultural waste to solve
the highlighted environmental issue. All these methods were
found to utilize any type of agricultural waste without any hassle.
Every method has its own set of advantages and pullbacks which
need to be further considered prior to the selection for the production of magnetic biochar. In terms of machinery, the co-precipitation method was found to be the simplest due to its simple
steps consisting of mixing and heating. This method focuses on the
molar ratio of transition metals ion being used during the mixing
for better characteristics of magnetic biochar being produced in
terms of magnetism and porosity. Furthermore, calcination also
utilizes a simple autoclave Teon method with heating for the
production of magnetic biochar. On the contrary, the conventional
and microwave heating were found to consist of heavy machinery
system with additional requirement such as inert gas ow. The
inert gas ow is generally required to ush out air molecules
during the heating process to create zero oxygen ambient, leading
to the production of magnetic biochar with a smooth surface
morphology, high BET surface value and pore volume. In addition,
microwave heating requires the installation of quartz tube for the
ease of heating at a very high temperature. On the contrary, iron
based metallic salt were found to be more favourable compared
with other metallic salt for the production of magnetic biochar.
This might be due to the already established literature review
which provides good information on the utilization of iron based
metallic salt for the synthesis of magnetic biochar based on various methods. Certain studies also established good characteristics
of magnetic biochar by employing nickel, cobalt, aluminum and
manganese based metallic salt. Hence, the selection of these metallic salts would be made by examining its cost and the magnetic
strength of the magnetic biochar produced utilizing these metallic
salt.
2. Application of magnetic biochar
The signicant characteristics of magnetic biochar were the
major key for its extensive growth in various applications. The idea

266

Table 2.4
Summary of co-precipitation process on production of magnetic biochar with different biomass.
Raw material

Reagent

Magnetic biochar

Operating Condition

Powdered cocunut

CuCl2 and FeCl3

CuFe2O4-loaded magnetic
biochar

Process were carried out at pH10 and the suspension were heated to 98100 C for 2 h.
Molar ratio of 1:2 of Cu2 :Fe3

Characteristic of magnetic biochar

Reference

 CuFe2O4 exhibited spinel strucutre

[15]
 Highest MS value of 5.93 emu/g obtained for 1:1 ratio of
CuFe2O4:biochar

 Highest BET surface area of 558 m2/g obtained for 1:2 ratio
of CuFe2O4:biochar

 Highest micro-pore volume of 0.153 cm3/g obtained for 1:2

ratio of CuFe2O4:biochar

 Magnetic biochar were found to consists of ne particles of

Fe2(SO4)3.nH2O (n: 6 9)
and FeSO4

Magnetic oak wood biochar and magnetic oak

bark biochar

Process were carried out at pH10 to pH11 and the

suspension were aged at room temperature for
24 h






Two types of commercial biochar consisting of mixed wood chips known

as Bio and OrgBio

FeSO4
7H2O and

FeCl3
6H2O

MagBio and MagOrgBio

Process were carried out at pH10 to pH11 and the

suspension were stirred for 1 h and rested
overnight.
Molar ratio of 1:2 of Fe2 :Fe3

 BET surface area of Bio and OrgBio was 261 and 6.1 m2/g [46]



Kans grass straw (Saccharum

spontaneum)

FeSO4
7H2O and

FeCl3
6H2O

MKGB

Biochar were suspended in 200 mL mixed in

FeSO4 and FeCl3 solutions, under N2 ow in ammonia solution at 30C for 2 h
Molar ratio 2:1 of Fe2 :Fe3

respectively while the BET surface area of MagBio and

MagOrgBio was 219 and 68 m2/g
All the magnetic biochar had a higher specic open surface
areas compared to their prisitne form due to the high
specic open surface areas of iron oxides.
Measured mass magnetic suspectibility of MagBio and
MagOrgBio was 108.3 and 178.6 m3/kg

 MGKB were found to have a high MS value of 45.7 Am2/kg [142]

and exhibit a ferromagnetic behaviour

 MGKG showed a higher thermal stability

 MGKB showed a more porous surface due to the good
dispersion of Fe3O4

 A high BET surface area and total pore volume of 31.45 m2/
g and 0.1771 cm3/g

Corncob

Peeled pine wood (Pinus massoniana)

MgCl2 and CaCl2

Hydrous-manganeseoxide (HMO)

Ca-Mg/biochar

HMO-loaded biochar

Corncob was suspended in MgCl2 (ratio of 1:3)

and CaCl2 (ratio of 1:3) and were further heated
under N2 ow

Biochar were loaded in different concentration of

HMO and was further stirred for 24 h at 25 C

 A high BET surface area value of 487.49 m2/g at a heating [49]

temperature of 600C

 Ca-Mg/biochar exhibits mesoporous strucutre and col-





Sugarcane baggase (SCB)

FeCl3 and FeSO4

Magnetic modied sugarcane bagasse (MSCB)

Mixture dissolved in an ammonia solution and

proceed with ultrasound irradiation at 60C.
Molar ratio of Fe3 :Fe2 is 1:2

lapsed at a higher temperature post the co-precipitation

process. The opening of porous leads to an increase in the
BET surface area.
Lowest concentration of HMO led to generation of mag- [29]
netic biochar with the highest BET surface area and pore
volume value of 361 m2/g and 0.194 cm3/g
Excess loading of HMO leads to pore bloackage resulted in
a decrease in surface area and pore volume
Magnetic biochar were produced with a morphology of
micron-sized HMO particles dispersed on the surface of
biochar

 Magnetic biochar exhibited a smooth and highly porous [22]

structure

 A large amount of carboxyl groups found on the surface of

SCB which made the surface more negatively charged.

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

Oak wood and oak bark

CuFe2O4 covering specic part of biochar and this is the

reason behind the constant high surface area in biochar
Magnetic oak wood were produced with a surface area of [26]
2.04 m2/g while magnetic oak back were produced with a
surface area of 25.4 m2/g
Both magnetic biochar exhibit macro porosity.
Needle and star shaped crystalline forms are found separated in both magnetic biochar
MS value of magnetic oak wood and magnetic oak bark
were 8.87 and 4.47 emu/g respectively.

stability

ferromagnetic behaviour

 Magnetic biochar produced were well crystallined

 Magnetic biochar produced exhibited a good thermal

spherical shapes

 Highest MS value of 55.3 emu/g were obtained, exhibiting a

 Fe3O4 particles on the surface of biochar presents in [27]

The mixed solution was stirred under N2 at 80 C

for total of 2 h in ammonia solution
Molar ratio of Fe2 :Fe3 is 1:0.75
FeCl2
4H2O and Fe2O3
(present in the red mud
itself)
Red mud

Fe3O4-loaded red mud

magnetic biochar

noncrystalline hemicellulose and lignin

Highest MS value of 11.87 emu/g were obtained in which
the MS value differ according to the content of Fe3O4
MWS can be re-used 10 times with recycling efciency of
80%

FeCl3
6H2O and

FeSO4
7H2O
Wheat straw

Fe3O4-loaded wheat straw Mixture dissolved in an ammonia solution with

magnetic biochar (MWS) the presence of N2 and the temperature of mixture was raised to 70 C and held for 4 h.
Molar ratio of Fe3 :Fe2 is 2:1

 Wheat straw mainly consists of crystalline cellulose and

[143]

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

267

of magnetizing a biochar employed from various types of biomass

has caught the attention of researchers from different parts of
world. On that note, magnetic biochar were found to be widely
used in the water treatment industry as an adsorbent. The need of
clean water is given a very high priority in every part of the world,
especially in third world countries. The major reason behind the
contamination of water would be due to the discharge of hazardous efuent such as heavy metals from industries such as
mining, battery, metal plating and paper industries or organic
substances and dyes from textile industries into the nearby source
of water without any treatment [89]. Hence, to provide a clean
water source to the end user, various wastewater techniques such
as ion exchange [90], membrane ltration [91], biological treatment [92] and adsorption [93] were opted to solve this issue.
Every method of wastewater treatment was found to have its own
set of advantages and disadvantages.
The ion exchange method is one of the ways to remove unwanted dissolved particles from solutions. All natural waters
bodies contain dissolved salts in varied concentrations and remain
dissociated in water in the form of ions. Positively charged ions are
called cations and negatively charged ions are called anions. Ion
exchangers exchange one ion for another that has the same kind of
charge, hold it temporarily, and then release it to a regenerate
solution [94]. In an ion exchange system, undesirable ions are
replaced with ions of higher afnity. For example, in a sodium
zeolite softener, calcium and magnesium ions are replaced with
sodium ions [95]. The standard ion exchange process has been
modied in many systems to reduce the production of waste and
the use of costly regenerating materials. Such modications include the use of weakly acidic or basic resins, decarbonators and
degassers, using strongly basic anion caustic waste for regeneration of weakly basic anion exchangers, and partial regaining of
spent caustic for subsequent regeneration cycles [96,97]. The ion
exchange process is employed to swap one ion for another for the
purpose of demineralization. The process is primarily used for
removing the hardness by replacing calcium and magnesium ions
with other specic ions. However, these days it is being used more
frequently for the removal of other dissolved ionic species.
On the contrary, the membrane ltration technique gained
popularity due to its advantage of controlled pore size distribution
with high exibility and strength [97]. Membrane separation
processes are different from other separation techniques because
of the mechanism involved and size of the separated particles.
Membranes provide a physical barrier that permits the passage of
selective materials based on their size, shape or character. Owing
to the increasingly stringent legislation and continuous advancement in membrane technology, application of the technology in
wastewater treatment has expanded greatly over the last decades.
One of the signicant implementations of membrane technology is
in the membrane bioreactor (MBR). The MBR system is a technique
used for the separation of biological solids and is applied as one of
the alternatives to the aerobic sludge process. The process is very
effective due to the retention of all the microbes by the membrane
[98].
On the other hand, biological treatment of wastewater occurs
mostly by biological mechanisms which are generally classied as
aerobic and anaerobic wastewater treatment. Aerobic wastewater
treatment is a process in which bacteria uses oxygen to degrade
organic matter lowering the biochemical oxygen demand or BOD
of the water and removes other pollutants [99]. The two most
basic types of aerobic wastewater systems are activated sludge
system [100] and aerated stabilization basin [101]. Anaerobic
treatment is the process in which pollutants and organic matter
are converted into less harmful compounds by microorganisms in
the absence of dissolved oxygen [102,103]. However, anaerobic
bacteria can use oxygen present in the form of oxides, or they can

268

Table 2.5
Summary of calcination process on production of magnetic biochar with different biomass.
Reagent

Magnetic biochar

Operating Condition

Characteristic of magnetic biochar

Reference

Rice hull

Ferric acetylacetonate, Fe
(C5H7O2)3

Fe3O4-loaded rich hull magnetic biochar

Calcined at 100C in a tube

furnace for 1 h

 Well-crystallined magnetic biochar were produced with a surface covered with a good [144]

FeCl3
6H2O

Magnetic chitosaniron(III)
hydrogel (MCh-Fe)

Calcinied at 200C for 16 h

 Tiny particles of Fe3O4 were found to be attached on the surface of MCh-Fe

[145]
 Shape of MCh-Fe is irregular with the high density attachment of spherical Fe3O4 mi-

dispersion of Fe3O4 particles

 Magnetic biochar exhibtied superparamagnetic behaviour with no coercivity and remanance, with MS value of 14.3 emu/g

Chitosan

crosphers in its surface

 Well-crystallined MCh-Fe were produced

 A mild MS value of 4.58 emu/g were produced which is attributed to the presence of ChFe cross linked complex in the MCh-Fe composites

Clay (bentonite)

FeCl3
6H2O

Fe3O4-loaded bentonite magnetic biochar

Calcined at 190C for 8 h.

Fe3O4-loaded microalgae
magnetic biochar

Calcined at different temperatures for 6 h

 Well-developed Fe3O4 particles produced with controlled size on the surface of the [88]
bentonite homogenously due to the vigorous boiling solvent

 Magnetic biochar exhibtied a MS value of 36.18 emu/g with no remanence, indicating

superparamagnetism behaviour due to the attachment of Fe3O4 microspheres

Blue-green microalgae FeSO4
6H2O

 Highest loading of FeSO4
6H2O provided highest BET surface area value of 128.3 m2/g [87]
and pore volume value of 0.029 cm3/g.

 The saturation magnetization, MS value of magnetic biochar was found 39.8 emu/g, in
which exhibits a ferromagnetic behaviour

 Magnetic biochar showed a good 96% recovery after three consecutive adsorption-desorption cycles, indicating its ability to be reused.

Corncob

FeCl3
6H2O

Fe3O4-loaded corncob magnetic biochar

Calcined at 180 C for 6 h

 BET surface area of magnetic biochar was calculated to be 153.89 m2/g and it found to be [23]
higher than biochars surface area (69.45 m2/g)

 Attachment of Zn2 on the corncob biochar yields a carbonaceous structure composed

of polycyclic aromatic carbon sheets under a low calcination temperature.

 Magnetic biochar produced showed a good reusability and easy separation property in
regeneration studies.

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

Raw material

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

obtain it from organic material within the waste water. Digestion

of organic matter in the absence of oxygen is usually used to treat
sludge in the initial steps of a wastewater treatment plant [104].
This process is popular because it can stabilize the water with little
biomass production. Anaerobic treatment occurs in many different
stages. The essential microorganisms involved are methane formers and acid formers. The acid formers are microbes that create
acids from the sludge [92]. Methane formers convert the acid into
methane [105].
An adsorption process denes all the solid substances which
attracts to molecules of gases or solutions to their surfaces when
kept in contact. Solids that adsorb gases or dissolved substances
are called adsorbents. The adsorbed molecules are called as the
adsorbate. The adsorption by solid adsorbents is one of the most
efcient methods for the removal of organic contaminants and
waste water treatment. Adsorption involves simpler design and
low investment regarding both space and cost as compared to
other methodologies. It holds great attention from the researchers
because of its widespread use for treatment of industrial waste
water. Researchers are in search of inexpensive adsorbents with
binding capacities to a wider range of pollutants [93,106]. Locally
available materials such as agricultural and industrial wastes can
be utilized as low-cost adsorbents.
Among various water treatment technologies, adsorption was
found to be the favourite choice of the industry due to its signicant advantage such as low cost, availability, ease of operation,
low cost and protability [107,108]. Generally, carbon based material is opted as an adsorbent and on that note; magnetic biochar
possessed all the required characteristics to be used as an adsorbent with an advantage of easy separation by an external
magnet from treated solution. Groundwater contamination is given equal importance due to the tendency of contaminants
transferring into our daily drinking water. On that note, groundwater can be easily contaminated due to the highly toxic heavy
metal such as arsenic which is naturally available in the Earths
crust in which the consumption of arsenic contaminated water
brings a serious threat to the public health and it has already affected millions of people around the world [109]. The abundantly
available biomass such as cottonwood [110], pinewood [16], hickory chips [111] and corn straw [112] were developed into magnetic
biochar to be used as adsorbent for the removal of arsenic from
groundwater which indeed showed a remarkable adsorption with
a high adsorption capacity value. This extensive study indirectly
solves the water pollution and the abundantly available waste
management issue. On the other hand, heavy metals such as zinc
[113], lead and cadmium [25,114], tin [115], chromium [116] and
copper [117] were also discarded from a contaminated water
source by the application of magnetic biochar as adsorbent in a
simple adsorption process. Likewise, the textile industry is a constantly growing industry due to the never ending demand of
fashion in current generation. This industry consumes large
amount of water and hence, produces high volume of waste water
from processes such as colouring and nishing which is rich in
different colours. The discharge of this coloured waste water
which contains harmful chemicals into any water source is highly
undesirable and a proper treatment before the discharge is highly
recommended. The same adsorption process utilizing magnetic
biochar as the adsorbent were employed for the treatment of
these coloured waste water, in which synthetic dye compounds
such as methylene blue [118,119], malachite green [120], crystal
violet [121] and congo red [122] were adsorbed prior to discharging the efuent to nearby sources of water. Besides that, hydrophobic organic compounds (HOCs) and eutrophication anion such
as nitrogen and phosphate were found to be one of the major
contributions for water pollution as well. Consequently, the lack of
oxygen for the growth of algae and respiration of sh has

269

impacted the aquatic habitants badly. Certain studies were done

employing magnetic biochar as the adsorbent for the treatment of
the water source contaminated by elements such as naphthalene
(NAPH), p-nitrotoluene (p-NT) and phosphate [31], tetracycline
[123], pentachlorophenol [82] and phenanthrene [124] in which
the simple adsorption process provided a signicant treatment
process by removing all these pollutants in the contaminated
water. These entire positive outcomes boost the production of
magnetic biochar from different biomass in a bigger scale for its
application in waste water treatment. Table 2.6 demonstrates the
summary of application of magnetic biochar in waste water
treatment.
Another upcoming application of magnetic biochar would be in
the electronic industry, ranging from conductive polymer to supercapacitor. The growth of technology in the year 2015 has been
remarkable and the constant discovery of new small gadgets like
smartphones, tablets and smartwatch acknowledges the increase
in the demand of smaller integrated circuits and chips to be placed
in the gadgets. A smaller yet high performance integrated circuit
and chips are denitely costly to be produced. On that note, supercapacitors (known as electrochemical capacitors) emerges to
be one of the important alternative power sources for batteries
due to its higher power density and longer life cycle compared
with the batteries. Besides that, supercapacitors were found to
have a higher energy density than the dielectric capacitors as well
[125127]. In general, the characteristics of supercapacitor are
determined by the material of electrode being used in which metal
oxides and conductive polymers already been roped and tested for
its application as the electrode in supercapacitor. Although conductive polymer such as polyaniline [128] and polypyrrole [129]
exhibited a high capacitance value, its low surface area and poor
stability prevent its further commercialization in a bigger scale. On
that note, magnetic biochar produced from a variety of biomass
exhibited signicant characteristics such as high surface area, excellent conductivity and stability to be opted as an electrode material for supercapacitor [130]. On par with this statement, magnetic biochar developed from different biomass such as rice husk
[131], soft tissues of watermelon [132], chitosan [133], corn stover
[130], walnut shell [32] and cotton stalk [134] in the presence of
metal salt solution such ZnCl2, MnO2, NiO, and Fe3O4 were employed as the electrode material in a supercapacitor in which a
remarkable high capacitance, high current density and high electrical conductivity value were produced. The development of a
waste material into a material to be integrated into a conductive
circuit is indeed remarkable. Recently, conductive polymers which
are obtained through the conductive through the conjugated bond
system along the polymer backbone are cooperated into the supercapacitor as the electrode material due to its ability to store
charge in the bulk of the material, leading to an increase in the
total energy stored in the supercapacitor [135]. The most common
polymer, polyaniline (PANI) and polypyrrole (Ppy) were successfully cooperated with magnetic biochar derived from different
biomass such as wood sawdust [136], hemp (Cannabis sativa L.)
[137,138] and banana bers [139] through process such as in-situ
polymerization and solution casting. This conductive magnetic
biochar/polymer composite provided an impressive increase in the
capacitance and current density value, indicating feasibility in
supercapacitor without any major pullback. The application of
magnetic biochar in the supercapacitor industry along with conductive polymer is an on-going research. Table 2.7 summarises the
few notable applications of magnetic biochar in the related sector.
3. Future challenges of magnetic biochar
The demand of magnetic biochar has been growing for the past
few years due to its signicant characteristic and remarkable

270

Table 2.6
Brief Summary of application of magnetic biochar in removal of contaminants from wastewater.
Magnetic biochar

Adsorbate

Optimized Condition

Adsorption Capacity (mg/g)

Remarks

Hematite, -Fe2O3 loaded pinewood magnetic biochar

Pine bark/magnetic biochar composite (MBC)

As (V)

Constant concentration of 20 mg/L, dosage

of magnetic biochar of 0.5g
pH 5 of respective aqueous metal ion solution, equilibrium time of 120 min

0.429

 Adsorption data tted well by Langmuir model which de- [16]

Pb (II) and Cd (II)

Reference

scribe monolayer adsorption processes

3.177 0.07 (Pb2 ), 2.727 0.06

(Cd2 )

 An increase from pH 2 to pH 5 saw an increase in the ad- [25]

 Adsorption capacity of magnetic biochar increases as the pH [146]

sorption capacity of MBC

 Kinetic data t well to the pseudo-second-order rate model

 Equilibrium data tted well to the Sips isotherm model
compared to Langmuir and Freundlich isotherm models

FeCl3-loaded empty fruit bunch

(EFB) magnetic biochar

Methylene blue (MB) and Orange-G (OG)

pH 2, dosage of 1.0g and contact time of

120 mins (pH 10 as well for MB only)

31.25 for MB and 32.36 for OG

Chitosan-modied MnFe2O4 magnetic biochar

Cu (II)

Initial Cu2 concentration of 50 mg/L and

100 mg/L, contact time of 500 mins, pH
6.5 of aqueous solution

65.1

of solution, contact time and adsorbent dosage increases.

Freundlich isotherm model

 Adsorption data ts well with Langmuir isotherm model

[147]
 Adsorption kinetic agrees well with pseudo second order


Zero-valent iron-loaded paper mill

magnetic biochar composites
(ZVI-MBC)

Pentachlorophenol (PCP)

Fe3O4-loaded corn stalks magnetic

biochar (MBC)

Crystal violet (CV)

MgO and FeO-loaded conocarpus

magnetic biochar

NO3

Fe3O4 -loaded corncob magnetic

biochar
Fe3O4-loaded microalgae magnetic
biochar

FeSO4:NaBH4 molar ratio of 1:10, 0.7% of

adsorbent dosage, ZVI: biochar ratio of 1:2

Not available

pH 6.0 of aqueous solution, 40 C of adsorption temperature, initial CV concentration of 400 mg/L

Initial pH of 2.0 and initial NO3 concentration of 1.0 mg/L for both adsorbent

349.40




45.36 for MgO and 20.27 for

FeO




 Adsorption data were well tted with Langmuir isotherm [148]

model and Type 1 pseudo second order kinetic model

 MgO-loaded magnetic biochar had a higher adsorption ca-

Methylene blue (MB)

Initial MB concentration of 150 mg/L

163.93

Tetracycline (TC)

3.0g of dried microalgae and 6.0 mmol of

iron salt

95.86





Fe(NO)3-loaded cotton fabric magnetic biochar

Cr (VI)

Pb (II) and Cd (II)

Magnetic oak wood biochar
(MOWBC) and magnetic oak bark
biochar (MOBBC)

Initial Cr (VI) concentration of 4.0 mg/L, ad- 3.74

sorbent dosage of 2.0g and pH 3 of aqueous
solution
pH of 5.0 for both solution
MOWBC (Pb2 :10.13 and
Cd2 :2.87) MOBBC (Pb2 : 30.2
and Cd2 : 7.4)

model with pseudo second rate constants (K2) of 0.0468 and

0.00189g/mg/min for initial Cu2 ions of 50 and 100 mg/L
Adsorption capacity increases as the pH of the aqueous solution and contact time increases while decreases as the
initial Cu2 concentration increases
100% PCP removal from an industrial efuent were achieved [82]
after 480 mins of adsorption
Complete dechlorination of the PCP in the efuent by the
ZVI-MBC matrix.
Adsorption capacity of re-collected MBC was 73.31 mg/g
[121]
Adsorption of CV is spontaneous and endothermic





Magnetic corn stover biochar

(MCSBC)

Flouride

pH 2.0 of aqueous solution

4.11







Ni-doped bamboo charcoal magnetic biochar

Pb (II)

pH 5.0 of aqueous solution

142.7





pacity due to its high surface area and strong ionic

complexation
Adsorption data were well tted with Langmuir isotherm
model and Type 1 pseudo second order kinetic model
Adsorption capacity is inuenced by the surface area and
functional groups on the surface of magnetic biochar
Adsorption data were well tted with Langmuir isotherm
model
Adsorption capacity does not increase sharply as the total
iron content increases, indicating that the biochar has little
pore for TC to attach on iron oxide
Microwave heated magnetic biochar provided a higher adsorption capacity compared with conventionally heated
Complete Cr (VI) removal within 10 min
Adsorption data were well tted with Langmuir and
Freundlich isotherm model
Kinetic data t well to the pseudo-second-order rate model
Adsorption capacity increases with temperature
Kinetic data t well to the pseudo-rst-order rate model
Adsorption capacity decreases as the temperature increases
Adsorption data well tted with Langmuir, Redlich-Peterson,
Sips, Koble Carrigan and Toth
Kinetic data t well to the pseudo-second-order rate model
Adsorption data were well tted with Langmuir isotherm
model
Adsorption of Pb2 was spontaneous and exothermic

[23]
[87]

[68]

[26]

[149]

[141]

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

 Kinetic data t well to the pseudo-second-order rate model

 Equilibrium data were well tted by both Langmuir and

FeCl3-loaded empty fruit bunch

(EFB) magnetic biochar

Zn (II)

Magnetic kans grass biochar

(MGKB)

As (III) and As (V)

Magnetic chitosan

Co (II)

pH 10 of aqueous solution, adsorbents dosage of 0.09g, agitation speed of 120 rpm

and agitation time of 120 min

1.18

 Adsorption data were well tted with both Langmuir and [113]
Freundlich isotherm model

 Kinetic data t well to the pseudo-second-order rate model

 Magnetic biochar exhibited a higher adsorption capacity
compared to CNTs

Adsorbent dosage of 0.01g, Equilibrium time As (III): 2.0 and As (V): 3.1
of 3.4 h, 25 C of adsorption temperature
pH 5.5 of aqueous solution

27.5

 Adsorption data were well tted with Langmuir isotherm [142]

model

 Kinetic data t well to the pseudo-rst-order rate model

 Adsorption data were well tted with Langmuir isotherm [150]
model

 Adsorption process was exothermic in nature with an enthalpy change of 12.04 kJ/mol.

Magnetic CuFe2O4 activated coconut powder

Acid orange II

Hydrous-manganese-oxide loaded
magnetic peeled pine wood

Pb (II)

pH 7.0 of aqueous solution

404

 Adsorption data were well tted with Freundlich isotherm [15]

model

 Presence of CuFe2O4 increased the catalytic activity of

magnetic biochar

121.8

 Adsorption data were well tted with Langmuir isotherm [29]

model

 The negative value of G and positive value of H indicates

Ca and Fe modied magnetic rice

husk (RH)

As (V) and Cr (VI)

Magnetic energy cane biochar

Pb (II)

pH 7.0 of aqueous solution

pH 4.0-5.0 of aqueous solution

1000 and 58.48 of As (V) and Cr

(VI) based on Ca and Fe magnetic RH
35.66






Fe3O4 modied magnetic wheat

straw

Methylene blue (MB)

Fe3O4 modied magnetic wheat

straw

As (III) and As (V)

FeCl3 modied date pits magnetic

biochar

Methylene blue (MB)

0.1g of adsorbent dosage and pH 7.0 of

aqueous solution

1374.6

79 for As (III) of aqueous solution

As (V)



pH 3.0 for As (V) of aqueous solution and pH 3.898 and 8.062 for As (III) and 


pH 7 of aqueous solution, 0.5g/l of adsorbent 259.25

dosage and 4.5 h of contact time





Fe and Co loaded magnetic bamboo Cr (VI)

charcoal

pH 3 of aqueous solution

Fe loaded magnetic chitosan

pH 3 of aqueous solution

Cr (VI)

51.7



169.5






that the Pb (II) sorption process is spontaneous and

endothermic.
Adsorption data were well tted with Freundlich isotherm
model
All modied magnetic biochar exhibited a better removal of
As (V) compared to Cr (VI)
Adsorption data were well tted with Freundlich, Langmuir,
RedlichPeterson, Sips, Radke and Prausnitz, Toth and Koble
and Corrigan models.
Kinetic data t well to Lagergren rst order and pseudo
second order model.
Adsorption data were well tted with Langmuir, Sips, Peterson and Freundlich isotherms.
Kinetic data t well to the pseudo-rst-order rate model
Removal efciency increases with temperature
Adsorption data were well tted with Langmuir isotherm
model
Adsorbent can be regenerated and reused for a minimum of
ten cycles for arsenic adsorption.
Adsorption data were well tted with Sips isotherm model
Kinetic data t well to the pseudo-second-order rate model
Adsorption of MB were found to be spontaneous and
endothermic
Adsorption data were well tted with Langmuir isotherm
model
Kinetic data t well to the pseudo-second-order rate model
Adsorption of Cr (VI) were found to be spontaneous, exothermic and dominated by ion exchange mechanism
Adsorption data were well tted with Langmuir isotherm
model
Kinetic data t well to the pseudo-second-order rate model
Adsorption are more favourable at higher temperature with
an endothermic nature
Adsorbent were found to be stable in the condition used

[151]

[152]

[153]

[143]

[17]

[19]

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

pH 5.0 of aqueous solution

[145]

271

272

Table 2.7
Brief Summary of application of magnetic biochar and magnetic biochar conductive polymer composite.
Magnetic/Biochar Polymer
Composite

Morphology

Electrical and Capacitance

Value

Remarks

Nickel loaded hydrochar (derived

from rice husk) composite

 Ni particles were well dispersed on the surface of hydrochar

 Specic capacitance: 174.5 F/  The existence of the nickel particles can contribute to the trans- [131]
g

FeCl3 oxidized Microbrillated cellulose (MFC)/Ppy composite

Boron doped wood sawdust

(BAWDC) /PANI composite

 Composite was in the form of a black sheet which had a thick-  Conductivity: 1.5 S/cm







ness of roughly 1.5 mm.

It was mechanically stable but relatively brittle.
Composite exhibited an open, porous structure of intertwined
bers
BET surface area of composite was 89 m2/g
Composite exhibits irregular framework structure with some
particles of BAWDC attached to the surface
Less porous structure indicating attachment of PANI layer
blocking the pores of BAWDC
Highest BET surface area of 25.8 m2/g of composite obtained




 Specic capacitance: 421 F/g  Higher capacitance value is attributed to the improved BET surface [136]




Fe3O4 loaded magnetic chitosan

mission of electron in solution and help to the increase of

capacitance.
Nickel/hydrochar composite exhibited a better capacitance behaviour compared to nickel/activated carbon composite
[154]
Brittleness is inuenced by the Ppy-Ppy bonds
Composite showed electroactive with an ion-exchange capacity for
Cl- of 289 C/g (80 mAh/g)

 Fe3O4 particles were well dispersed on the surface of the carbon  Specic capacitance value of 

substrate
composite: 299 F/g
 Fe3O4 particles were highly wrapped by the ake like carbon
materials with a mean size of approximately 1 mm

 Composite exhibited an amorphous phase

 BET surface area value of composite were measured to be

area, enhanced electron transfer, and electrochemical reactivity due

to boron doping.
Larger CV area is attributed to the synergistic effect of composite
Specic capacitance value of electrodes decrease with the increase
of scan rates due to more difcult penetration and diffusion of the
electrolyte ions under higher scan rates.
Composite exhibited a high energy density value of 45.2 Wh/kg at
power density of 876 W/kg
Composite as an electrode exhibited an excellent recycling stability [155]
The specic capacitance retention was measured to be 83% and the
specic capacitance can still retain up to 215 F/g after 2000 cycles at
current density 1 A/g
Electrode material exhibited a high energy density of 135 Wh/kg at
power density of 1598 W/kg

272.5 m2/g

MnO2 loaded magnetic cotton stalk

 Non-uniform micron spherical particles of MnO2 are disperse  Specic capacitance value of  Composite also exhibited a capacitance retention ratio of 99.2% after [156]
throughout the surface of activated cotton stalk

 Composite exhibited an amorphous structure

 BET surface area of composite was measured to be 1.481 m2/g

Nitrogen doped wood derived carbon

(NKWC)/PANI composite

composite: 169 F/g

500 cycles

 Composite exhibited a better capacitance behaviour compared with

porous carbon

 The chemical properties and wettability of the composite material

 PANI particles were well grown on the porous surface of NKWC  Specic capacitance value of 
through the in-situ polymerization process

 BET surface area of composite were measured to be 26.4 m2/g

2

lower compared to NKWCs value of 129.8 m /g but much

higher than PANIs value of 21.9 m2/g

composite: 347 F/g

can provide a higher ionic concentration and lower resistance of

supercapacitor
Composite exhibited an energy density of 44.4 Wh/kg at power [157]
density of 922 W/kg
Composite retains about 76% and 67% of its original capacitance
after 1000 and 2500 cycles respectively

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

Reference

K.R. Thines et al. / Renewable and Sustainable Energy Reviews 67 (2017) 257276

application in various industries. However, this extensive demand

faces few complications which should be solved for further production of magnetic biochar in a bulk scale. One of the major
pullbacks would be the selection of raw material. As mentioned
earlier, the availability of agricultural waste material is huge and it
has been increasing day by day due to the complication faced in
the waste management sector. The selection of raw material for
the production of magnetic biochar based on this agricultural
waste is solely based on its characterization such as moisture
content, ash content, carbon content, and surface area. These
characterizations play a vital role on the morphology and properties of the magnetic biochar being produced. Hence, a rough
scan of the agricultural wastes characteristics has to be done prior
to developing it into magnetic biochar. Furthermore, the handling
of these agricultural wastes has to been given extra attention to
avoid the spread of unwanted contaminants from these wastes to
the surrounding environment either through water or air source.
Similarly, the transportation cost of these agricultural wastes in a
bulk scale to the respected industry also should be taken into
consideration. The excessive dumping of agricultural waste into an
open eld which provides a negative impact to the surrounding
either by burning it or burying it certainly can reduced by utilizing
it for the production of magnetic biochar. Hence, other than its
extensive properties, the magnetic biochar will also be known as
an environmental friendly product.
On the other hand, the successfully developed magnetic biochar would face a problem in the marketing section. It would be
difcult to convince other industrialist to rely on an agricultural
waste for their respected application either in waste water treatment or electrical industry. Hence, a series of test and preliminary
results of the application of magnetic biochar in the required
sector should be done in a laboratory scale prior to its large scale
production. If these products obtain fame quickly among the end
user, fellow industrialists would be more convinced to invest in
the development of magnetic biochar from agricultural waste.
Likewise, a continuous improvement on magnetic biochar in terms
of its properties and characterization is required to sustain its need
in its respected market. Magnetic biochar can either be coated
with other carbon materials such as carbon nanotubes or graphene
or with polymers to improve its properties and expand its application in other industries as well. On the other hand, agricultural
wastes are meant to be run out of supply after certain period of
time. Hence, a continuous search on other carbon related materials
with the same characterizations of these agricultural wastes are
required as well.

4. Conclusion
The improper management of agricultural waste has been
highlighted as one of the concerned sustainability issues which
have a huge impact on the surrounding health of habitants. This
issue is addressed by the production of biochar utilizing the
abundantly available agricultural wastes which are welcomed by
the industrialists. The extensive application of biochar in various
industries required a continuous improvement which triggered
the production of novel magnetic biochar. Magnetic biochar were
produced with signicant properties by employing the modied
production method of biochar. There were three main production
methods of magnetic biochar which were denoted as successful on
producing magnetic biochar with high porosity, magnetic strength
and signicant morphology to provide a good performance in
various applications. Magnetic biochar which were produced from
various types of agricultural waste exhibited a high adsorption
capacity towards contaminants such lead, chromium, copper, tetracycline, methylene blue and crystal violet with a maximum

273

adsorption capacity value of 142.7, 169.5, 65.1, 95.86, 259.25 and

349.40 m2/g respectively. Furthermore, magnetic biochar loaded
with different metallic salts ion also exhibited an impressive
performance as an electrode with a high specic capacitance,
energy density and power density value with and without the
attachment of polymer as a composite. We are convinced that the
development of magnetic biochar utilizing abundantly available
agricultural waste through few selected different production
methods is expected to create a major breakthrough in the coming
future.

Acknowledgment
This research is nancially supported by Ministry of Higher
Education FRGS Grant (FRGS/2/2013/TK05/UTM/01/5).

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