Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

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Journal of the Taiwan Institute of Chemical Engineers

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

Efficient removal of lead from aqueous solution by urea-functionalized

magnetic biochar: Preparation, characterization and mechanism study
Xiaohui Zhou, Yaochi Liu∗, Jianjun Zhou, Jing Guo, Jialin Ren, Fang Zhou
College of Chemistry and Chemical Engineering, Central South University, 410083 Changsha, China

a r t i c l e i n f o a b s t r a c t

Article history: A novel urea-functionalized magnetic biochar (MBCU) was prepared, characterized and evaluated for re-
Received 3 February 2018 moval of lead (II) from aqueous solution. The results of SEM, BET, XPS, FTIR, VSM and Zeta-potential
Revised 8 April 2018
exhibited a successful fabrication of MBCU. The magnetism magnitude of magnetic biochar could si-
Accepted 13 April 2018
multaneously affect the adsorption and recovery efficiency of lead (II) on magnetic biochar. Hence, the
Available online 5 July 2018
optimum mass ratio range of MBCU was determined to be 1.7:1–2.3:1, which could guarantee high re-
Keywords: moval (> 73.14%) and recovery (> 78.35%) efficiency. The experimental results indicated that the adsorp-
Magnetic biochar tion isotherm and kinetics were well described by the Sips model and pseudo-second-order model, re-
Separation spectively. The maximum adsorption capacity of lead (II) on MBCU was 188.18 mg/g at 323 K. Five-cycle
Modification reusability tests demonstrated MBCU could be effectively recovered and repeatedly used with a small
Palm fiber adsorption loss (< 20%). Mechanism study demonstrated that the adsorption process involved in elec-
Lead (II)
trostatic interaction, ion exchange and complexation. The unique features of its outstanding adsorption
performance, reusability and separation efficiency suggested that the magnetic biochar can be potentially
applied in elimination of lead (II) from wastewater.
© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction terials have been designed and conducted as adsorbents to elim-

Due to the rapid development of industrialization, water pol-
lution by heavy metals is a global issue owing to its high toxi-
city, carcinogenicity, wide sources and non-biodegradable proper-
ties. Most seriously, it can cause continuous threat to the envi-
ronment and human health and has become more serious than
ever before [1,2]. Among these heavy metals, lead deserves spe-
cial attention, because it’s highly toxic to human beings even in
small quantity [3]. Lead can be easily accumulated in various in-
dustrial wastewaters, then assimilated and concentrated in body
system, causing anaemia, chills, diarrhea and dysfunction of the
kidney [4,5]. Removal lead from aqueous environments is impor-
tant and urgent to ensure purified and recycled water.
Several methods for lead removal from wastewater have been
investigated, including chemical precipitation [6], ion exchange [7],
filtration [8], electroplating [9], reverse osmosis [10], and adsorp-
tion [11]. Among these methods, adsorption has been considered to
be the most promising one because of its easy operation, high ef-
ficiency and low cost, which can be used for removal lead at a low
content. The widely successful application of adsorption largely de-
pends on the efficient development of adsorbent, thus diverse ma-
∗
Corresponding author.
E-mail address: liuyaochi72@163.com (Y. Liu).
inate lead from wastewater in both academic research and in-
dustrial application [12]. While the activated carbon, ion-exchange
resins, natural clay has impeded the wide application of adsorption
owing to its expensive produce cost [13,14]. Biochar is black carbon
which is the pyrolytic product of biomass under oxygen-limited
condition. Biochar, as adsorbent, has been received increasing in-
terest because of its several potential environmental applications
in soil amendment, carbon sequestration and contaminant reme-
diation [15,16]. Biochar could immobilize many kinds of contami-
nants including organic pollutants and heavy metals [17,18]. Hence,
biochar shows a great potential in the wastewater treatment.
However, the powered biochars are difficult to be separated
from the aqueous solution due to the small particle sizes and lower
density, which restricts its further practical industrial application
in the wastewater treatment process. A system which can capture
the heavy metal ions with great competence and then to isolate
them out with ease is essential [19]. Maybe the magnetic biochar
could achieve the goal. Introducing magnetic compounds to the
biochar enables the magnetic biochar to be effectively separated
by magnetic separating technique. It is well known that Fe3 O4
process rapidly magnetic responsibility when the external mag-
netic field is applied. However, the magnetization of the biochar
partially reduced its heavy metal adsorption efficiency due to the
biochar’s surface pores becoming plugged with iron oxide parti-
cles. In literatures, many efforts have been devoted to removing

https://doi.org/10.1016/j.jtice.2018.04.018
1876-1070/© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
458 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
contaminates from aqueous solution by magnetic biochars, which
was fabricated from various raw materials. For example, the mag-
netic biochar derived from peanut hull was applied to eliminate
chromium (VI) from wastewater [20]. The waste marine macro-
algal biomass was used as the precursor to fabricate magnetic
biochar for removal cadmium, copper and zinc [21]. But the appli-
cation of palm fiber biochar remains limited. The widespread and
low-cost palm fiber is a common nature vegetable fiber with large
elastic modulus, high strength, highly developed porous and regen-
erative nature. Hence, the palm fiber may be the ideal resource to
produce biochar. Lu et al. has testified the pristine biochar for re-
moval of lead, but achieved adsorption capacity is still unsatisfac-
tory [22]. Thus the functional modification of biochar is required
to improve the adsorption capacity and selectivity [23]. The urea
NH2 CONH2 is extensively found in natural products and is an at-
tractive functional moiety. The groups-nitrogen and oxygen of urea
can offer multitude of bonding potentials owing to its electron pair,
which plays a key role in adsorption of heavy metals.
To overcome the aforesaid challenges, we prepared a novel
magnetic palm fiber biochar via magnetic and functional modifi-
cation for elimination of lead (II) in aqueous solution. The biochar
derived from palm fiber was used as the support to load Fe3 O4
nano-particles on the surface, then the composites were coated a
layer of 3-Triethoxysilylpropylamine, which could immobilize the
Fe3 O4 nano-particles sites on the surface of biochar. In order to fur-
ther increase the adsorption sites and selectivity to lead, the mag-
netic biochar was modified with urea containing amino groups.
The magnetic modified biochar was characterized by SEM, BET,
FTIR, XPS, VSM and Zeta potential. The effects of pH, contact time,
and initial concentration of lead on the removal of lead (II) from
the aqueous solution by the magnetic biochar were investigated.
This work will provide an alternately low cost, high adsorption
and separation efficiency adsorbent for detoxification of lead from
wastewater.
2. Experimental and methods
2.1. Chemicals and material
FeSO4 •7H2 O and FeCl3 •6H2 O were purchased from Sinopharm
Chemical reagent Company. 3-Triethoxysilylpropylamine (TSA),
epichlorohydrin (EC), urea and other chemicals were purchased
from Honghua Reagent Co. Ltd. (Changsha, China). Lead (II) stock
solution (500 mg/L) was prepared by dissolving lead nitrate in dis-
tilled water and then diluted to appropriate concentrations. All the
chemicals used in this study were of analytical grade, and dis-
tilled water (18.2 M, 25 °C) from a Milli-Q plus purification sys-
tem (Millipore) was utilized throughout the experiments for solu-
tion preparation and glassware cleaning. About 50 g of palm fiber
was purchased from a local market, which is shaped with broom,
cut into about 0.5 cm filaments, thoroughly washed with tap water
to clear the dust and other adhering impurities, soaked in 10 0 0 mL
of 1 mol/L NaOH for 12 h, washed with distilled water for several
times and then dried at 323 K.
2.2. Preparation of Fe3 O4 nano-particles
Fe3 O4 nano-particles were prepared by chemical co-
precipitation of in Fe3+ /Fe2+ solution. Typically, 2.3967 g of
FeSO4 •7H2 O and 4.6634 g of FeCl3 •6H2 O were dissolved in 150 mL
of distilled water in a flask. The mixture was stirred for 30 min
under the protection of N2 , then 28%NH3 •H2 O was gradually
added in the flask, until the pH of the mixture was around 10.0.
The suspension was vigorously stirred in an oil bath for 5 h at
353 K. The black precipitate was collected by a magnet and then
washed with distilled water several times, dried at 323 K for 12 h
and then stored in polyethylene bag.
2.3. Fabrication of magnetic biochar (MBCU)
The pretreated palm fiber was converted into biochar by pyrol-
ysis in a muffle furnace at 400 °C with a heating rate of 10 °C/min
under the protection of N2 for 2 h. The pristine biochar was re-
ferred to as BC.
The method to synthesize the magnetic biochar (MBC) was
based on the previous study by Zhou [24] and it was amended
and optimized in this study. As shown in Scheme 1, the procedure
was as follows: A certain mass ratio of biochar and Fe3 O4 nano-
particles were mixed in 100 mL distilled water and then 5.0 mL
of 3-Triethoxysilylpropylamine (TSA) was later added to the solu-
tion. The mixture was stirred in an oil bath for 8 h at 323 K. The
magnetic biochar named as MBC was subsequently washed with
ethanol and distilled water several times after being separated by
a magnet.
Next, 4 mL epichlorohydrin (EC) was dissolved in 100 mL mixed
solvent with acetone/distilled water (V:V = 1:1)solution and 2.0 g
of MBC was later added to the media for cross-linking, the mix-
ture was constantly stirred for 12 h in an oil bath at 303 K. Then,
4.0 g of urea and 50 mL of 1 mol/L NaOH were added into mixture
and stirred in an oil bath at 333 K for 12 h. After being separated
with magnet, the materials were subsequently washed with ace-
tone, ethanol and distilled water and finally oven-dried for 24 h at
323 K. The resulting biochar sample was referred as MBCU.
2.4. Characterization of biochar
The surface morphologies of the biochars were analyzed by
scanning electron microscopy measurement (JSM-6360LV, Japan).
The functional groups of biochars before and after modification
were measured by a Fourier transform infrared (FTIR) spectroscopy
(Nicolet 6700, USA) using the KBr pellet technique and were exam-
ined in the 40 0 0–40 0/cm region. The BET surface area (SBET , m2 /g),
total pore volume (VT , m3 /g) and average diameter (Dp , nm) for
the investigated biochar were determined through N2 adsorption/
desorption isotherms at 77 K using a surface area analyzer (Gemini
Ⅶ2390, USA). The surface chemical composition was confirmed by
the X-ray Photoelectron Spectroscopy (ESCALAB 250Xi, USA). The
Zeta potential was measured at different pH using a Zeta potential
analyzer (JS94H, China). Magnetic property of the MBCU was de-
termined by magnetization curve using the vibrating sample mag-
netometer (Lake Shore 7404, USA).
2.5. Batch sorption equilibrium experiments
Batch experiments were conducted to examine the adsorption
efficiency of BC, MBC and MBCU for removal lead (II) from aque-
ous solution. Generally, a certain amount of biochar was mixed
with lead (II) solution in a flask. Then the mixture was shaken in
a thermostatic shaker at 160 rpm at the investigated temperature
for 24 h. After that, the separated solution was drawn out for ab-
sorbance measurement with a UV–vis spectrophotometer (UV759S,
China).
MBCU adsorbent was used to study the dosage effects on lead
removal. The pH values of solution ranging from 2.0 to 8.0 were
adjusted by 0.01 mol/L HCl and 0.01 mol/L NaOH solution. The
equilibrium adsorption isotherms for lead on MBCU were deter-
mined using 0.0400 g biochar with 40 ml lead solutions of differ-
ent concentrations ranging from 25 to 300 mg/L in a batch of con-
ical vessels. The adsorption kinetic experiments were conducted at
different time intervals, ranging from 5 to 120 min, with 100 mg/L
lead solution at pH 6.5.
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
Scheme 1. The systemic procedure of the magnetic biochar of MBCU.
In order to assess the reusability of the magnetic biochar,
adsorption-desorption experiments were conducted. MBCU with
adsorbed lead was treated by 0.1 mol/L Na2 EDTA for 1 h and
rinsed with distilled water for three times. Afterwards, the des-
orbed biochar was rinsed, dried and added to lead solution
(100 mg/L, 40 mL) in a flask again and the experimental condition
and measurements were the same as adsorption. The adsorption-
desorption process was repeated six cycles. The equilibrium ad-
sorption amount Qe (mg/g) was calculated according to the follow-
ing equations:
(C0 − Ce ) × V
Qe =
m
Where Ce and Co are the equilibrium and the initial concentra-
tions of lead (mg/L), respectively. V is the volume of solution (L)
and m is the weight of added biochar (g).
3. Results and discussion
3.1. Characterization of the biochars before and after modification
3.1.1. Surface morphology
The surface morphologies of BC, MBC and MBCU were illus-
trated in Fig. 1, which showed that BC had a highly developed
porous structure. When comparing the SEM images of BC and MBC,
it was clearly showed that splendent particles appeared on the sur-
face of MBC, which can be attributed to the existence of Fe3 O4
nano-particles. Due to the wrinkled surface of BC, the Fe3 O4 nano-
particles can be easily loaded into the porous. The porous surface
of BC was preserved after magnetization and modification and the
Fe3 O4 nano-particles were not uniformly distributed on the sur-
face of BC. Compared with MBC, there was no obvious change after
459
functional modification in MBCO, which suggested that the surface
morphology of MBC was hardly influenced by the functional mod-
ification.
3.1.2. Surface functional groups
The surface functional groups are the main chemical factor of
biochars that affect the heavy metal adsorption. Fig. 2 showed the
FTIR spectra of BC, MBC and MBCU. The was a strong absorbance
peak appeared at 568/cm and 1110/cm owing to the Fe-O vibra-
tion of Fe3 O4 and the Si-O vibration of silane coupling agent, re-
spectively, which indicated that the Fe3 O4 nano-particles and 3-
(1) Triethoxysilylpropylamine have been successfully loaded on the
surface of the biochar as demonstrated by the SEM results. The
peak at 3427/cm corresponded to the O-H stretching vibration of
-OH, which was wider and stronger in MBCU than that of in MBC
due to the existence of hydrogen bond between -OH and -NH2 .
The absorbance peak at 1377/cm and 1585/cm were the charac-
teristic peak of -C-O and -C = O, respectively. These observations
confirmed MBC was successfully modified with urea.
3.1.3. XPS analysis
The oxidation states and surface elemental composition of BC
and MBCU were studied by XPS analysis. Fig. 3a and b showed
the wide scan spectra of BC and MBCU. Compared to the raw BC,
the new element peaks at 399.76 eV, 711.28 eV and 152.87 eV ap-
peared in MBCU ascribed to the binding energy of N1s, Fe2p and
Si2s, respectively, which illustrated that the Fe3 O4 nano-particles
and 3-Triethoxysilylpropylamine has been successfully grafted on
the surface of BC and MBC has been successfully modified with
urea as proved in FTIR analysis. The Fe2p peaks at 711.24 eV and
724.81 eV corresponded to the Fe2p3/2 and Fe2p1/2 spin-orbit peak
460 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
a b
Fig. 1. The SEM images of BC (a), MBC (b) and MBCU (c).
Fig. 2. The FTIR spectra of BC, MBC and MBCU.
of magnetic compounds, which was an evidence to further verify
the Fe oxides were attached to the biochar matrix.
Moreover, the percentage of surface elements composition in
BC and MBCU were listed in Table 1S. As shown in Table 1S, the
%C and %O were the highest in BC followed by MBC and MBCU
and the %N was the opposite order. The %Fe detected in BC was
negligible, while MBC and MBCU had 17.29% and 16.36% of Fe, re-
spectively. The elements analysis indicated that the N and O ele-
ments highly increased after magnetic and functional modification
and the magnetic and functional modification of BC with Fe3 O4
nano-particles and urea was successful.
3.1.4. Elemental composition and porous structure
The specific surface area, total pore volume advantage pore di-
ameter are the physical factors of biochar that affect the heavy
metal adsorption. It was notable that BC had a high surface are of
169.73 mg/g, while the MBC has lower surface area of 103.87 mg/g.
The decrease in the surface area of MBC was expected because the
MBC was composed of a high surface area carbonaceous and a low
surface area of Fe3 O4 , since the Fe3 O4 nano-particles could block
some of the pores of the BC. The lower surface area of magnetic
composites compared to pristine biochar has also been observed in
other study [25]. Compared with the MBC, there was little change
of MBCU in surface area, which indicated that the functional mod-
ification had a negligible effect on surface area of biochar.
3.1.5. Magnetic properties
The magnetic hysteresis loops of the prepared magnetic
biochars and Fe3 O4 nano-particles were obtained from the plot
c
of the magnetization (emu/g) against the flied strength (Oe). As
shown in the loop seen in Fig. 1S, the magnetization sharply in-
creased with the decrease of the mass ration of BC: Fe3 O4 nano-
particles and the saturation magnetization (Ms ) reached to 10.2,
15.5, 16.9, 20.1, 32.3 emu/g for MBCU(3:1), MBCU(2:1), MBCU(2:1),
MBCU(1:1) and Fe3 O4 nano-particles, respectively, which revealed
that the magnetization of MBCU can be adjusted by the mass ra-
tion of BC: Fe3 O4 nano-particles. The super-paramagnetic behav-
ior was caused by the modification of biochar with Fe3 O4 nano-
particles, which could guarantee the MBCU can be readily recol-
lected from the suspended solution by applying the external mag-
netic field, which makes the repeated use of the MBCU in the real
wastewater treatment process possible.
3.2. Adsorption study
3.2.1. Effect of solution pH on lead (II) adsorption
The pH is a pivotal parameter in the adsorption process which
has been demonstrated in literatures, because it not only affects
the degree of ionization and speciation of the heavy metals, but
also the charges and states of the functional groups of adsorbent.
To study the influence of pH upon adsorption of lead, the experi-
ments were conducted in the pH range of 2–8 and the results were
shown in Fig. 4b. The adsorption capacity of lead (II) on BC, MBC
and MBCU remarkably increased with the increase of pH from 2
to 6.5, after that, it decreased when pH value greater than 6.5,
which indicated that the adsorption of lead on the biochar was
strongly depended on the pH of the system. The Zeta-potential
changes of BC, MBC and MBCU at pH 2–12 were shown in Fig. 4a.
The values of Zeta-potential decreased with the increase of pH and
the point of zero charge (PZC) of BC, MBC and MBCU was 3.65,
4.00 and 4.72, respectively. When the pH value was less than the
PZC, the biochars were protonated and positively charged; when
pH value was more than the PZC, the biochars were negatively
charged, which was in favor of lead (II) adsorption as lead (II) was
positively charged.
It is well reported in literatures that lead is present in various
forms i.e. Pb2+ , Pb(OH)+ , Pb(OH)2 0 , and Pb(OH)3 − at different pH
values [26]. At relatively low pH, Pb2+ is the predominant form
and it would compete with the excess H+ for the adsorption sites
on the surface of biochar, on the other hand, the surface groups
could be protonated and repel the lead (II), so low uptake capac-
ity was observed at low pH region. Along with the increase of pH
value, the decrease of H+ could reduce the competitive adsorption,
leading to the increase of adsorption capacity [24]. However, at
pH > 6.5, the lead (II) would hydrolyze and the surface of biochar
would be covered with the hydrolysis product of lead, which has
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 461

Fig. 3. XPS spectra of (a) BC, (b) MBCU and (c) MBCU after lead adsorption; (d) XPS of C1s before and after lead (II) adsorption; (e) XPS of O1s before and after lead (II)
adsorption; (f) XPS of N1s before and after lead (II) adsorption.
462 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
Fig. 4. (a) The Zeta potential of BC, MBC and MBCO at different pH. (b) Effect of pH on lead (II) removal by BC, MBC and MBCU (C0 = 100 mg/L, dosage = 1.0 g/L, contact
time = 12 h, adsorption temperature = 293 K).
Fig. 5. Lead (II) removal percentage and adsorption capacity versus MBCU dosage
(C0 = 100 mg/L, pH = 6.5, contact time = 12 h, adsorption temperature = 293 K).
adverse effect on the adsorption process. Therefore, the adsorption
capacity reduced in the pH range from 6.5 to 8 and the maximum
adsorption capacity of lead (II) on magnetic biochar was observed
at pH 6.5.
3.2.2. Effect of adsorbent dosage
Adsorbent dosage is a significant impact factor of adsorp-
tion process. It determines the adsorbent-adsorbate equilibrium of
the adsorption system. The removal efficiency of lead increased
from 12% to 100% as the adsorbent dosage increased from 0.1
to 1.5 g/L. On the other hand, the maximum adsorption capac-
ity of 106.6 mg/g was achieved at the dosage of 0.1 g/L and de-
creased with the adsorbent dosage (Fig. 5). MBCU was demon-
strated with super removal efficiency to lead from aqueous solu-
tion. This remarkable adsorption performance was due to the ex-
istence of abundant active sites and multiple interactions between
MBCU with lead, namely electrostatic interaction, ion exchange and
complexation, which would be discussed in 3.2.8. Thus, all the
following adsorption experiments were carried out at adsorbent
dosage of 1.0 g /L, which could guarantee the relatively excellent
adsorption capacity and removal efficiency at the same time.
Fig. 6. Effect of the mass ratio of BC: Fe3 O4 nano-particles on the magnetic biochar
in term of adsorption capacity of lead (II) and recovery efficiency (C0 = 100 mg/L,
pH = 6.5, contact time = 12 h, adsorption temperature = 293 K).
3.2.3. Optimum iron loading for magnetization
Though the magnetic biochar could be effectively recovered
from aqueous solution, the adsorption efficiency reduced at the
same time due to the pores in the surface of biochar becom-
ing plugged with iron oxide particles. Hence, it is essential to
determine the optimum mass ratio of BC: Fe3 O4 nano-particles
that maximize the magnetic biochar’s separation efficiency without
sacrificing its adsorption efficiency. Fig. 6 represents the adsorp-
tion capacity and recovery efficiency of lead (II) on the magnetic
biochar from the aqueous solution when the mass ratio of BC:
Fe3 O4 nano-particles was 0:1,1:1,1.5:1,2:1,3:1,1:0 to impart magne-
tization. It was clearly observed that the adsorption capacity and
recovery efficiency of the magnetic biochar displayed the opposite
tendency depending on the mass ratio. The adsorption capacity of
lead (II) on the biochar decreased from 99.89 to 12.91 mg/g as the
mass ratio of BC: Fe3 O4 nano-particles decreased. Contrary to the
adsorption capacity, the recovery efficiency of the magnetic biochar
increased as the mass ratio decreased. Based on the results, it
is essential to determine the optimum mass ratio of BC: Fe3 O4
nano-particles that maximize the magnetic biochar’s separation
efficiency without sacrificing its adsorption capacity of lead (II).
To achieve these controversial purposes, namely high adsorption
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 463

Fig. 7. (a) The adsorption kinetic plots of BC, MBC and MBCU. (b) Linear fit for pseudo-first-order model of kinetic data. (c) Linear fit for pseudo-second-order model of
kinetic data. (d) Intra-particle diffusion model plot of kinetic data. (C0 = 100 mg/L, dosage = 1.0 g/L, pH = 6.5, adsorption temperature = 293 K).

capacity and recovery efficiency, the optimum mass ratio range
was determined to be 1.7:1–2.3:1. At the mass ratio of 2:1, the
magnetic biochar showed a high adsorption capacity of 88.9 mg/g
for lead (II) and recovery efficiency of 97.9% for magnetic biochar.
Meanwhile, research concerning additive materials which can
maintain the magnetic properties and reinforce the adsorption
ability of biochar after magnetization is required in the future.
3.2.4. Adsorption kinetics
Fig. 7a showed the effects of the modification the adsorption
kinetics of lead (II) by various biochars. It is observed that the ad-
sorption capacity of lead (II) on BC was biter weaker than MBC,
which may be result from the coating of coupling agent and fill-
ing up with Fe3 O4 nano-particles. In addition, the MBCU modified
with urea showed the highest adsorption capacity of lead (II). That
was because the amine groups were introduced to the surface of
the magnetic biochar, which played an essential role in lead (II)
adsorption.
It is noteworthy that the adsorption capacity of lead (II) was
markedly ascended within the first 5 h for all biochars, and a
further increase in contact time barely affected the adsorption
efficiency, because adsorption equilibrium was reached. To fur-
ther investigate the potential adsorption mechanism of adsorption
process, the pseudo-first-order reported by Lagergren [27] and
pseudo-second-order reported by Ho and McKay [28] were em-
ployed to describe the adsorption kinetic data, given by Eqs.
(2) and (3).
In(Qe − Qt ) = InQe − k1 t (2)
t 1 1
= + t (3)
Qt k2 Qe 2 Qe
Where Qe and Qt (mg/g) are the amounts of lead (II)adsorbed
onto magnetic biochar at equilibrium and at time t (min), re-
spectively; k1 (1/min) and k2 (g/(mg•min)) are the rate constant of
pseudo-first-order and pseudo-second-order. The plots of log (Qe -
Qt ) versus t and t/ Qt versus t give the values of k1 and Qe , k2 and
Qe , respectively. The fitting plots were showed in Fig. 7b and c and
the corresponding fitting parameters were listed in Table 2S. It can
be obviously observed that the pseudo -first-order model was not
suitable to describe the kinetic profiles, while they were accurately
described by the pseudo-second-order model. The regression coef-
ficients (R2 > 0.99) obtained from pseudo-second-order non-linear
fits was much larger than that of pseudo-first-order non-linear fits.
In addition, the experimental results of adsorbed lead (II) amount
464 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
at equilibrium were in very good agreement with those calcu-
lated from the pseudo-second-order model, which indicated that
the pseudo-second-order model was more appropriate to describe
the adsorption behavior of lead (II) on biochars. The results sug-
gested that chemical adsorption of the lead (II) on the MBCU was
dominant.
Since the pseudo-first-order and pseudo-second-order model
were based on the whole adsorption process and could not pro-
vide the control step in different adsorption stages. Hence, the
kinetic data were also fitted by intra-particle diffusion model
(Eq. (4)) originated from Fick’s second law [29]. It can be seen
that the curves present multi linearity shown in Fig. 7d and the
order of diffusion rate constant was kp 1 > kp 2 > kp 3 , implying that
intra-particle diffusion did not limit the whole adsorption process
(Table 3S). Additional, the diffusion rate constant was different for
the three biochar and the order was MBCU>MBC>BC, which could
be owing to the kinds and amount of functional groups [24].Based
on the pore-diffusion theory, the adsorption process can be de-
scribed by three steps [30]: (1) the adsorption happened quickly
and could be ascribed to film diffusion (transport of lead (II)from
the boundary film to the exterior surface of adsorbent); (2) the
adsorption rate decreased and could be ascribed to intra-particle
diffusion (transfer of lead (II) from the surface to the pores of ad-
sorbent); (3) the adsorption equilibrium reached and could be as-
cribed to equilibrium stage (adsorption of lead (II) on the interior
surface of adsorbent was saturated).
Qt = k pi t 1/2 + Ci
kpi (mg/(g min−1/2 )) is intra-particle diffusion rate constant of stage
i, Ci is a parameter about the thickness of the boundary layer.
3.2.5. Adsorption isotherm
The adsorption isotherm study was performed at different tem-
peratures i.e. 293, 303, 313, 323 K by adjusting initial lead (II) con-
centration from 25 to 300 mg/L and the adsorption isotherm curves
were presented in Fig. 8a. It was clearly that the absorbed lead
(II) on MBCU increased with the increasing of initial lead (II) con-
centration and the isotherms were L-type with an initial moderate
slope until reached a plateau value for the higher lead (II) concen-
tration.
The study of adsorption isotherms is very vital to understand
the interaction behavior between adsorbent and heavy metals. It’s
necessary to establish an appropriate correlation of adsorption
equilibrium to optimum the adsorption system for efficient adsorp-
tion of heavy metals in practical application. For this adsorption
system, three isotherm models including Langmuir, Freundlich and
Sips were used to fit the isotherm data. The Langmuir isotherm
assumes the adsorption occurs in the monolayer way with no
interaction between the adsorbed molecular [31]. The Freundlich
isotherm assumes the multilayer and non-ideal adsorption on the
heterogeneous surface with a non-uniform distribution of adsorp-
tion activation energy [32]. In between, the Sips isotherm effec-
tively reduces to the Freundlich isotherm at low adsorate concen-
tration whereas at high adsorate concentration, it displays a mono-
layer adsorption characteristic of the Langmuir isotherm [33]. The
non-linear form of the three isotherms model could be expressed
in Eqs. (5) –(7):
Qm · b · Ce
Langmuir : Qe =
1 + b · Ce
Freundlich : Qe = KF · Ce n
Qm · b · Ce n
Sips : Qe =
1 + b · Ce n
Where Ce (mg/L) and Qe (mg/g) are the equilibrium concentra-
tion of adsorate and the amount of adsorate adsorbed at equilib-
rium, respectively. Qm (mg/g) denotes the maximum adsorption ca-
pacity. The b (L/mg) related to the heat of adsorption is the Lang-
muir constant. The Kf (mg/g (L/mg)1/n ) related to the relative ad-
sorption capacity and n related to the intensity of adsorption are
the Freundlich constant, being the latter a measure of the hetero-
geneity of surface adsorption sites. All these parameters appeared
in the Sips equation maintain the same meanings.
The plots of Qe versus Ce of the three isotherm models were
shown in Fig. 8 and the parameters of mathematical modeling
were listed in Table 4S. The comparison of regression coefficients
for the non-linear plots of Langmuir and Freundlich isotherm in-
dicated that the experimental data was better fitted with the
Langmuir equation rather than the Freundlich model. However,
the comparison with Sips model revealed that the latter isotherm
could even better fit the experimental data since the R2 was always
higher than that of Langmuir or Freundlich model. Furthermore,
as Table 4S showed, the saturation adsorption capacities of lead
(II) on MBCU were closed to the maximum adsorption capacities
obtained from the Sips model at 293, 303, 313, and 323 K. There-
fore, it can be concluded that the adsorption of lead (II) on MBCU
mainly entailed the formation of a superficial monolayer, but there
was a certain degree of heterogeneity.
The separation factor (RL ) is a dimensionless constant, which is
used to determine whether the adsorption was favorable or not.
The RL is expressed as follows:
(4)
1
RL = (8)
1 + b · C0
Where C0 and b represent the initial concentration of lead (II)
and Sips constant, respectively. The RL value classified the nature of
adsorption to be irreversible (RL = 0), favorable (0 < RL < 1) and un-
favorable (RL > 1). For the current adsorption system, the RL values
for MBCU were calculated to be 0.022–0.214, 0.015–0.159, 0.010–
0.112 and 0.008–0.094 with initial concentration ranging from 25
to 300 mg/L at 293, 303, 313, and 323 K, which indicated that the
favorability of the adsorption process as RL was between 0 and
1. Furthermore, the adsorption capacity of lead (II) on MBCU in-
creased with the increasing of adsorption temperature, which in-
dicated that the adsorption process was an endothermic reaction
and higher temperature would benefit to the adsorption. That was
partly because the increase of temperature may cause a swelling
effect on pore volume of MBCU, which favored the lead (II) diffu-
sion both in the boundary layer and internal pores of the MBCU
[34].
The comparison of bibliography evidences the major adsorption
capacities found in the present study (Table 1). The results showed
that the maximum adsorption capacity of MBCU was higher than
that of other materials. Moreover, it was worthy to remark the sig-
nificant capacity of MBCU to remove lead (II) from aqueous so-
lution, being possible to achieve an adsorption percentage higher
than 90% when the initial lead (II) concentration was lower than
100 mg/L. This result was especially relevant when this magnetic
modified material was considered to be applied in practical appli-
cation.
3.2.6. Recycle and desorption of MBCU
The recycle and desorption potential of adsorbents was investi-
(5)
gated to make the adsorption process more economical. 0.1 mol/L
Na2 EDTA was applied as the desorbing solution for the recovery
(6) of the lead (II) from the Pb-loaded MBCU. The lead (II) removal
efficiency remained > 80% and the desorption efficiency of each
cycle maintained > 93.1% after six successive cycles, as shown in
Fig. 9. It was observed that the lead (II) adsorption efficiency only
(7)
decreased by 18.7% after six successive cycles compared with the
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 465

Fig. 8. (a) Adsorption isotherm of lead (II) on MBCU at different temperatures. (b) The non-linear fit of Freundlich isotherm model. (c) The non-linear fit of Langmuir
isotherm model. (d) The non-linear fit of Sips isotherm model. (pH = 6.5, dosage = 1.0 g/L, contact time = 12 h).

Table 1
Comparison of adsorption capacity of lead (II) on different adsorbents.

Adsorbents Conditions Qm (mg/g) Ref.

Biomass fly ash T = 293 K,pH = 5.0,D. = 0.83 g/L 6.30 [35]

L-proline silica gel T = 303 K,pH = 5.5,D. = 2 g/L 22.22 [36]
Agriculture soil T = 293 K,pH = 6.5,D. = 4 g/L 20.16 [37]
NCS/PU/PPG-glu T = 293 K, pH = 6.0, D. = 4 g/L 169.52 [38]
Porous leather particles T = 328 K, pH = 5.0, D. = 2 g/L 31.66 [5]
GO composite T = 298 K, pH = 6.0, D. = 0.25 g/L 72.18 [39]
Activated carbon T = 293 K,pH = 6.0,D. = 1.0 g/L 163.93 [13]
Anaerobic digestion sludge biochar T = 313 K,pH = 6.0,D. = 1.0 g/L 53.96 [26]
40% MnOx-loaded biochar T = 298 K,pH = 5.0,D. = 2.0 g/L 86.50 [40]
MBCU T = 323 K,pH = 6.5,D. = 1.0 g/L 188.18 This study

first cycle, indicating a good regeneration and reusability of MBCU.
In addition, the magnetic property of MBCU could effectively pro-
mote the separation process and significantly reduced the loss of
MBCU with repetitive usage. Therefore, the advantage of magnetic
property and remarkable reusability for the effectively removal
lead (II) made MBCU as a promising candidate in wastewater
treatment.
3.2.7. The adsorption selectivity of MBCU
To investigate the adsorption selectivity of MBCU for different
heavy metal ions, the competitive heavy metal adsorption experi-
ment was carried out at 293 K for 12 h using solutions separately
containing of 100 mg/L Cd(II), Zn(II), Cu(II), Ni(II) and Pb(II). Af-
ter the adsorption equilibrium was reached, the adsorption capac-
ities of these heavy metals were determined and the results were
showed in Fig. 2S. It can be seen that the order was Pb(II)> Cd(II)>
Ni(II)> Cu(II)> Zn (II), which indicated that the MBCU showed high
selectivity for lead (II). Indeed, the adsorption capacity of Pb(II)
was 1.5 times higher than that of Cd(II), 4 times for Cu(II), 6 times
for Ni(II) and 3 times for Pb(II), that is, Pb(II) was well-formed
into complexes with the functional groups(-NH2-,-C=O and -OH)
on the surface of MBCU [26]. The magnetic MBCU produced by
bio-material was able to selectively remove lead (II) from aqueous
solution. Hence, owing to its availability, selectivity, reusability and
466 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
Fig. 9. The adsorption and desorption efficiency of lead (II) on MBCU in five suc-
cessive regeneration cycles.
efficient separation, the MBCU could be a promising adsorbent for
removal lead (II) from aqueous solution.
3.2.8. The adsorption mechanism of lead (II) on MBCU
XPS analysis of MBCU and MBCU-Pb(II), as exhibited in
Fig. 3(c)–(f), provided the further illustration of adsorption mech-
anism of Pb(II) on MBCU. The C1s of MBCU was deconvoluted
into five components: C-H at 283.86 eV, C-C/C=C at 284.61 eV, C-
N at 285.31 eV, C-O at 286.40 eV and 287.82 eV. Although the C1s
of MBCU after Pb (II) adsorption exhibited the same functionali-
ties as the MBCU, there was a certain degree of the binding en-
ergy after Pb (II) adsorption. Compared with MBCU spectrum, the
four components of O1s corresponded to O-H at 532.88 eV, O = C
at 531.49 eV, O-C at 530.44 eV and O-Si at 529.76 eV shifted to
532.91 eV, 531.52 eV, 530.50 eV and 529.87 eV, respectively. Two
major peaks in N1s at 401.87 and 399.74 eV could be attributed to
the N-C and N-H, respectively. After adsorption Pb (II), the peak of
N-C and N-H shifted to 402.06 and 399.84 eV, respectively, which
implied that the lone pairs of electron in N and O was shared with
Pb(II), leading to the decrease of electron density and the increase
of binding energy of nitrogen and oxygen atoms[24]. It mainly re-
sulted from the formation of complexation between Pb(II) and ni-
trogen, oxygen atoms of the functional groups [41]. The possible
adsorption complexation mechanism of Pb(II) on MBCU was pre-
sented by the formation of the complexation shown in Eqs. (9)–
(11).
Meanwhile, the final pH of the solution after adsorption equi-
librium and the Zeta-potential change of MBCU and MBCU-Pb(II)
were shown in Fig. 3S (a) and (b). It is remarkable that the pH vari-
ation during Pb(II) adsorption was not varying significantly: at low
pH (below pH 5.5), a slight increase of the equilibrium pH (below
0.37 pH unit) was observed, while above pH 5.5, the equilibrium
pH tended to slightly decrease (variation being less than 0.22 pH
unit), which indicated that the grafting of functional groups con-
tributed to smooth this pH variation effect. Compared with MBCU,
the pH at PZC and Zeta-potential of MBCU-Pb(II) transferred to a
higher value and more positive direction, because the formation of
ionic bonds in the complexes of MBCU with Pb(II)(e.g., MBCU•NH2 -
Pb(II), MBCU•C = O-Pb(II) and MBCU•OH-Pb(II)) brought more pos-
itive charge to the surface of MBCU. For MBCU-Pb(C), at pH below
5.3, the density of positive charge was high, because the –NH2 on
MBCU was protonated at low pH, resulting in the formation of –
NH3 + . Then, –NH3 + enhanced the electrostatic repulsion between
the positively charged Pb(II) and MBCU, besides, the abundant
H+ also competed for the adsorption sites on MBCU with Pb(II) via
ion-exchange. Therefore, the adsorption capacity of Pb(II) on MBCU
was poor at pH < 5.3. When pH was above 5.5 but below 7, the
density of negative increased substantially, resulting in the dra-
matic charge neutralization activity at this stage, which could en-
hance the adsorption process via electrostatic interactions and ion-
exchange. Additionally, the release of cation (ion-exchange) was
also proved by the Pb-O binding energy at ∼138 Ev [42]. Beyond
pH 7.0, the Zeta-potential of MBCU-Pb(II) kept a steady stage, the
adsorption capacity decreased owing to the formation of Pb(OH)2
precipitation. Hence, the possible ion-exchange adsorption mecha-
nism occurred in functional groups of MBCU with lead (II), which
was showed in Eqs. (12) and (13).
Complexation : R–NH2 +Pb(II ) ⇔ R–NH2 –Pb(II ) (9)
R–C = O + Pb(II ) ⇔ R–C = O–Pb(II ) (10)
R–OH + Pb(II ) ⇔ R–OH–Pb(II ) (11)
Ion–exchange : R–NH3 + +Pb(II ) ⇔ R–NH2 –Pb(II )+H+ (12)
 
(R − OH )2 +Pb(II ) ⇔ R−O− 2 −Pb(II ) + 2H+ (13)
Where R represented the other component of MBCU. In conclu-
sion, Pb (II) adsorption experiments and XPS analysis coindicated
the adsorption mechanism of Pb (II) on MBCU could be involved
in chemical adsorption including electrostatic interaction, ion ex-
change and complexation. The ion exchange was occurred between
Pb (II) with the protons in the functional groups of MBCU. The
electrostatic interaction of the deprotonated functional groups en-
hanced adsorption of Pb (II). The N atoms in −NH2 groups and
O atoms in -OH, and –C = O could donate their electrons to form
coordination complexes or covalent binding with Pb (II). More-
over, MBCU showed multi-porous structure with high surface area,
which offered tremendous adsorption sites. Together with the mul-
tiple chemical interactions, MBCU could be considered as a supe-
rior adsorbent to remove Pb (II) from wastewater.
Conclusion
A novel urea-functionalized magnetic biochar (MBCU) was syn-
thesized via magnetic and functional modification for remove of
lead (II) from aqueous solution. The results of SEM, BET, XPS, FTIR,
VSM and Zeta-potential indicated that the Fe3 O4 nano-particles
and urea were successfully grafted on the surface of biochar. The
experimental results exhibited the adsorption isotherm can be well
fitted by Sips model and the adsorption kinetic data was fitted
well with pseudo-second-order model. The maximum adsorption
capacities of lead (II) on MBCU calculated from the Sip model were
154.95, 166.78, 175.36 and 188.18 mg/g at 293, 303, 313 and 323 K,
respectively, which was higher than that of other adsorbents pub-
lished in references. The lead (II) removal efficiency of MBCU re-
mained > 80% and the desorption efficiency maintained > 93.1% af-
ter five adsorption/desorption cycles. The saturation magnetization
of MBCU reached to 16.9 emu/g, which could guarantee the MBCU
could be easily and effectively separated from the solution by ap-
plying the external magnetic field. The sustainable and low-cost
magnetic adsorbent MBCU has great potential to be a promising
candidate for lead (II) removal.
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467
Acknowledgments
We acknowledge the Fundamental Research Funds for Central
Universities of Central South University (No. 1053320171391) and
the Hunan Provincial Science and Technology Plan Project, China
(No. 2016TP1007) for financial support of this research.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jtice.2018.04.018.
References
[1] López-Muñoz MJ, Arencibia A, Cerro L, Pascual R, Melgar Á. Adsorption of
Hg(II) from aqueous solutions using TiO2 and titanate nanotube adsorbents.
Appl Surf Sci 2016;367:91–100.
[2] Li Z, Ma Z, van der Kuijp TJ, Yuan Z, Huang L. A review of soil heavy metal
pollution from mines in China: pollution and health risk assessment. Sci Total
Environ 2014;468–469:843–53.
[3] Li B, Yang L, Wang CQ, Zhang QP, Liu QC, Li YD, et al. Adsorption of Cd(II) from
aqueous solutions by rape straw biochar derived from different modification
processes. Chemosphere 2017;175:332–40.
[4] Pragst F, Stieglitz K, Runge H, Runow KD, Quig D, Osborne R, et al. High
concentrations of lead and barium in hair of the rural population caused by
water pollution in the Thar Jath oilfields in South Sudan. Forensic Sci Int
2017;274:99–106.
[5] Yan T, Luo X, Lin X, Yang J. Preparation, characterization and adsorption prop-
erties for lead (II) of alkali-activated porous leather particles. Colloids Surf A
Physicochem Eng Asp 2017;512:7–16.
[6] Ali H, Khan E, Sajad MA. Phytoremediation of heavy metals-concepts and ap-
plications. Chemosphere 2013;91:869–81.
[7] Berber-Mendoza MS, Leyva-Ramos R, Alonso-Davila P, Fuentes-Rubio L, Guer-
rero-Coronado RM. Comparison of isotherms for the ion exchange of Pb(II)
from aqueous solution onto homoionic clinoptilolite. J Colloid Interface Sci
2006;301:40–5.
[8] Cotte L, Waeles M, Pernet-Coudrier B, Sarradin P-M, Cathalot C, Riso RD. A
comparison of in situ vs. ex situ filtration methods on the assessment of dis-
solved and particulate metals at hydrothermal vents. Deep Sea Res Part I
Oceanogr Res Pap 2015;105:186–94.
[9] Wong KK, Lee CK, Low KS, Haron MJ. Removal of Cu and Pb from electro-
plating wastewater using tartaric acid modified rice husk. Process Biochem
2003;39:437–45.
[10] Shrestha J, Li J. Influence of permeate from domestic reverse osmosis fil-
ters on lead pipes corrosion and plastic pipes leaching. J Water Process Eng
2017;18:126–33.
[11] Wang C, Fan X, Wang P, Hou J, Ao Y, Miao L. Adsorption behavior of lead on
aquatic sediments contaminated with cerium dioxide nanoparticles. Environ
Pollut 2016;219:416–24.
[12] Shen Z, Zhang Y, Jin F, McMillan O, Al-Tabbaa A. Qualitative and quantitative
characterisation of adsorption mechanisms of lead on four biochars. Sci Total
Environ 2017;609:1401–10.
[13] Largitte L, Brudey T, Tant T, Dumesnil PC, Lodewyckx P. Comparison of the
adsorption of lead by activated carbons from three lignocellulosic precursors.
Micropor Mesopor Mat 2016;219:265–75.
[14] Anantha RK, Kota S. Removal of lead by adsorption with the renewable
biopolymer composite of feather (Dromaius novaehollandiae) and chitosan
(Agaricus bisporus). Environ Tech Innov 2016;6:11–26.
[15] Godlewska P, Schmidt HP, Ok YS, Oleszczuk P. Biochar for compost-
ing improvement and contaminants reduction: a rev. Bioresour Technol
2017;246:193–202.
[16] Zhu F, Li YB, Xue SG, Hartley W, Wu H. Effects of iron-aluminium oxides and
organic carbon on aggregate stability of bauxite residues. Environ Sci Pollut
Res Int 2016;23:9073–81.
[17] Zou Q, An WH, Wu C, Li WC, Fu AQ, Xiao RY, Chen HK, Xue SG. Red mud-modi-
fied biochar reduces soil arsenic availability and changes bacterial composition.
Environ Chem Lett 2017;15:1–8.
467
[18] Oliveira FR, Patel AK, Jaisi DP, Adhikari S, Lu H, Khanal SK. Environmen-
tal application of biochar: current status and perspectives. Bioresour Technol
2017;246:110–22.
[19] Zhou JJ, Liu YC, Zhou XH, Ren JL, Zhong CB. Magnetic multi-porous bio-ad-
sorbent modified with amino siloxane for fast removal of Pb(II) from aqueous
solution. Appl Surf Sci 2018;427:976–85.
[20] Han Y, Cao X, Ouyang X, Sohi SP, Chen J. Adsorption kinetics of mag-
netic biochar derived from peanut hull on removal of Cr (VI) from aque-
ous solution: effects of production conditions and particle size. Chemosphere
2016;145:336–41.
[21] Son EB, Poo KM, Chang JS, Chae KJ. Heavy metal removal from aqueous
solutions using engineered magnetic biochars derived from waste marine
macro-algal biomass. Sci Total Environ 2018;615:161–8.
[22] Lu H, Zhang W, Yang Y, Huang X, Wang S, Qiu R. Relative distribution of Pb2+
sorption mechanisms by sludge-derived biochar. Water Res 2012;46:854–62.
[23] Chen YD, Ho SH, Wang D, Wei ZS, Chang JS, Ren NQ. Lead removal by a mag-
netic biochar derived from persulfate-ZVI treated sludge together with one-pot
pyrolysis. Bioresour Technol 2018;247:463–70.
[24] Jj Zhou, Yc Liu, Xh Zhou, Jl Ren, Cb Zhong. Removal of mercury ions from aque-
ous solution by thiourea-functionalized magnetic biosorbent: preparation and
mechanism study. J Colloid Interface Sci 2017;507:107–18.
[25] Reguyal F, Sarmah AK, Gao W. Synthesis of magnetic biochar from pine saw-
dust via oxidative hydrolysis of FeCl2 for the removal sulfamethoxazole from
aqueous solution. J Hazard Mater 2017;321:868–78.
[26] Mohan S, Kumar V, Singh DK, Hasan SH. Effective removal of lead ions using
graphene oxide-MgO nanohybrid from aqueous solution: isotherm, kinetic and
thermodynamic modeling of adsorption. J Environ Chem Eng 2017;5:2259–73.
[27] Lagergren S. About the theory of the so-called adsorption of soluble substance.
Kung Sven Vete Hand 1898;24:1–39.
[28] Ho SH, Chen YD, Yang ZK, Nagarajan D, Chang JS, Ren NQ. High-efficiency re-
moval of lead from wastewater by biochar derived from anaerobic digestion
sludge. Bioresour Technol 2017;246:142–9.
[29] Tang D, Zhang G. Efficient removal of fluoride by hierarchical Ce–Fe bimetal
oxides adsorbent: Thermodynamics, kinetics and mechanism. Chem Eng J
2016;283:721–9.
[30] Rout PR, Bhunia P, Dash RR. Modeling isotherms, kinetics and understanding
the mechanism of phosphate adsorption onto a solid waste: ground burnt pat-
ties. J Environ Chem Eng 2014;2:1331–42.
[31] Langmuir I. The adsorption of gases on plane surfaces of glass, mica and plat-
inum. J Am Chem Soc 1918;40:1361–402.
[32] Freundlich H. Kinetic and energies of gas adsorption. Trans Farad Soc
1932;28:195–201.
[33] Sips R. Structure of a catalyst surface. J Chem Phys 1948;16:490–5.
[34] Zhou K, Liu Y, Yang Z, Liu H, Xie T. High-capacity sorption of U (VI) from aque-
ous solution using a bio-based oxidized polymeric material. J Taiwan Ins Chem
Eng 2016;63:453–62.
[35] Novais RM, Buruberri LH, Seabra MP, Labrincha JA. Novel porous fly-ash con-
taining geopolymer monoliths for lead adsorption from wastewaters. J Hazard
Mater 2016;318:631–40.
[36] Kushwaha AK, Gupta N, Chattopadhyaya MC. Adsorption behavior of lead onto
a new class of functionalized silica gel. Arab J Chem 2017;10 pp. S81–S9.
[37] Ahmed IM, Helal AA, El Aziz NA, Gamal R, Shaker NO, Helal AA. Influence
of some organic ligands on the adsorption of lead by agricultural soil. Arab
J Chem 2015 in press. doi:10.1016/j.arabjc.2015.03.012.
[38] Saranya M, Latha S, Reddi MR, Gomathi T, Sudha PN, Anil S. Adsorption studies
of lead(ii) from aqueous solution onto nanochitosan /polyurethane /polypropy-
lene glycol ternary blends. Int J Biol Macromol 2017;104:1436–48.
[39] Zhang Y, Cao B, Zhao L, Sun L, Gao Y, Li J, et al. Biochar-supported reduced
graphene oxide composite for adsorption and coadsorption of atrazine and
lead ions. Appl Surf Sci 2018;427:147–55.
[40] Faheem, Yu H X, Liu J, Shen J Y, Sun X Y, Li J S, et al. Preparation of MnOx
-loaded biochar for Pb2+ , removal: adsorption performance and possible mech-
anism. J Taiwan Ins Chem E 2016;66:313–20.
[41] Wang F, Li H, Liu Q, Li Z, Li R, Zhang H, et al. A graphene oxide/amidoxime
hydrogel for enhanced uranium capture. Sci Rep 2016;6:19367.
[42] Xi Y, Mallavarapu M, Naidu R. Reduction and adsorption of pb2+, in aqueous
solution by nano-zero-valent iron—a SEM, TEM and XPS study. Mater Res Bull
2010;45:1361–7.