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Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320

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Journal of the Taiwan Institute of Chemical Engineers


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

Preparation of MnOx -loaded biochar for Pb2+ removal:


Adsorption performance and possible mechanism
Faheem, Hongxia Yu, Jia Liu, Jinyou Shen, Xiuyun Sun, Jiansheng Li, Lianjun Wang
Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of
Science and Technology, Nanjing 210094, Jiangsu Province, China

a r t i c l e

i n f o

Article history:
Received 21 December 2015
Revised 5 April 2016
Accepted 8 July 2016
Available online 21 July 2016
Keywords:
Biochar
Manganese oxide
Adsorption
Heavy metal
Mechanism

a b s t r a c t
In order to increase Pb2+ adsorption capacity of biochar derived from rice husk, the present work explored a facile modication route based on the loading of manganese oxide (MnOx ) nanoparticles. SEM,
BET, TEM, FTIR and XPS analysis conrmed the successful loading of MnOx nanoparticles onto biochar.
The maximum Pb2+ adsorption capacity for MnOx loaded biochar (MOLBC) with MnOx coverage of 40%
was as high as 86.5 mg g1 , while that for blank biochar was as low as 14.7 mg g1 . Specic surface area
as high as 340.0 m2 g1 was exhibited by 40%MOLBC, while the specic surface area of blank biochar
was only 234.8 m2 g1 . The MOLBC demonstrated relatively high adsorption capacity for Pb2+ , due to the
formation of MnOx sphere complexes especially monodentate, as well as oxygen complexes on biochar
surface. Besides this, -electron cloud system, decrease of electron density from -band of graphenic
nature carbon due to addition of -COOH and induced vacancy defect of graphenic basal plane created
on biochar surface was also considered to play a key role in Pb2+ adsorption. The results suggested that
MOLBC could be promisingly implemented as an environmentally friendly and inexpensive adsorbent for
Pb2+ removal from wastewater.
2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Agriculture wastes such as rice husk are available in excess in
various zones all over the world. Normally, agriculture waste has
been used as a low-grade energy resource and sometime burned
directly in the agriculture eld, causing serious air pollution problem. Agriculture wastes such as rice husk mainly consist of lignin,
cellulose, hemi-cellulose and silica [1]. After thermal and chemical
modication, active binding sites can be provided by these compositions for the adsorption of various organic and inorganic pollutants. Therefore, increasing attention has been paid on the thermal
or chemical modication of agriculture wastes for their ecient
reuse.
Biochar is often derived from agriculture wastes through pyrolysis process in which the biomass is subjected to thermochemical
conversion under oxygen-limited condition [2]. Fast pyrolysis
technique is a superior way for the valorization of agriculture
wastes to generate biochar. The oxygen-limited pyrolysis of carbon
rich biomass such as coconut shell, maize cob, rice husk, grape

Corresponding author. Fax: +86 25 84303965.


Corresponding author. Fax: +86 25 8431594.
E-mail addresses: shenjinyou@mail.njust.edu.cn, shenjinyou-1981@163.com
(J. Shen), wanglj@mail.njust.edu.cn (L. Wang).

stalk and peanut shell, at temperature range of 30 010 0 0 C, often


yields biochar possessing large surface area and porous structure
[2]. However, blank biochar often exhibits relatively low adsorption eciency. Rich husk ash has been applied for Pb2+ removal
but its maximum adsorption capacity was low as 12.4 mg g1 [3].
Therefore, chemical modication has been suggested in order to
improve adsorption capacity of biochar [4].
Recent studies have revealed that nanoparticles, such as aluminum oxide, nickel oxide, zero valent ion, MnOx , titanium oxide,
cerium oxide and magnesium oxide, could be used as ecient
adsorbents for heavy metals removal from polluted environment
[5,6]. However, these nanoparticles were prone to agglomeration
due to their nano-scale size, which limited their direct application as adsorbents [7]. This imperfection could be solved by the
development of biochar based composite adsorbents through the
loading of these metal oxides onto biochar surface [8]. Han et
al. [9] conrmed that nano-sized MnOx particles coated on sand
surface provide higher surface area due to their polymorphic
structure, which resulted in adsorption superiority. MnOx loaded
biochar (MOLBC) has been prepared, and the reported maximum
adsorption capacities for Pb2+ were higher than that of blank
biochar [10,11]. Thus, it gave us an idea to use composite adsorbent consist of nano MnOx and porous biochar for the removal of
heavy metals from wastewater.

http://dx.doi.org/10.1016/j.jtice.2016.07.010
1876-1070/ 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

314

Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320

Selection of MnOx here was due to its relatively higher sorption attraction for many heavy metals than Fe and Al oxides [12].
Wang et al. [10] indicated that Pb2+ removal by MOLBC could
be attributed to precipitation mechanism, complex formation
with surface functional groups and cation replacement. Moreover,
cation- interaction could be another important contributor to
heavy metal adsorption [13]. Ding et al. [14] attributed Pb2+ sorption by baggase biochar to ion exchange, intraparticle diffusion,
complex formation as well as P-induced precipitation. Furthermore, ion exchange mechanism was suggested when amorphous
MnO2 functionalized porous diatomaceous adsorbent was applied
for Pb2+ removal [15]. Especially, during the preparation of MOLBC,
besides the formation of surface dentate complexes, oxidation at
higher temperature often resulted in the change of biochar surface
chemistry such as cation- interaction and formation of vacancy
defects on biochar surface. Therefore, adsorption mechanism and
interaction type between the adsorbent and adsorbate are still
doubtful as far.
Herein, MOLBC with different Mn loading was synthesized. The
structure of the as-prepared adsorbents was studied by FT-IR, TEM,
SEM-EDS, XPS and BET analysis. The adsorption performance of
the as-prepared MOLBC, the adsorption kinetics and isotherms of
40%MOLBC were investigated in detail. In addition, the possible
mechanism involved in the Pb2+ removal by MOLBC was proposed.
2. Materials and methods
2.1. Preparation of blank biochar
The rice husk was washed with distilled water to remove adhering impurities. Then it was subjected to drying process at 90 C
and nally passed through sieves to obtain the particles with the
size less than 0.6 mm. The obtained rice husk was then carbonized
in mue furnace at 800 C for 3 h under nitrogen atmosphere to
obtain blank biochar [2].

2 mL H2 O2 (30%). Pb2+ concentration was determined by atomic


absorption spectrophotometer.
2.4. Adsorption experiments
Both as-obtained MOLBC and blank biochar were used as the
adsorbent in the adsorption study. To investigate the adsorption
performance, 0.1 g of blank biochar or modied biochar was added
into 100-mL Erlenmeyer asks containing 50 mL Pb2+ solution. The
dosage of blank biochar or modied biochar was chosen according to Wang et al. [10]. The initial pH of the solutions was adjusted to 5.0 0.1 through the addition of HNO3 (0.01 mol L1 ) and
NaOH (0.01 mol L1 ). Then Erlenmeyer asks were placed on rotary shaker at 150 rpm and 25 C. For the adsorption kinetic study,
the suspensions were immediately ltered through 0.22 m lter
at each sampling time, and then subjected to analysis. For the adsorption isothermal experiment, initial Pb2+ concentrations were
selected in the range of 15250 mg L1 . Pb2+ adsorbed (qe ) was
calculated by Eq. (1) based on mass balance, while the removal efciency was calculated by Eq. (2).

qe =
p=

(Co Ce )V
w

(Co Ce )
Co

100%

(1)
(2)

where C0 (mg L1 ) is referred to initial Pb2+ concentration, Ce (mg


L1 ) is referred to Pb2+ concentration at equilibrium, V (L) is the
solution volume and w (g) is concerned to weight of the adsorbent.
The results were reported as an average of three independent
experiments. Maximum deviations from the average (error bars)
were indicated.
3. Results and discussion
3.1. Characterization of MnOx-loaded biochar

2.2. Synthesis of MOLBC


For the synthesis of MOLBC, 5 g blank biochar was immersed
in 50 mL KMnO4 solution at desired concentrations. Then, these
suspensions were subjected to ultrasonically treatment for 2 h and
dried at 80 C for 5 h. The KMnO4 modied biochar was further
subjected to heat treatment under nitrogen atmosphere at 800 C
for 20 min. Finally, the obtained MOLBC was rinsed thoroughly using deionized water until the pH of leachate reached 7.0. Different
weight ratio of KMnO4 and blank biochar was chosen, i.e., 1:20
(5%), 1:10 (10%), 2:5 (40%) and 2.5:5 (50%). Correspondingly, the
products were labeled as 5%MOLBC, 10%MOLBC, 40%MOLBC and
50%MOLBC, respectively.
2.3. Characterization
To characterize the biochar surface morphology and elemental
composition, SEM coupled with EDS was applied. The elements
weight percent of C, O, N, Si and Mn were determined. The BET
surface area (SBET ) and micropores width was analyzed by nitrogen adsorption data at 77 K. Both blank biochar and MOLBC samples were dried to constant weight and then analyzed by FT-IR
spectrometer for conrmation of available functional groups on
biochar surface. FE-TEM was used to visualize the dispersion of
MnOx nanoparticle on biochar surfaces. XPS analysis was also carried out to conrm the metallic state of Mn and quantitative information about the nature of surface oxygen containing groups. The
loaded Mn bulk content on biochar surface was analyzed by digestion method [11]. The digestion experiments was carried out by using a mixture of 2 mL HF (40%), 10 mL HNO3 (69%), 2 mL HClO4 and

In this study, blank biochar was prepared by carbonization and


then was immersed in KMnO4 solution under ultrasonically treatment. Further heat treatment exposure (800 C) for 20 min in N2
environment accelerated KMnO4 conversion into MnOx nanoparticles. Fig. 1 showed the SEM and TEM images of blank biochar and
40%MOLBC. The SEM image showed rough surface of 40%MOLBC
as compared to smooth surface of blank biochar due to deposition of MnOx nanoparticles (Fig. 1a and 1b). Comparing with
blank biochar, elemental analysis conrm the increase of O and
Mn content, while C, N and Si contents decreased after modication, which could be explained by the strong oxidation and
MnOx nanoparticles deposition on modied biochar surface (Table
1). Furthermore, TEM analysis conrmed the successful deposition
of nano-sized MnOx particles on 40%MOLBC surface (Fig. 1c). These
nano-sized MnOx particles possesses nanoparticles lattice fringes
of about 3 A (Fig. 1d), which was consistent with the previous
study [16].
No MnOx nanoparticles could be found on blank biochar, which
has been further conrmed by XPS characterization, as indicated
in Fig. 2. However, the sharp peak for Mn mineral was exhibited
on the as-obtained MOLBC (Fig. 2a). As shown in Fig. 2b, binding
energy values of Mn(2p) for 40%MOLBC are in the range of 641.7642.0 eV, suggesting the existence of Mn mineral as oxidation state
between Mn3+ and Mn4+ [9]. Fig. 3a summarizes the surface area
and pore size of the as-prepared MOLBC with different Mn loading.
The surface area rstly increased from 234.8 m2 g1 to 430.2 m2
g1 when the Mn loading amount increased from 0% to 10%, and
then decreased for samples loaded by more MnOx nanoparticles.
The initial increase might be explained by the deposition of MnOx

Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320

315

Fig. 1. SEM of blank biochar (a) and 40%MOLBC (b), TEM of 40%MOLBC (c and d).
Table 1
Elements weight percent and removal percentage of blank biochar and MOLBC.
Sample

Blank biochar
5%MOLBC
10%MOLBC
40%MOLBC
50%MOLBC

Elemental weight percentage (%)


C

Si

Mn

24.84
22.05
21.75
15.37
14.89

1.60
1.49
1.28
0.90
0.62

44.59
46.42
47.54
51.91
53.61

28.96
28.83
27.17
24.97
23.92

1.21
2.26
6.85
6.96

Actual loaded Mn
content (mg g1 )

Lead removal (%)

20.16 1.75
29.33 1.53
42.10 2.26
97.79 2.43
83.20 1.61

14.32 0.66
28.73 1.10
114.02 1.12
144.65 2.93

Table 2
Textural characteristics of blank biochar and MOLBC.

Sample

BET surface area


(m2 g1 )

Average pore width


(nm)

Total pore volume


(cm g_1 )

Micropore area
(m2 g1 )

External surface
area (m2 g1 )

Blank biochar
5%MOLBC
10%MOLBC
40%MOLBC
50%MOLBC

234.8
420.9
430.2
340.0
260.0

3.34
2.87
2.66
2.46
2.18

0.101
0.123
0.092
0.056
0.030

151.7
301.6
338.6
264.2
194.5

83.1
119.3
91.6
75.8
65.5

nanoparticles and generation of more micropores, while the decrease at high loading is likely due to excess deposition of MnOx
nanoparticles, which may lead to the pores blockage and destruction of some microspore structure. With the increase of Mn loading
amount from 0% to 50%, the pore size decreased from 3.34 nm to
2.18 nm (Fig. 3a), conrming the existence of pore-blocking. In addition, with the increase of Mn loading amount, total pore volume,
micropore area and external surface area increased rstly, then decreased with the further increase of Mn loading amount (Table 2).
Highly excessive KMnO4 dosage, i.e., 50%MOLBC, often led to high
burn-off level of the inner structure of biochar, resulting in the formation of mesopores due to collapse and growth of existing micropores structure [17].
FT-IR spectroscopy was used to study the surface functional
groups of the as-prepared MOLBC. The broad and strong band observed at 3448 cm1 could be assigned to the stretching vibration
of hydroxyl functional groups (Fig. 3b). The two bands appearing
at 1620 and 1400 cm1 correspond to the C=C and C=O stretching vibration, while the band at 1100 cm1 can be assigned to

the C-O stretching vibration. After KMnO4 treatment, the increase


of surface oxygen containing functional groups was also observed
through elemental analysis (Table 1). All of these results demonstrate that the as-prepared MOLBC possess rich hydrophilic groups
on the surface, which is favorable for the removal of Pb2+ from
aqueous solution.
The loading amount of MnOx nanoparticles could be readily
controlled by tuning the weight ratio of KMnO4 and blank biochar
during the synthesis of MOLBC. Moreover, MnOx nanoparticles
could be successfully loaded onto biochar, as was indicated by the
high Mn bulk content on biochar surface (>80%), which was evaluated after comparison between determined values and calculated
values for all samples (Table 1). Adsorption experiment was carried out to investigate the potential application of the as-prepared
MOLBC in the removal of Pb2+ . The series of as prepared materials
such as 5%MOLBC, 10%MOLBC, 40%MOLBC, 50%MOLBC as well as
blank biochar were applied for Pb2+ removal. As shown in Table 1,
Pb2+ removal eciency increased with the increase of Mn loading
from 0% to 40%, and then decreased with the further increase of

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Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320

Fig. 3. Pore size and BET surface area relationship (a), FTIR spectra of blank biochar
and 40%MOLBC (b).

Fig. 2. XPS wide scan of blank biochar and 40%MOLBC (a), XPS showing Mn2p core
level in blank biochar and 40%MOLBC (b).

Mn loading to 50%. For 50%MOLBC, lower adsorption eciency


could be attributed to excess loading of MnOx nanoparticles,
which resulted in the decrease of surface area and pore size.
Therefore, 40%MOLBC was chosen for further investigation.
3.2. Adsorption performance of MnOx-loaded biochar towards Pb2+
Pseudo-second order kinetics models was implemented to conrm their tness with the adsorption data obtained experimentally
for Pb2+ removal by blank biochar and modied biochar. Besides
the value of coecient R2 , the best t kinetic model can be veried through sum of squared errors (SSE) analysis. The higher value
of R2 along with lower SSE value often indicates better tness of
model to be applied.
The Eq. (3) shows the linear trend for pseudo-second order kinetics model, and Eq. (4) shows the calculation of sum of squared
errors (SSE):

t
1
t
=
+
qt
qe
kqe 2

SSE, % =



(3)

qe,exp qe,cal
N

values such as qe and k were deduced from the slope and intercept
of straight line plot between t/qt and t.
The adsorption data revealed that a rapid initial sorption phase
was observed in the rst 15 min, after that saturation phase dominated and nally equilibrium stage reached within 80 min (Fig. 4a).
The high R2 for Pb2+ adsorption data and slightly difference between qe (cal) and qe (exp) indicated that Pb2+ adsorption data
was best tted to pseudo-second order kinetics model (Fig. 4b), as
compared to pseudo-rst order kinetics model and intra-particle
diffusion model. In general, a small k value indicates a higher
sorption rate [18]. In our experiment, the k value for 40%MOLBC
was 6.3 times lower than that of blank biochar, conrming that
sorption rate of 40%MOLBC was much higher than that of blank
biochar (Table 3). It was probably due to more active site available on the surface of 40%MOLBC as compared to blank biochar.
In addition, the low value of SSE also indicated a better tness
of pseudo-second order kinetics (Table 3). These results implied
that adsorption of Pb2+ onto 40% MOLBC were mainly controlled
by chemisorption, including exchange and sharing of valence
electrons.
Generally, adsorption isotherms are applied to describe the
phenomenon controlling the release or movement of adsorbate
from liquid to solid media. Isotherms models such as Langmuir
(equation (5)) and Freundlich (equation (6)) were applied in this
study to describe the adsorption of Pb2+ by blank biochar and 40%
MOLBC.

1
1
1
=
+
qe
qmax
qmax KLCe

2
(4)

where k is referred to pseudo-second order rate constant, N represents number of data points, qe and qt are adsorbent sorption capacity (mg g-1 ) at equilibria and time t, respectively. The parameter

log qe = log K f +

1
n

(5)

log Ce

(6)

Here equilibrium liquid phase and solid-phase concentration of


Pb2+ are represented by Ce (mg L-1 ) and qe (mg g-1 ), respectively.

Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320

317

Fig. 4. Pb2+ sorption by 40%MOLBC (a) and pseudo-second-order model tting (b), qe for 40%MOLBC at different initial Pb2+ concentrations (c) and Langmuir isotherm tting
(d).
Table 3
Pseudo-second order kinetics and Langmuir isotherm model for Pb2+ adsorption on blank biochar and
40%MOLBC at 25 C.
Model

Parameters

40% MOLBC

Blank Biochar

Pseudo-second order kinetics

qe(cal) (mg g-1 )


qe(exp) (mg g-1 )
k (g mg -1 min-1 )
R2
SSE%
qmax (mg g-1 )
KL (L mg1 )
R2

60.97
60.69 0.16
0.004
0.999
0.174
86.5
0.568
0.988

9.91
9.65 0.15
0.029
1.0 0 0
0.166
14.7
0.107
0.983

Langmuir isotherm model

The qmax (mg g-1 ) and KL (L mg-1 ) are associated to the maximum
adsorption capacity of metals ions per unit weight of adsorbent
and adsorption energy of binding sites, respectively. The parameters such as KL and qmax were yielded from intercept and slope
of the plot 1/Ce versus 1/qe . The constant Kf is related to adsorption capacity, while 1/n is related to adsorption strength. The slope
(1/n) and intercept (LogKf ) of the plot between logqe and logCe
gives us the numerical value of n and Kf , respectively.
Langmuir isotherm is valid if adsorption mechanism is only limited to formation of monolayer between adsorbent and adsorbate
due to nite number of identical sites present on adsorbent surface. This model has some limitations such as uniform energies of
adsorption taken place onto the surface and there is no further
interaction of adsorbate in the same plane of adsorbent surface.
In addition, in case of nonimitative and reversible adsorption over
heterogeneous surface, adsorption process are commonly described
by Freundlich isotherm model [19].
Effect of initial Pb2+ concentration on qe was also studied
for both 40%MOLBC and blank biochar. For 40%MOLBC, qe increased with the increase of C0 up to 235 mg g1 and then

became constant (Fig. 4c). Pb2+ adsorption by both blank biochar


and 40%MOLBC could be well described by Langmuir, as indicated
by the high R2 of Langmuir (Table 3 and Fig. 4d), indicating that
the adsorption mechanism involved was only limited to formation of monolayer. However, Pb2+ adsorption by both blank biochar
and 40%MOLBC could not be well described by Freundlich isotherm
model, as indicated by the R2 lower than 0.9. According to Langmuir model, 40%MOLBC exhibited qmax as high as 86.5 mg g-1 at
room temperature, which was almost ve times larger than that of
blank biochar, which was only 14.7 mg g-1 .
Furthermore, adsorption capacity of 40%MOLBC for Pb2+ removal was compared with other adsorbents cited in literatures,
as shown in Table 4. Bagasse biochar and rice husk ash had
exhibited the maximum capacity of 21.0 and 12.4 mg/g, which
was comparable with that of the blank biochar obtained in this
study [3,14]. MnOx loaded pine wood biochar was synthesized
by two different modication methods, i.e., pyrolyzation in the
presence of MnCl2 (MPB) and impregnation with birnessite via
precipitation following pyrolysis (BPB), which showed different
sorption capacities of 4.9 mg g-1 and 47.1 mg g-1 , respectively [10].

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Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320
Table 4
Comparison of maximum adsorption capacities for Pb2+ by various adsorbents.
Adsorbent

Rice Husk
Bagasse Biochar
Modied Diatomite
Modied Bentonite
Modied Wood Bicohar
40%MOLBC
Blank Biochar

Experimental conditions
qmax (mg g-1 )

R2

Dosage (g mL-1 )

pH

T (K)

Ref

12.4
21.0
99.0
31.9
47.1
86.5
14.7

0.999
0.970

0.996
0.923
0.988
0.983

0.1/50
1.7/1700

0.05/20
0.1/50
0.1/50

5
4

5.5
5
5

288
295
289
298
295
298
298

[3]
[14]
[20]
[21]
[10]
This work
This work

Fig. 5. XPS wide scan of 40%MOLBC: C1s (a), 40%MOLBC spectra after Pb(II) interaction (b), O1s conguration before Pb(II) adsorption (c), O1s conguration after Pb(II)
adsorption (d).

After modication by manganese oxide, the adsorption capacity


of diatomite and bentonite could be signicantly improved, with
the adsorption capacity of modied adsorbent as high as 99.0 mg
g-1 and 31.9 mg g-1 , respectively [20,21]. The adsorption capacity
of 40%MOLBC for Pb2+ removal was as high as 86.5 mg g-1 , which
was much higher than that of the reported biochar based adsorbent, demonstrating the high eciency of MOLBC for heavy metal
removal from wastewater.
3.3. Possible mechanism involved in Pb2+ removal by MOLBC
In order to elucidate the adsorption mechanism, XPS analysis were performed for both blank biochar and 40%MOLBC
(Fig. 5). The detail spectra of C1s before and after Pb2+ adsorption
is presented in Fig. 5a. Three peaks were observed at about 288 eV,
291.9 eV and 294.5 eV before adsorption, which can be assigned
to minor contribution of ketone functionality, - transition and
-electron existence, respectively. After adsorption of Pb2+ on
40%MOLBC surface, no peaks were observed at 288 eV, 291.9 eV
and 294.5 eV, which conrmed the interaction of ketones (or
lactone like, C=O and pyran-like ether groups in the vicinity
of biochar graphene disordered basal plane), electron density
reduction in -bond aromatic moieties due to the addition of

-COOH and delocalized -electron cloud system with Pb2+ ions,


respectively [22]. Incorporation of oxygen functionality such as
carboxyl group on biochar surface often causes the decrease of
electron density from -band of graphenic nature carbon available
in biochar. It may affect the cation- interaction to some extent
and favor the formation of inner surface complexes of Pb2+ due
to deprotonation of carboxylic acid functionalities. Similar results
were observed for the biochar pretreated with H2 O2 , whose cation
exchange capacity increased with the increase of H2 O2 dosage [23].
The Pb2+ adsorption took place due to elimination of H+
through -COOH, -OH and SiOH functional groups into aqueous
solution, which was reected by solution pH reduction. These
results are the evidence of interconnected building complexes
formation with oxygen containing functional groups available on
composite adsorbent surface [24].
+
P b2+ + 2( SiOH ) P b( SiO )+
2 + 2H

2(COOH ) + P b

2+

(COO )2 P b + 2H +

In addition, the peak at electron binding energy of 138.0 eV was


observed in Fig. 5b, which is reported to be related with PbO formation [25]. This indicates a preoccupation or xation of lead onto

Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320

40%MOLBC surface during the process as well as choking or intercalation into loaded MnOx surface.
After Pb2+ adsorption, the minor area ratio change (6.64%7.33%) was observed for the peak at 533.2ev (Fig. 5c), demonstrating that chemisorbed H2 O was also participated in the adsorption
up to limited extent due to increase in biochar hydrophilic nature.

C + 2H2 O  C H3 O+ + OH

319

adsorption capacity than blank biochar. XPS and FT-IR analyses revealed that the adsorption was not limited to the involvement of
nano sized manganese oxide loaded particles and available surface oxygen containing functional groups. The -clouds system,
vacancy defect of biochar graphenic basal plane and - transition (electron density reduction in -bond aromatic moieties due
to addition of -COOH) was also intended as adsorption controlling
factors.

(Biochar basic nature)

C : H3 O+ + P bOH + C : P bOH + + H3 O+

Acknowledgments

(pH reduction)
Moreover, the remarkable area ratio changes were found in case
of peaks appeared at 531.4 eV and 532.4ev imputed to C-OH and
M-OH, respectively (Fig. 5d). After Pb2+ adsorption, the peak area
for C-OH and M-OH increased from 14.24% and 22.8% to 21.9%
and 41.98%, respectively. By contrast, for the peak at 530.1 eV, this
could be assigned to M-O decreased from 56.3% to 28.7% after Pb2+
adsorption. This was due to formation of relatively more monodentate complexes than bidentate mononuclear, bidentate binuclear and multidentate during Pb2+ adsorption. It is cleared from
proposed complicated adsorption mechanism conceptual model, a
monodentate surface complex embedded one additional -OH group
on adsorbent surface as compared to bidentate and mutidentate
surface complexes [26]. Moreover, surface -OH groups involved as
bridging with the metal centers to form dentate complexes.
The literature data revealed that graphene sheets of plantderived biochars at high temperature also possessed an abundance
of -electron. Highest occupied molecular orbital (HOMO) of unsaturated system such as hexagonal rings of aromatic compounds
and C-C triple bond was mainly composed of -electron. With the
increase of pyrolysis temperature, the amorphous characteristics of
biochar structure gradually converted into a turbostratic char material, which was mainly made of disordered graphitic crystallites.
In present study, ultrasonically chemical treatment with KMnO4
and further heat treatment of biochar caused vacancy defects generation in biochar graphenic basal plane. Pb2+ adsorption by lactone like, C=O and pyran-like ether groups available at vacancy
defect as well as cation- interaction could also be considered
as a key factor because of carbon atom graphenic properties of the
MOLBC. Similar trend was observed when vacancy defect was induced into prepared graphene sheet after thermal treatment [27].
Moreover, cation- clouds involvement was noncovalent bonding
or electrostatic interaction in between monopole (Pb2+ ) and quadrpole ( -system) benzene rings associated with existing graphene
sheets of biochar [28]. These results were well in agreement with
literature study in which unsaturated and aromatic system of commercial activated carbon causes Pb2+ - cloud bonding [29].

This research is nanced by Fundamental Research Funds for


Jiangsu Province Biomass Energy and Materials Laboratory (No. JSBEM201408) and Fundamental Research Funds for the Central Universities (No. 30916011312).

C : +P b2+ C : P b2+
(C -cation interaction)
Moreover, involvement of surface-bound persistent free radical
formed by the electron transfer from adsorbate to the metal
through chemisorption mechanism might contribute to Pb2+
adsorption [30]. Finally these active sites serve as a Lewis base or
electron-pair donor and Pb2+ act as Lewis acid or electron-pair
acceptor.
4. Conclusion
The present work focused on the adsorption performance improvement and possible removal mechanism of Pb2+ by MOLBC.
In comparison to the blank biochar, high adsorption capacity for
Pb2+ was observed for MOLBC. The enhanced Pb2+ adsorption by
MOLBC was attributed to the loaded manganese oxide nanoparticles onto biochar. 40%MOLBC exhibited almost ve times higher

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