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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
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.
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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].
qe =
p=
(Co Ce )V
w
(Co Ce )
Co
100%
(1)
(2)
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
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 )
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
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
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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).
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)
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
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
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
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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).
2(COOH ) + P b
2+
(COO )2 P b + 2H +
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.
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].
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
References
[1] Zhang H, Ding X, Chen X, Ma Y, Wang Z, Zhao X. A new method of utilizing rice husk: Consecutively preparing d-xylose, organosolv lignin, ethanol and
amorphous superne silica. J Hazard Mater 2015;291:6573.
[2] Alvarez J, Lopez G, Amutio M, Bilbao J, Olazar M. Upgrading the rice husk char
obtained by ash pyrolysis for the production of amorphous silica and high
quality activated carbon. Bioresour Technol 2014;170:1327.
[3] Feng Q, Lin Q, Gong F, Sugita S, Shoya M. Adsorption of lead and mercury by
rice husk ash. J Colloid Interface Sci 2004;278:18.
[4] Liu W-J, Jiang H, Yu H-Q. Development of Biochar-based functional materials:
toward a sustainable platform carbon material. Chem Rev 2015;115:1225185.
[5] Hua M, Zhang S, Pan B, Zhang W, Lv L, Zhang Q. Heavy metal removal
from water/wastewater by nanosized metal oxides: a review. J Hazard Mater
2012;211:31731.
[6] Mahmoud AM, Ibrahim FA, Shaban SA, Youssef NA. Adsorption of heavy metal
ion from aqueous solution by nickel oxide nano catalyst prepared by different
methods. Egypt J Petrol 2015;291:2735.
[7] Tyson BM, Al-Rub RKA, Yazdanbakhsh A, Grasley Z. A quantitative method
for analyzing the dispersion and agglomeration of nano-particles in composite materials. Compos Part B Eng 2011;42:1395403.
[8] Zhang M, Gao B, Yao Y, Xue Y, Inyang M. Synthesis of porous MgO-biochar
nanocomposites for removal of phosphate and nitrate from aqueous solutions.
Chem Eng J 2012;210:2632.
[9] Han R, Zou W, Zhang Z, Shi J, Yang J. Removal of copper (II) and lead (II) from
aqueous solution by manganese oxide coated sand: I. Characterization and kinetic study. J Hazard Mater 2006;137:38495.
[10] Wang S, Gao B, Li Y, Mosa A, Zimmerman AR, Ma LQ, et al. Manganese oxide
modied biochars: Preparation, characterization, and sorption of arsenate and
lead. Bioresource Technol 2015;181:1317.
[11] Wang M, Sheng G, Qiu Y. A novel manganese-oxide/biochar composite for efcient removal of lead (II) from aqueous solutions. Int J Environ Sci Technol
2015;12:171926.
[12] OReilly SE, Hochella MF. Lead sorption eciencies of natural and synthetic Mn
and Fe-oxides. Geochim Cosmochim Acta 2003;67:447187.
[13] Song Z, Lian F, Yu Z, Zhu L, Xing B, Qiu W. Synthesis and characterization of a
novel MnOx-loaded biochar and its adsorption properties for Cu2+ in aqueous
solution. Chem Eng J 2014;242:3642.
[14] Ding W, Dong X, Ime IM, Gao B, Ma LQ. Pyrolytic temperatures impact lead
sorption mechanisms by bagasse biochars. Chemosphere 2014;105:6874.
[15] Li S, Li D, Su F, Ren Y, Qin G. Uniform surface modication of diatomaceous
earth with amorphous manganese oxide and its adsorption characteristics for
lead ions. Appl Surf Sci 2014;317:7249.
[16] Lee H, Park SH, Kim S-J, Park Y-K, Kim B-J, An K-H, et al. Synthesis of manganese oxide/activated carbon composites for supercapacitor application using
a liquid phase plasma reduction system. Int J Hydrogen Energ 2015;40:7549.
[17] Hsi H-C, Horng RS, Pan T-A, Lee S-K. Preparation of activated carbons from raw
and biotreated agricultural residues for removal of volatile organic compounds.
J Air Waste Manage 2011;61:54351.
[18] Maliyekkal SM, Sharma AK, Philip L. Manganese-oxide-coated alumina: a
promising sorbent for deuoridation of water. Water Res 2006;40:3497506.
[19] Ghasemi M, Naushad M, Ghasemi N, Khosravi-Fard Y. Adsorption of Pb (II)
from aqueous solution using new adsorbents prepared from agricultural waste:
Adsorption isotherm and kinetic studies. J Ind Eng Chem 2014;20:21939.
[20] Al-Degs Y, Khraisheh M, Tutunji M. Sorption of lead ions on diatomite and
manganese oxides modied diatomite. Water Res 2001;35:37248.
[21] Eren E. Removal of lead ions by Unye (Turkey) bentonite in iron and magnesium oxide-coated forms. J Hazard Mater 2009;165:6370.
[22] Sanchez-Polo M, Rivera-Utrilla J. Adsorbent-adsorbate interactions in the adsorption of Cd (II) and Hg (II) on ozonized activated carbons. Environ Sci Technol 2002;36:38504.
[23] Huff MD, Lee JW. Biochar-surface oxygenation with hydrogen peroxide. J Environ Manage 2016;165:1721.
[24] 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;46:85462.
320
Faheem et al. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313320