You are on page 1of 8

Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320

Contents lists available at ScienceDirect

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 modification route based on the loading of manganese oxide (MnOx ) nanoparticles. SEM,
BET, TEM, FTIR and XPS analysis confirmed 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 g−1 , while that for blank biochar was as low as 14.7 mg g−1 . Specific surface area
as high as 340.0 m2 g−1 was exhibited by 40%MOLBC, while the specific surface area of blank biochar
was only 234.8 m2 g−1 . 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, π -electron cloud system, decrease of electron density from π -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 field, 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
modification, 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 modification of agriculture wastes for their efficient
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 0–10 0 0 °C, often
yields biochar possessing large surface area and porous structure
[2]. However, blank biochar often exhibits relatively low adsorption efficiency. Rich husk ash has been applied for Pb2+ removal
but its maximum adsorption capacity was low as 12.4 mg g−1 [3].
Therefore, chemical modification 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 efficient
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] confirmed 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.

Furthermore.01 mol L−1 ). The BET surface area (SBET ) and micropores width was analyzed by nitrogen adsorption data at 77 K. cation-π interaction could be another important contributor to heavy metal adsorption [13]. Si and Mn were determined. 2 mL H2 O2 (30%).4. The results were reported as an average of three independent experiments. SEM-EDS.0 ± 0. N. Wang et al. 5 g blank biochar was immersed in 50 mL KMnO4 solution at desired concentrations. complex formation with surface functional groups and cation replacement. which was consistent with the previous study [16]. 10%MOLBC. The loaded Mn bulk content on biochar surface was analyzed by digestion method [11]. Characterization To characterize the biochar surface morphology and elemental composition. TEM analysis confirmed the successful deposition of nano-sized MnOx particles on 40%MOLBC surface (Fig. Moreover. qe = p= (Co − Ce )V w (Co − Ce ) Co × 100% (1) (2) where C0 (mg L−1 ) is referred to initial Pb2+ concentration. N and Si contents decreased after modification. 1:20 (5%). while the removal efficiency was calculated by Eq. 2. complex formation as well as P-induced precipitation. The adsorption performance of the as-prepared MOLBC.01 mol L−1 ) and NaOH (0.2. i. SEM coupled with EDS was applied. intraparticle diffusion. the possible mechanism involved in the Pb2+ removal by MOLBC was proposed. Results and discussion 3. The obtained rice husk was then carbonized in muffle furnace at 800 °C for 3 h under nitrogen atmosphere to obtain blank biochar [2]. 1 showed the SEM and TEM images of blank biochar and 40%MOLBC. O. The initial increase might be explained by the deposition of MnOx . the obtained MOLBC was rinsed thoroughly using deionized water until the pH of leachate reached 7. Especially. Then it was subjected to drying process at 90 °C and finally passed through sieves to obtain the particles with the size less than 0. XPS analysis was also carried out to confirm the metallic state of Mn and quantitative information about the nature of surface oxygen containing groups. Pb2+ concentration was determined by atomic absorption spectrophotometer. Adsorption experiments Both as-obtained MOLBC and blank biochar were used as the adsorbent in the adsorption study. Different weight ratio of KMnO4 and blank biochar was chosen. XPS and BET analysis. these suspensions were subjected to ultrasonically treatment for 2 h and dried at 80 °C for 5 h. The initial pH of the solutions was adjusted to 5. For the adsorption kinetic study. MOLBC with different Mn loading was synthesized. Preparation of blank biochar The rice husk was washed with distilled water to remove adhering impurities. besides the formation of surface dentate complexes.5:5 (50%). 2. which has been further confirmed by XPS characterization. the suspensions were immediately filtered through 0. Furthermore. 2 mL HClO4 and In this study.7642. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 Selection of MnOx here was due to its relatively higher sorption attraction for many heavy metals than Fe and Al oxides [12]. Fig. Then. Therefore. Characterization of MnOx-loaded biochar 2. [10] indicated that Pb2+ removal by MOLBC could be attributed to precipitation mechanism. V (L) is the solution volume and w (g) is concerned to weight of the adsorbent. Maximum deviations from the average (error bars) were indicated. As shown in Fig. Then Erlenmeyer flasks were placed on rotary shaker at 150 rpm and 25 °C. FE-TEM was used to visualize the dispersion of MnOx nanoparticle on biochar surfaces.0.6 mm.314 Faheem et al. suggesting the existence of Mn mineral as oxidation state between Mn3+ and Mn4+ [9]. 1a and 1b). 2:5 (40%) and 2. [10]. 40%MOLBC and 50%MOLBC. binding energy values of Mn(2p) for 40%MOLBC are in the range of 641. Correspondingly. 10 mL HNO3 (69%). and then decreased for samples loaded by more MnOx nanoparticles. oxidation at higher temperature often resulted in the change of biochar surface chemistry such as cation-π interaction and formation of vacancy defects on biochar surface. 1c). For the adsorption isothermal experiment. TEM. 1d). In addition.1. the adsorption kinetics and isotherms of 40%MOLBC were investigated in detail. during the preparation of MOLBC. (2).e. These nano-sized MnOx particles possesses nanoparticles lattice fringes of about 3 A˚ (Fig. Herein.1. The SEM image showed rough surface of 40%MOLBC as compared to smooth surface of blank biochar due to deposition of MnOx nanoparticles (Fig.22 μm filter at each sampling time. while C. To investigate the adsorption performance. Further heat treatment exposure (800 °C) for 20 min in N2 environment accelerated KMnO4 conversion into MnOx nanoparticles. initial Pb2+ concentrations were selected in the range of 15–250 mg L−1 . Both blank biochar and MOLBC samples were dried to constant weight and then analyzed by FT-IR spectrometer for confirmation of available functional groups on biochar surface. the products were labeled as 5%MOLBC. 2. Pb2+ adsorbed (qe ) was calculated by Eq.1 g of blank biochar or modified biochar was added into 100-mL Erlenmeyer flasks containing 50 mL Pb2+ solution. (1) based on mass balance. adsorption mechanism and interaction type between the adsorbent and adsorbate are still doubtful as far. The elements weight percent of C. 1:10 (10%). the sharp peak for Mn mineral was exhibited on the as-obtained MOLBC (Fig.1 through the addition of HNO3 (0. Fig. 2a). The dosage of blank biochar or modified biochar was chosen according to Wang et al. No MnOx nanoparticles could be found on blank biochar. and then subjected to analysis. Finally. respectively. Ce (mg L−1 ) is referred to Pb2+ concentration at equilibrium. Ding et al. The structure of the as-prepared adsorbents was studied by FT-IR. which could be explained by the strong oxidation and MnOx nanoparticles deposition on modified biochar surface (Table 1). as indicated in Fig. The KMnO4 modified biochar was further subjected to heat treatment under nitrogen atmosphere at 800 °C for 20 min. Materials and methods 2.8 m2 g−1 to 430. The surface area firstly increased from 234. Comparing with blank biochar.2 m2 g−1 when the Mn loading amount increased from 0% to 10%.. Synthesis of MOLBC For the synthesis of MOLBC. The digestion experiments was carried out by using a mixture of 2 mL HF (40%).0 eV. blank biochar was prepared by carbonization and then was immersed in KMnO4 solution under ultrasonically treatment.3. 3. 0. 2b. However. [14] attributed Pb2+ sorption by baggase biochar to ion exchange. elemental analysis confirm the increase of O and Mn content. 2. ion exchange mechanism was suggested when amorphous MnO2 functionalized porous diatomaceous adsorbent was applied for Pb2+ removal [15]. 3a summarizes the surface area and pore size of the as-prepared MOLBC with different Mn loading.

34 2.37 14.5 83.90 0. Highly excessive KMnO4 dosage. the increase of surface oxygen containing functional groups was also observed through elemental analysis (Table 1).33 ± 1.9 430.8 65.101 0. the pore size decreased from 3.59 46. with the increase of Mn loading amount. and then decreased with the further increase of .61 14.21 2.2 194..28 0. resulting in the formation of mesopores due to collapse and growth of existing micropores structure [17]. Table 1 Elements weight percent and removal percentage of blank biochar and MOLBC.5 nanoparticles and generation of more micropores.6 338.34 nm to 2.84 22. as was indicated by the high Mn bulk content on biochar surface (>80%).91 53.85 6.42 47.6 264.43 83. Sample BET surface area (m2 g−1 ) Average pore width (nm) Total pore volume (cm³ g_1 ) Micropore area (m2 g−1 ) External surface area (m2 g−1 ) Blank biochar 5%MOLBC 10%MOLBC 40%MOLBC 50%MOLBC 234. Sample Blank biochar 5%MOLBC 10%MOLBC 40%MOLBC 50%MOLBC Elemental weight percentage (%) C N O Si Mn 24.26 6.79 ± 2.92 – 1. SEM of blank biochar (a) and 40%MOLBC (b).62 44. As shown in Table 1.96 Actual loaded Mn content (mg g−1 ) Lead removal (%) – 20. while the band at 1100 cm−1 can be assigned to the C-O stretching vibration. In addition. which was evaluated after comparison between determined values and calculated values for all samples (Table 1).49 1.65 ± 2.54 51.53 42.46 2.0 3.1 119. total pore volume.66 28.26 97. 50%MOLBC as well as blank biochar were applied for Pb2+ removal. while the decrease at high loading is likely due to excess deposition of MnOx nanoparticles.60 1. 50%MOLBC. Pb2+ removal efficiency increased with the increase of Mn loading from 0% to 40%.056 0. i.32 ± 0.092 0.97 23. often led to high burn-off level of the inner structure of biochar.8 420. confirming the existence of pore-blocking.e.18 0. After KMnO4 treatment.10 ± 2.61 28.12 144. 1. 40%MOLBC.75 15.73 ± 1.66 2.16 ± 1. The broad and strong band observed at 3448 cm−1 could be assigned to the stretching vibration of hydroxyl functional groups (Fig. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 315 Fig.89 1. FT-IR spectroscopy was used to study the surface functional groups of the as-prepared MOLBC.0 260.030 151. Moreover. micropore area and external surface area increased firstly.123 0.2 340. The series of as prepared materials such as 5%MOLBC. 10%MOLBC.17 24. TEM of 40%MOLBC (c and d). which may lead to the pores blockage and destruction of some microspore structure.05 21.6 75.83 27.02 ± 1. With the increase of Mn loading amount from 0% to 50%.10 114. 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.75 29. 3b). Adsorption experiment was carried out to investigate the potential application of the as-prepared MOLBC in the removal of Pb2+ .87 2. which is favorable for the removal of Pb2+ from aqueous solution. MnOx nanoparticles could be successfully loaded onto biochar.3 91. 3a). All of these results demonstrate that the as-prepared MOLBC possess rich hydrophilic groups on the surface.18 nm (Fig. then decreased with the further increase of Mn loading amount (Table 2).93 Table 2 Textural characteristics of blank biochar and MOLBC.Faheem et al.96 28. The two bands appearing at 1620 and 1400 cm−1 correspond to the C=C and C=O stretching vibration.20 ± 1.7 301.

respectively. . Generally. % =  (3) qe. 4a). including exchange and sharing of valence electrons. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 Fig. the best fit kinetic model can be verified through sum of squared errors (SSE) analysis. In general.316 Faheem et al. Mn loading to 50%. For 50%MOLBC. 3. It was probably due to more active site available on the surface of 40%MOLBC as compared to blank biochar. and Eq. 2. FTIR spectra of blank biochar and 40%MOLBC (b). after that saturation phase dominated and finally equilibrium stage reached within 80 min (Fig. 3. (3) shows the linear trend for pseudo-second order kinetics model. Fig.2. 40%MOLBC was chosen for further investigation. 1 1 1 = + qe qmax qmax KLCe 2 (4) where k is referred to pseudo-second order rate constant. In our experiment. 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. (4) shows the calculation of sum of squared errors (SSE): t 1 t = + qt qe kqe 2  SSE. lower adsorption efficiency could be attributed to excess loading of MnOx nanoparticles. the low value of SSE also indicated a better fitness of pseudo-second order kinetics (Table 3). Adsorption performance of MnOx-loaded biochar towards Pb2+ Pseudo-second order kinetics models was implemented to confirm their fitness with the adsorption data obtained experimentally for Pb2+ removal by blank biochar and modified biochar. respectively. The adsorption data revealed that a rapid initial sorption phase was observed in the first 15 min.3 times lower than that of blank biochar. as compared to pseudo-first order kinetics model and intra-particle diffusion model. which resulted in the decrease of surface area and pore size. 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 ). the k value for 40%MOLBC was 6. XPS wide scan of blank biochar and 40%MOLBC (a). The higher value of R2 along with lower SSE value often indicates better fitness of model to be applied. confirming that sorption rate of 40%MOLBC was much higher than that of blank biochar (Table 3). Pore size and BET surface area relationship (a). 4b). These results implied that adsorption of Pb2+ onto 40% MOLBC were mainly controlled by chemisorption. a small k value indicates a higher sorption rate [18]. XPS showing Mn2p core level in blank biochar and 40%MOLBC (b). The Eq. qe and qt are adsorbent sorption capacity (mg g-1 ) at equilibria and time t. In addition. Besides the value of coefficient R2 .cal N values such as qe and k were deduced from the slope and intercept of straight line plot between t/qt and t. adsorption isotherms are applied to describe the phenomenon controlling the release or movement of adsorbate from liquid to solid media. The high R2 for Pb2+ adsorption data and slightly difference between qe (cal) and qe (exp) indicated that Pb2+ adsorption data was best fitted to pseudo-second order kinetics model (Fig. N represents number of data points.exp − qe. Therefore.

The slope (1/n) and intercept (LogKf ) of the plot between logqe and logCe gives us the numerical value of n and Kf .999 0. as indicated by the high R2 of Langmuir (Table 3 and Fig. respectively.107 0. In addition. Langmuir isotherm is valid if adsorption mechanism is only limited to formation of monolayer between adsorbent and adsorbate due to finite number of identical sites present on adsorbent surface.65 ± 0. 40%MOLBC exhibited qmax as high as 86.9 mg g-1 and 47.. 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. as indicated by the R2 lower than 0. indicating that the adsorption mechanism involved was only limited to formation of monolayer.568 0.988 9. 4c). Furthermore. According to Langmuir model. while 1/n is related to adsorption strength. adsorption process are commonly described by Freundlich isotherm model [19]. which was almost five times larger than that of blank biochar. qe increased with the increase of C0 up to 235 mg g−1 and then became constant (Fig. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 317 Fig.15 0.7 0. which was comparable with that of the blank biochar obtained in this study [3. in case of nonimitative and reversible adsorption over heterogeneous surface.7 mg g-1 . Effect of initial Pb2+ concentration on qe was also studied for both 40%MOLBC and blank biochar. For 40%MOLBC.004 0.5 0.029 1. respectively. respectively [10]. 4.Faheem et al. adsorption capacity of 40%MOLBC for Pb2+ removal was compared with other adsorbents cited in literatures.16 0. The parameters such as KL and qmax were yielded from intercept and slope of the plot 1/Ce versus 1/qe . Table 3 Pseudo-second order kinetics and Langmuir isotherm model for Pb2+ adsorption on blank biochar and 40%MOLBC at 25 °C. Pb2+ sorption by 40%MOLBC (a) and pseudo-second-order model fitting (b).14].0 0 0 0. 4d). Bagasse biochar and rice husk ash had exhibited the maximum capacity of 21.1 mg g-1 . Pb2+ adsorption by both blank biochar and 40%MOLBC could not be well described by Freundlich isotherm model.5 mg g-1 at room temperature. i.0 and 12. The constant Kf is related to adsorption capacity. qe for 40%MOLBC at different initial Pb2+ concentrations (c) and Langmuir isotherm fitting (d).e. . However. 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 mg−1 ) R2 60. as shown in Table 4.69 ± 0.4 mg/g.166 14.174 86. which showed different sorption capacities of 4. which was only 14.91 9.9. Pb2+ adsorption by both blank biochar and 40%MOLBC could be well described by Langmuir. pyrolyzation in the presence of MnCl2 (MPB) and impregnation with birnessite via precipitation following pyrolysis (BPB). MnOx loaded pine wood biochar was synthesized by two different modification methods.97 60.983 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.

0 eV was observed in Fig.5 14.923 0. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 Table 4 Comparison of maximum adsorption capacities for Pb2+ by various adsorbents. which was reflected by solution pH reduction. respectively [20. After modification by manganese oxide. 291. The Pb2+ adsorption took place due to elimination of H+ through -COOH. The adsorption capacity of 40%MOLBC for Pb2+ removal was as high as 86. with the adsorption capacity of modified adsorbent as high as 99.7 0.7/1700 – 0.9 eV and 294. 3.3. These results are the evidence of interconnected building complexes formation with oxygen containing functional groups available on composite adsorbent surface [24]. 5a. Similar results were observed for the biochar pretreated with H2 O2 .318 Faheem et al. Three peaks were observed at about 288 eV. XPS wide scan of 40%MOLBC: C1s (a). The detail spectra of C1s before and after Pb2+ adsorption is presented in Fig.9 eV and 294. which was much higher than that of the reported biochar based adsorbent. 5). This indicates a preoccupation or fixation of lead onto .5 5 5 288 295 289 298 295 298 298 [3] [14] [20] [21] [10] This work This work Fig.999 0. O1s configuration after Pb(II) adsorption (d). 5b.970 – 0.0 mg g-1 and 31.988 0. Possible mechanism involved in Pb2+ removal by MOLBC In order to elucidate the adsorption mechanism. -OH and ≡SiOH functional groups into aqueous solution.5 mg g-1 .1/50 – 5 4 – 5. After adsorption of Pb2+ on 40%MOLBC surface. which is reported to be related with PbO formation [25]. respectively [22].9 mg g-1 . π -π ∗ transition and π -electron existence. C=O and pyran-like ether groups in the vicinity of biochar graphene disordered basal plane).1 86. 291. the peak at electron binding energy of 138.π interaction to some extent and favor the formation of inner surface complexes of Pb2+ due to deprotonation of carboxylic acid functionalities.1/50 0.5 eV.0 99. respectively. XPS analysis were performed for both blank biochar and 40%MOLBC (Fig.4 21. Incorporation of oxygen functionality such as carboxyl group on biochar surface often causes the decrease of electron density from π -band of graphenic nature carbon available in biochar. Adsorbent Rice Husk Bagasse Biochar Modified Diatomite Modified Bentonite Modified Wood Bicohar 40%MOLBC Blank Biochar Experimental conditions qmax (mg g-1 ) R2 Dosage (g mL-1 ) pH T (K) Ref 12. no peaks were observed at 288 eV. whose cation exchange capacity increased with the increase of H2 O2 dosage [23]. which can be assigned to minor contribution of ketone functionality.21].996 0.5 eV before adsorption. 40%MOLBC spectra after Pb(II) interaction (b). electron density reduction in π -bond aromatic moieties due to the addition of -COOH and delocalized π -electron cloud system with Pb2+ ions. It may affect the cation.1/50 1. 5. demonstrating the high efficiency of MOLBC for heavy metal removal from wastewater. which confirmed the interaction of ketones (or lactone like.0 31.9 47. the adsorption capacity of diatomite and bentonite could be significantly improved.05/20 0.983 – 0. + P b2+ + 2(≡ SiOH ) ↔ P b(≡ SiO )+ 2 + 2H 2(−COOH ) + P b 2+ → (−COO )2 P b + 2H + In addition. O1s configuration before Pb(II) adsorption (c).

A quantitative method for analyzing the dispersion and agglomeration of nano-particles in composite materials. In comparison to the blank biochar. Adsorption of Pb (II) from aqueous solution using new adsorbents prepared from agricultural waste: Adsorption isotherm and kinetic studies. 40%MOLBC exhibited almost five times higher References [1] Zhang H. Zhao X. [23] Huff MD. Preparation of activated carbons from raw and biotreated agricultural residues for removal of volatile organic compounds. [6] Mahmoud AM. Huang X. Jiang H. Yang Y. This research is financed by Fundamental Research Funds for Jiangsu Province Biomass Energy and Materials Laboratory (No. Yu H-Q. Dong X. J Environ Manage 2016. [24] Lu H. Zhu L. Wang Z. the remarkable area ratio changes were found in case of peaks appeared at 531. Adsorption of lead and mercury by rice husk ash. Conclusion The present work focused on the adsorption performance improvement and possible removal mechanism of Pb2+ by MOLBC. Sharma AK. this could be assigned to M-O decreased from 56. Lv L. Sheng G. Chemosphere 2014.165:17–21. Upgrading the rice husk char obtained by flash pyrolysis for the production of amorphous silica and high quality activated carbon. which was mainly made of disordered graphitic crystallites. respectively. Chem Eng J 2012. Gao B. Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions. . (Biochar basic nature) ≡ C : H3 O+ + P bOH + →≡ C : P bOH + + H3 O+ Acknowledgments (pH reduction) Moreover. Tutunji M. Ghasemi N. Sugita S. Mosa A. Yang J. ethanol and amorphous superfine silica. Adsorbent-adsorbate interactions in the adsorption of Cd (II) and Hg (II) on ozonized activated carbons. 5c). Kim S-J.46:854–62. Grasley Z.105:68–74.67:4471–87. Hochella MF. Gong F. Olazar M.8% to 21. Ma Y.137:384–95. Naushad M.115:12251–85.4ev imputed to C-OH and M-OH. [21] Eren E. Inyang M. ultrasonically chemical treatment with KMnO4 and further heat treatment of biochar caused vacancy defects generation in biochar graphenic basal plane. Chem Rev 2015.2ev (Fig.211:317–31. Pan B.4 eV and 532. Zhang W. With the increase of pyrolysis temperature. By contrast. Removal of copper (II) and lead (II) from aqueous solution by manganese oxide coated sand: I.1 eV. JSBEM201408) and Fundamental Research Funds for the Central Universities (No. Water Res 2012. C=O and pyran-like ether groups available at vacancy defect as well as cation. Sorption of lead ions on diatomite and manganese oxides modified diatomite. Relative distribution of Pb2+ sorption mechanisms by sludge-derived biochar. Horng RS. [11] Wang M.Faheem et al. Water Res 2006. A new method of utilizing rice husk: Consecutively preparing d-xylose.40:754–9. [4] Liu W-J. [19] Ghasemi M. Finally these active sites serve as a Lewis base or electron-pair donor and Pb2+ act as Lewis acid or electron-pair acceptor. Zhang Z. Al-Rub RKA. Chem Eng J 2014. Highest occupied molecular orbital (HOMO) of unsaturated system such as hexagonal rings of aromatic compounds and C-C triple bond was mainly composed of π -electron. Lee S-K. Zhang W. Rivera-Utrilla J. 30916011312).36:3850–4. Zimmerman AR.7% after Pb2+ adsorption. Su F. The π -clouds system. [5] Hua M. et al.3% to 28. [14] Ding W. A novel manganese-oxide/biochar composite for efficient removal of lead (II) from aqueous solutions.278:1–8. The enhanced Pb2+ adsorption by MOLBC was attributed to the loaded manganese oxide nanoparticles onto biochar. Shi J. Moreover. et al. Amutio M. Pyrolytic temperatures impact lead sorption mechanisms by bagasse biochars. Yao Y. a monodentate surface complex embedded one additional -OH group on adsorbent surface as compared to bidentate and mutidentate surface complexes [26]. [9] Han R. J Air Waste Manage 2011.33%) was observed for the peak at 533. It is cleared from proposed complicated adsorption mechanism conceptual model. Manganese-oxide-coated alumina: a promising sorbent for defluoridation of water. [16] Lee H. Park Y-K. Lopez G. J Hazard Mater 2012. Pan T-A. Synthesis of porous MgO-biochar nanocomposites for removal of phosphate and nitrate from aqueous solutions. Egypt J Petrol 2015. Lian F. Shoya M. Removal of lead ions by Unye (Turkey) bentonite in iron and magnesium oxide-coated forms. Heavy metal removal from water/wastewater by nanosized metal oxides: a review. Int J Environ Sci Technol 2015. Khraisheh M. [20] Al-Degs Y. [3] Feng Q. Ibrahim FA. Adsorption of heavy metal ion from aqueous solution by nickel oxide nano catalyst prepared by different methods. Lead sorption efficiencies of natural and synthetic Mn and Fe-oxides.40:3497–506. bidentate binuclear and multidentate during Pb2+ adsorption. Philip L. This was due to formation of relatively more monodentate complexes than bidentate mononuclear. Li Y.π interaction could also be considered as a key factor because of carbon atom graphenic properties of the MOLBC. The literature data revealed that graphene sheets of plantderived biochars at high temperature also possessed an abundance of π -electron. [2] Alvarez J. ≡ C : +P b2+ →≡ C : P b2+ (Cπ -cation interaction) Moreover. Bioresource Technol 2015. the amorphous characteristics of biochar structure gradually converted into a turbostratic char material. Xing B. for the peak at 530. In present study.242:36–42. Zhang S. [22] Sanchez-Polo M. Water Res 2001. 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. Gao B.9% and 41. Chen X. cation-π clouds involvement was noncovalent bonding or electrostatic interaction in between monopole (Pb2+ ) and quadrpole (π -system) benzene rings associated with existing graphene sheets of biochar [28]. J Hazard Mater 2006.291:27–35. / Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 40%MOLBC surface during the process as well as choking or intercalation into loaded MnOx surface. Moreover.20:2193–9.210:26–32. Ma LQ. Biochar-surface oxygenation with hydrogen peroxide. Zou W. Qiu R. Synthesis and characterization of a novel MnOx-loaded biochar and its adsorption properties for Cu2+ in aqueous solution. vacancy defect of biochar graphenic basal plane and π -π ∗ transition (electron density reduction in π -bond aromatic moieties due to addition of -COOH) was also intended as adsorption controlling factors. [17] Hsi H-C. Yazdanbakhsh A. Appl Surf Sci 2014. Gao B. the peak area for C-OH and M-OH increased from 14. Geochim Cosmochim Acta 2003. Youssef NA.170:132–7. Ren Y. characterization. respectively (Fig. surface -OH groups involved as bridging with the metal centers to form dentate complexes. Park SH. Bioresour Technol 2014. Environ Sci Technol 2002. [15] Li S. [10] Wang S. Wang S. Synthesis of manganese oxide/activated carbon composites for supercapacitor application using a liquid phase plasma reduction system.181:13–17. Qiu W. demonstrating that chemisorbed H2 O was also participated in the adsorption up to limited extent due to increase in biochar hydrophilic nature.35:3724–8.42:1395–403. J Hazard Mater 2015.165:63–70. organosolv lignin. Compos Part B Eng 2011. Manganese oxide– modified biochars: Preparation. Kim B-J. Development of Biochar-based functional materials: toward a sustainable platform carbon material.291:65–73. Lin Q.317:724–9. and sorption of arsenate and lead. J Ind Eng Chem 2014. [13] Song Z. −C π + 2H2 O  −C π − H3 O+ + OH − 319 adsorption capacity than blank biochar. Pb2+ adsorption by lactone like. the minor area ratio change (6. 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]. high adsorption capacity for Pb2+ was observed for MOLBC. Ding X. [12] O’Reilly SE. Qiu Y. 4. [18] Maliyekkal SM. J Colloid Interface Sci 2004. Yu Z. [7] Tyson BM. Qin G.98%. Li D. Characterization and kinetic study. Xue Y.24% and 22. Ime IM. Similar trend was observed when vacancy defect was induced into prepared graphene sheet after thermal treatment [27]. Shaban SA.12:1719–26. An K-H.61:543–51. Int J Hydrogen Energ 2015. Ma LQ. After Pb2+ adsorption. Lee JW. Bilbao J. Khosravi-Fard Y. [8] Zhang M. These results were well in agreement with literature study in which unsaturated and aromatic system of commercial activated carbon causes Pb2+ -π cloud bonding [29]. Zhang Q. 5d).64%7. After Pb2+ adsorption. J Hazard Mater 2009.

/ Journal of the Taiwan Institute of Chemical Engineers 66 (2016) 313–320 [25] Taty-Costodes VC. Li N.105:121–42. Biniak S. Environ Sci Technol 2014. by adsorption onto sawdust of Pinus sylvestris. et al. Sato Y. from aqueous solutions. Carbon 2014. [29] Swiatkowski A. Gao J. Kleber M.75:81–94. Delacroix A. Uchizawa S. Carbon 2004. Porte C. . Walczyk M. Mater Chem Phys 2012. Pakula M.320 Faheem et al. Wen Q. et al. Zhou D. Dionysiou DD.48:1902–10.136:538–44.43:3421–9. [30] Fang G. Hirose-Takai K. Liu C. Adsorption mechanism of copper and lead ions onto graphene nanosheet/δ -MnO2 . [28] Keiluweit M. [26] Ren Y.42:3057–69. Fauduet H. [27] Yamada Y. Suzuki Y. J Hazard Mater 2003. Functionalized graphene sheets coordinating metal cations. Wang Y. Key role of persistent free radicals in hydrogen peroxide activation by biochar: implications to organic contaminant degradation. Removal of Cd (II) and Pb (II) ions. Influence of the surface chemistry of modified activated carbon on its electrochemical behaviour in the presence of lead (II) ions. Environ Sci Technol 2009. Molecular-level interactions in soils and sediments: the role of aromatic π -systems. Yan N. Yasuda H. Feng J. Ma J.