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Chemical Engineering Journal 225 (2013) 5967

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Chemical Engineering Journal


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

Pleurotus ostreatus nanoparticles as a new nano-biosorbent for removal


of Mn(II) from aqueous solution
Lan Ma a, Yuhong Peng b, Bo Wu a, Daiyin Lei a, Heng Xu a,
a
b

Key Laboratory of Bio-resources and Eco-environment (Ministry of Education), College of Life Science, Sichuan University, Chengdu, Sichuan 610064, PR China
Yaan Vacational College, Yaan 625000, PR China

h i g h l i g h t s
 Pleurotus ostreatus was fabricated into nanoparticles by high-energy nano-impact grinding.
 P. ostreatus nanoparticles as a new nano-bisorbent for removal of Mn(II).
 The size distribution of PONP measured by small angle X-ray scattering.
 SEM, EDS and FTIR spectra were used to characterize the nano-biosorbent.
 The maximum Mn(II) adsorption capacity of PONP is higher than many other adsorbents.

a r t i c l e

i n f o

Article history:
Received 9 December 2012
Received in revised form 5 March 2013
Accepted 7 March 2013
Available online 16 March 2013
Keywords:
Pleurotus ostreatus
Nanoparticles
Nano-biosorbent
Mn(II)
Adsorption kinetic
Adsorption isotherm model

a b s t r a c t
The objective of this study was to investigate the use of Pleurotus ostreatus (P. ostreatus) nano-particles
(PONP) as a new nano-biosorbent to remove Mn(II) from aqueous solution. Scanning Electron Microscope
(SEM), Energy Dispersive Spectrometry (EDS), Fourier Transform Infrared Spectrometry (FTIR spectra),
Small-angle X-ray Scattering (SAXS) were used to characterize the nano-biosorbent. Adsorption experiments were carried out by batch experiments to investigate the effects of different experiment parameters including pH of the solution, adsorbent dose, initial Mn(II) ion concentration and contact time on
adsorption capacity of PONP. The adsorption equilibrium study exhibited that Mn(II) adsorption of PONP
was better tted by Langmuir isotherm model. The maximum Mn(II) adsorption capacity of PONP was
130.625 mg/g at 298.15 K, which was higher than many other adsorbents. Pseudo-second-order kinetic
model was the best one to predict the sorption kinetics with a maximum adsorption capacity of PONP
attained within 30 min. PONP showed great potential in wastewater treatment due to the high adsorption capacity.
Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.

1. Introduction
Nanotechnology, as a novel method, has become one of the
most popular technologies for the removal of metal cations from
aqueous solution over the past few decades. Nano-particles mainly
including nano-sized inorganic material derived from metals and
metal oxides (i.e., silver nano-particles, TiO2, SiO2, Al2O3 and ZnO,
Fe3O4 magnetic nano-particles), carbon nanotube and synthetic
nano particles (i.e., synthetic nanostructured Fe(III)Cr(III) mixed
oxide [1]) have been applied widely as adsorbents for the treatment of metal cations efuents. The advantages of various types
of nano-particles adsorbents are tiny in particulate diameter, large
external surface area, high density of reactive surface sites and
great intrinsic reactivity of surface sites and small internal diffusion resistance [2]. However, these nano-adsorbents have many
Corresponding author. Tel.: +86 28 85414644; fax: +86 28 85418262.
E-mail address: xuheng64@sina.com (H. Xu).

obvious shortcomings such as high preparation cost, strict operational conditions, high energy consumption. These shortcomings
which may restrict application areas of nano-particles adsorbents
in wastewater treatment already became a serious problem cannot
be ignored. Fortunately, a number of naturally available, low-cost
and effective adsorbents including activated olive bagasse [3],
Chitosan [4], Dehydrated peanut hull [5], Cedar sawdust [6] and
some types of edible mushrooms (such as Pleurotus platypus [7],
Lentinus sajor-caju [8]) have been successfully employed as adsorbents for removing various kinds of metal cations and dyes from
waste water in recent years. Pleurotus ostreatus is a normal edible
mushroom, which is extensively cultivated in South China. Because
of wide source of raw materials and technological innovation,
PONP combine the merits of nano-particles adsorbents and lowcost adsorbents. It retains high surface-area-to-volume ratio and
low capital and operational costs.
It is worthwhile to note that adsorbent particle size has a significantly effect on water pollutants removal in previous researches.

1385-8947/$ - see front matter Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.03.044

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L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

Investigators [913] found that adsorption capacity of heavy metals or dyes increased with the decrease in adsorbent particle size.
Tian et al. [9] studied spent Tricholoma lobayense for removal of
Congo Red (CR) from aqueous solution. The CR removal percentages increased from 81.27% to 92.75% when the particle size of
adsorbent decreased from 60 mesh to 200 mesh. They came to
the conclusion that both removal ratio of CR and adsorption capacity increased with the decrease in adsorbent particle size. Liu et al.
[10] used ammonium citrate modied spent Lentinus edodes as
adsorbent to remove Pb(II) from aqueous solution. Particle size of
adsorbent was proved by PlacketBurman design that it had a
positive effect on Pb(II) removal. Gupta et al. [11] studied on the
removal of Cr(VI) from aqueous solution using carbon slurry and
found that the adsorption capacity increased with the decreasing
of particle size of the adsorbent. Chen et al. [12] applied L. edodes
to the bioremediation of chromate contaminated water. Three
sizes of the biosorbent, 2 mm, 1 mm and 450 lm, were used in
100 mg/L Cr(VI) for adsorption. Total removal of Cr(VI) achieved
was the highest at 450 lm among these three sizes.
Albadarin et al. [13] removed chromium ions from aqueous solution using raw dolomite. Experiments were performed using different particle sizes of the adsorbent (0.1802.0 mm). Results specied
that the amount of Cr(VI) adsorbed onto dolomite decreases with an
increase in the particle size of the adsorbent. These results of such
studies can demonstrate that the adsorption capacity of adsorbent
particle may be enhanced by reducing the size of particle. But very
few literatures are available on metal ions removal using nanoparticles biosorbent.
Toxic metals contamination of the environment such as copper,
lead, cadmium, nickel, mercury, manganese is a severe global environmental issues. It has long been known that Mn is one of the
most widely used metals in the world and one of the important
indexes of the water pollutants. As an essential element for
humans, animals and plants, Mn is required for their growth,
development, and maintenance of health. But excess manganese
is detrimental to health. In China, the maximum recommended level of Mn(II) in drinking water is 0.1 mg/L as well as the provisions
of World Health Organization. Overdose exposure to Mn(II) in the
environment may result in the occurrence of manganese poisoning, which can adversely affect human body system such as nervous system, immune system and reproductive system. Chronic
inhalation of high levels of Mn can induce a neurodegenerative disorder, Parkinson, lung embolism and bronchitis [14].
To our knowledge, no similar report about nano-size mushroom
applied to waste water treatment is available up to now. Furthermore, our study was the rst one in which P. ostreatus was fabricated
into nanoparticles by high-energy nano-impact grinding (HENIG).
HENIG as a closed high-energy milling machine and through the
quick multidimensional swing motion of its tank, is able to make
the irregular motion of milling medium in the tank. The motion
can generate a tremendous impact force with increased impact
times, prolong the motion trace, augment the impact energy and lessen the impact blind spots. Its working efciency increased several
dozen times over the traditional ball millers. The particles of broken
substance processed by HENIG reach nano-grade. Because HENIG
are high-energy millers, mushroom nes are easy to be cooked
and carbonized in the quickly increasing temperature in the machines. To solve the problem, cycling water cooling in a jacket of
the tank are adopted to effectively control the temperature during
the processing. Numerous kinds of mushroom contain too much sugar or oil or colloid that might stick onto the balls and the tank or palletized in the ball miller, which reduce the milling effect. The humid
milling method have solved the problem of stickiness. To improve
milling effect, mushroom are crashed and water is added to form
specied size, and then made with ball miller into nano-size, nally
dried with spray after having reached milling effect.

First, material crushed with traditional method, second, crushed


with air ow, nally, the micro-grade materials are prepared into
nano-nes with high-energy ball milling. From the above steps,
machining time are shortened and decreased the pollution. Controlled in the rst two steps (crush, screen, crush with air ow
and screen again), the evenness can be achieved as expected.
Therefore, the main objective of this study was to investigate
the potential of the nanoparticles biosorbent as low-cost adsorbent
in the removal of the Mn(II) from aqueous solutions. In this research, PONP prepared by HENIG was characterized and used as
an adsorbent to remove Mn(II) from aqueous solution. The adsorption of Mn(II) ions onto PONP was studied in batch equilibrium
experiments conditions. The work investigates the effect of different parameters including pH, initial Mn(II) concentration,
adsorbent dose on Mn(II) adsorption. Adsorption isotherms and
kinetics models were conducted to describe the experimental data
and understand the adsorption mechanism.
2. Materials and methods
2.1. Reagents and adsorbate
All chemical reagent of analytical grade were purchased from
Kelong Chemical Reagent Factory, Cheng du, Sichuan province, China. Deionized water was always used in the experiments. A stock
aqueous solution of Mn(II) of 1000 mg/L was prepared by dissolving 3.6024 g manganese chloride tetrahydrate (MnCl24H2O) in 1 L
deionized water. MnCl24H2O with purity 99.99% has a molecular
weight of 197.91 g/mol. Diluting the stock solution to get the
required concentration of the Mn(II). Before adding adsorbent,
pH of Mn(II) solution were adjusted to desired values by adding
volume-negligible HNO3 (0.01 M, 0.1 M, 1 M) or NaOH (0.01 M,
0.1 M, 1 M). The pH value was measured by a pH meter (Model
pHS-25, calibrated with buffers of pH 4.00, 6.86 and 9.18). The concentration of Mn(II) ion in solutions was analyzed by ame Atomic
Absorption Spectrometer (AAS; VARIAN, SpectrAA-220Fs).
2.2. Preparation and characterization of nano-biosorbent
Fresh P. ostreatus which was obtained from a mushroom production base in the suburbs of Chengdu, Sichuan Province, China,
was washed with deionized water and later dried in an oven at
328.15 K. Then the dried P. ostreatus grounded into powder using
a pulverizing mill (Joyoung, JYL-350B) to obtain raw biomass for
further use. The dried P. ostreatus particle were dropped into the
HENIG (Taijihuan, CJM-SY-A) with 373.15 K drying 2 h and 10 h
of continuous milling. The small particles reach to a certain extent
will trigger oxidation which is caused by increased surface areas,
and then the phenomena of explosion will emerge. So nitrogen
was added to reaction vessels when the material in the process
of grinding to prevent oxidation and spontaneous combustion.
The FTIR spectra analysis of the nano-biosorbent used in this study
was characterized with a FTIR (NEXUS-650, America).
In order to directly observe the surface morphology of the nanobiosorbent, SEM (JSM-5900LV, Japan) was employed in this study.
For analyzing the elemental constitute of metal-free and metalloaded of PONP, as well as further conrming the identity of metal
ions onto PONP, EDS (JSM-5900LV, Japan) was used. The size distribution of PONP measured by small angle X-ray scattering (SAXS)
(MAX-2500, Japan).
2.3. Batch adsorption studies
To study important factors, all the experiments were performed
in 150 ml conical asks containing 50 ml solution in each ask at

L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

298.15 K on a constant temperature breeding shaker (SUKUN, SKY211B) with a shaking of 150 rpm.
The effects of pH (from 2 to 7, initial Mn(II) concentration
100 mg/L, adsorbent dose 0.4 g/L), initial Mn(II) concentration
(from 50 mg/L to 200 mg/L, pH 6, adsorbent dose 0.4 g/L) and
adsorbent dose (from 0.4 g/L to 14 g/L, pH 6, initial Mn(II) concentration 200 mg/L) were investigated by varying any one of the process parameters and keeping the other parameters constant. After
adsorption, suspension was centrifuged for 2 min at the speed of
3500 rpm in a low speed centrifuge (ZONKIA, SC-3610).The supernatant was diluted in order to achieve measuring range of AAS. The
Mn(II) adsorption capacity (qe)was calculated as follows:

qe mg=g

C0  Ct
M

The adsorption isotherms were studied by varying the concentration of Mn(II) solutions ranging from 50 to 200 mg/L at pH 6
with a known amount of adsorbent (0.4 g) and four different temperatures (278.15 K, 283.15 K, 293.15 K and 303.15 K), respectively. Three isotherm models, Langmuir, Freundlich and Temkin
isotherm model, were employed to explore the adsorption
mechanism.
The linear equation of Langmuir isotherm model [15] is expressed as follows:

where Ce represents the equilibrium concentration of the heavy metal ion in the solution (mg/L), qe represents the amount of metal ion
uptaken per unit mass of the biomass at equilibrium (mg/g). The value of Q represents the maximum amount of metal ion uptaken per
unit mass of the biomass (mg/g), b is the Langmuir constant related
to the energy of adsorption (L/mg). The values of Q and b can be
determined from the slope and intercept of the linear plot of Ce/qe
versus Ce, respectively.
To predict whether an adsorption system is favorable or unfavorable, the dimensionless separation factor of equilibrium parameter RL which dened by Webi and Chakravort [16] is calculated
using the following equation:

where C0 (mg/L) is the initial concentration of Mn(II) ions. The value


of RL indicates the type of the isotherm to be either unfavorable
(RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0).
The Freundlich linear equation [17] is written as follows:

ln qe  ln K f

1
ln C e
n

RT

qe

lnK T C e

RT
b

Eq. (5) can be expressed in its linear form as:

2.4. Adsorption isotherms

1
RL
1 bC 0

of adsorption or surface heterogeneity (g/L). The values of Kf and n


can be determined from the slope and intercept of the linear plot of
lnqe versus lnCe, respectively.
And linear form of Temkin isotherm [18] has been used in the
form as follows:

where C0 is initially concentrations (mg/L) of Mn(II), Ct is the Mn(II)


concentration (mg/L) at a given time t. M is the weight of adsorbent
(g/L).
All design experiments were repeated three times and the result was showed by calculation of average. Standard deviation
was under 2%. Besides, for each experiment, two controls were designed. One of the control groups, containing 50 mL of Mn(II) solution without adsorbent, was shaken simultaneously to determine
whether there was any adsorption on the walls of the conical
asks. The other control group with only 0.1 g of adsorbent in
50 ml of deionized water was shaken to check out if there was
any leaching of Mn(II) from the adsorbent.

Ce
1
Ce

qe Qb Q

61

where Kf is the Freundlich constant related to the adsorption capacity (mg/g), and n is the Freundlich exponent related to the intensity

qe B ln K T B ln C e

where B is Temkin isotherm constant related to heat of sorption and


KT (L/mg) is Tempkin isotherm energy constant; R is the universal
gas constant (8.314 J/mol K) and T (K) is the absolute temperature.
A linear plot of qe versus lnCe can determine the isotherm constants
B and KT from the slope and the intercept, respectively.

2.5. Adsorption kinetics


To estimate the time which is necessary to reach the sorption
equilibrium, kinetic studies of Mn(II) adsorption by the nano-biosorbent were conducted. The experiments were performed by adding 0.02 g of the adsorbent over 50 ml of a solution that contained
200 mg/L of Mn(II). The experiments were carried out under conditions of pH 6 and 298.15 K. 10 mL of solution was collected, ltered
and analyzed for Mn(II) at certain time intervals. In order to investigate the adsorption kinetic pattern, pseudo-rst order, pseudosecond order, Intra-particle diffusion model and Elovich model
were employed to t to the experimental data.
The linear form of Pseudo-rst-order kinetic model [19] can be
described as follows:

lnqe  qt ln qe  k1 t

where qt is the amounts of Mn(II) adsorbed (mg/g) at time t (min),


respectively. k1 is the pseudo-rst-order rate constant (min1) for
the adsorption process.
The mathematical expression of Pseudo-second-order kinetic
model [20] is as follows:

t
1
t

qt k2 q2e qe

where k2 (g mg1 min1) is the rate constant of the pseudo secondorder adsorption.
Intra-particle diffusion model [21] is expressed as follows:

qt kid t1=2 C

10

where kid is the intra-particle diffusion rate constant (mg g1 min)
and C is the lm thickness.
Elovich model [22] is also used to model the adsorption data,
which is described as follows:

Qt

1
1
lnxy ln t
y
y

11

where x (mg g1 min1) represents the initial rate of adsorption, y


(g/mg) represents the desorption constant.

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L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

3. Results and discussion


3.1. Characterization of biosorbent
3.1.1. SEMEDS
According to SEM micrograph of PONP, particles of P. ostreatus
processed through HENIG were spherical or approximately spherical. The result of SEM was showed in Fig. 1. It indicated that the
surface of PONP was not smooth. EDS of PONP before and after
adsorption with Mn(II) ions were showed in Figs. 2a and 2b. The
EDS pattern (Fig. 2a) for the pristine PONP showed that characteristic signals for carbon, potassium and oxygen. The presence of
peaks of manganese and chloride appeared after adsorption conrmed that Mn(II) was adsorbed on the surface of PONP.
3.1.2. SAXS
SAXS is a kind of X-ray scattering techniques that are used in
the characterization of materials. The data measured by SAXS can
provide information on the particle size distribution. Fig. 3 showed
that density distribution of PONP paticle size. The size of PONP are
under 300 nm. The particle size of 118 nm accounts for about
0.4% of the total. The particle size of 1896 nm, 1200 nm account
for about 5.1%, 16.1% of the total, respectively. The rest comprise
83.87% of all particle. The mean size of the nanoparticles measured
by SAXS was 229 nm.
3.1.3. FTIR spectra
FTIR spectra analysis is a useful tool to elucidate the characteristic functional groups of adsorbents, which are capable of adsorbing metal cations. Fig. 4 showed the FTIR absorption spectra of
PONP and Mn(II)-loaded PONP.
The remaining band near 3384 cm1 belongs to OH stretching
of carboxylic groups and stretching of NH groups. The peak is
wide because the polarity of hydroxyl groups is strong (3400
2500 cm1) [23]. The peaks appeared in the spectra at wave number 2927 cm1 due to the asymmetric stretch of alkane (CH) [24].
The strong absorption band around 1652 cm1 belonging to the
stretching vibration of COO. Besides, absorption bands at
1045 cm1 represent the stretching of COH, which is a characteristic peak of the polysaccharides [25]. This also implied that polysaccharides which were constituent parts of PONP play an
important role in the process of adsorption [26].
Comparison of the FTIR spectra of samples of the PONP and
Mn(II)-loaded PONP revealed that a strong characteristic bending
vibration and stretching vibration adsorption band for alcoholic
hydroxyl group(COH) at 1400 cm1 and 1045 cm1 were present
in the FTIR spectrum of the PONP [10]. The peak at 578 cm1 and
1241 cm1representing OCO scissoring and aromatic oxide
stretching vibration, respectively [27]. The absorption peak intensity of 3384, 1400, 2927, 1652, 1241, 1045 cm1 on the spectrum
of PONP before adsorption comparing with after adsorption
(3403, 1418, 2923, 1636, 1249, 1044 cm1) indicating that the
functional groups for Mn(II) binding on the PONP were hydroxide

Fig. 1. SEM of PONP sample.

(OH), alkane (CH), amide (NH2) and carboxyl (COOH). From


these ndings, it was proved that Mn(II) was adsorbed on functional groups of the PONP.
3.2. Batch adsorption studies
3.2.1. Effect of initial pH
pH has an important inuence on uptake of Mn(II) from aqueous solution by the nano-biosorbent. The pH value in the original
solution on the adsorption capacity removal of Mn(II) was showed
in Fig. 5. Manganese has an oxidation state between +2 and +4 under alkaline solution conditions [28]. It is demonstrated that the
suitable pH ranges for Mn(II) sorption should be performed below
7.
The sorption at the low pH took place with low adsorption
capacity. With the rise of pH (from 3 to 4), the adsorption capacity
showed an increasing rate (from 41.5032 mg/g to 53.0328 mg/g).
The results showed that the increase of pH from 4 to 7 had little
effect on the adsorption capacity of PONP. pH 6 is more close to
the pH value of Mn(II) solution before adding adsorbent. So pH 6
as experimental operating parameter is advantageous in reducing
the cost of adsorption process.
A possible mechanisms of adsorption of Mn(II) may be considered: at low pH, hundreds of billions of protons in solution that
competes with Mn(II) binding to the active sites such as carboxyl,
carbonyl, hydroxyl, and amino which were involved in metal binding [29]. With the increase of pH value, the number of protons was
obviously decreased which lead to a decrease in the competition
between proton and metal cations. It was ion exchange that played
the key function in the rising of adsorption ration when pH increased. Taking these results and theories into account, subsequent
experiments were carried out at pH equal to 6.
3.2.2. Effect of adsorbent dose
The adsorbent dose is one of the signicant parameters in
adsorption studies because it determines the capacity of adsorbent
for a given initial concentration of Mn(II) solution. The effect of
adsorbent dose on the Mn(II) adsorption capacity was showed in
Fig. 6. The adsorption capacity of PONP for removal of Mn(II) from
aqueous solution was found to decrease sharply with an increase
in adsorbent dosage. A possible reason for the change may attribute to that with the increase of adsorbent dosage, mutual occlusion was much more apt to occur on overlapped PONP, which
made it easy to block the combination Mn(II) with active sites of
PONP.
Considering the adsorption capacity, it can be concluded that
the optimal adsorbent dose was 0.4 g for the maximum adsorption
capacity of PONP from solution of 200 mg/L. Therefore, 0.4 g/L of
adsorbent was chosen for later studies on Mn(II) adsorption.
3.2.3. Effect of initial Mn(II) ion concentration and contact time on
adsorption capacity of PONP
The initial metal cations concentration and contact time were
evaluated as important factors in the wastewater treatment systems. Fig. 7 showed the effects of initial Mn(II) ion concentration
and contact time on the Mn(II) uptake on the PONP at 298.15 K.
It could be seen from the gure that the adsorption at Mn(II) concentrations with varying solution concentrations (50,100 and
200 mg/L) was rapid at the initial stages and then the adsorption
rate gradually decreased with the progress of adsorption until
the equilibrium reached in approximately 30 min. With increasing
of the initial concentration, the process of Mn(II) adsorption took
longer to reach equilibrium. The time of the adsorption equilibrium was found to be 20, 25, 30 min for initial Mn(II) ions concentration of 50, 100, 200 mg/L, respectively. This result could be
explained by the theory that a multitude of metal cations self

L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

63

Fig. 2a. EDS spectra of pristine PONP.

Fig. 2b. EDS spectra of Mn(II)-loaded PONP.

Fig. 4. FTIR spectra of PONP (b) and Mn(II)-loaded PONP (a).


Fig. 3. SAXS of PONP sample.

collision and competition for the active adsorption sites increased


that made metal cations take much longer to combine with adsorbent. This was in accordance with the ndings quoted by other
researchers [30,31].
The adsorption of PONP to Mn(II) was reached maximum
adsorption capacity so fast, which mean the efciency of the adsorbent in terms of usage in Mn(II)-containing wastewater treatment
application. The initial high adsorption rate may be due to a multitude of unoccupied binding sites available for Mn(II) uptake on
the surface of PONP. As a result, 30 min was xed as the equilibrium contact time. The slow rate of Mn(II) adsorption was probably
attributed to free binding sites that had been occupied and very

small uncovered surface. The adsorption capacity of PONP for


removal of Mn(II) from aqueous solution was found to increase
sharply with an increase in initial Mn(II) ion concentration. The
adsorption capacity of PONP increased from 39.3337 mg/g to
130.625 mg/g when the initial Mn(II) ion concentration increased
from 50 mg/L to 200 mg/L. When initial Mn(II) ion concentration
was low, the availability of various active sites and the uncovered
surface of PONP were relatively high. The higher initial Mn(II) ion
concentration, the more ions binding with adsorption sites of
PONP, thus resulting in a further increase in adsorption capacity
of PONP. The maximum Mn(II)adsorption capacity of PONP is
130.625 mg/g, which is signicantly superior to many other adsorbents such as lignite (25.84 mg/g) [28], clinoptilolite-Fe

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L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

oxide(27.12 mg/g) [32], pabeads SP70 resin (4.2 mg/g) [33], anular
activated carbon (2.54 mg/g) [34].
3.3. Adsorption isotherms

Fig. 5. Effect of pH on remove Mn(II) ions by PONP (adsorbent dose 1 g/L,


temperature 298.15 K, contact time 180 min, initial concentration 200 mg/L).

The sorption isotherm is the relationship between equilibrium


concentration of metal ions in the liquid phase and equilibrium
concentration of metal ions in the adsorbent at constant temperature during the adsorption process, and it can be expressed by
various isotherm models. The inuence of Ce on the qe of PONP
was showed in Fig. 8a. In this study, three common and important
isotherm equations, Langmuir, Freundlich and Temkin isotherms
were used to evaluate the adsorption process. The parameters obtained from the three models described the nature of interacts
with adsorbents and provided some insights into the surface properties of the adsorbent and its afnity to PONP.
The optimal operating conditions were determined from the
experiment described above as pH 6, absorbent dosage was
0.4 g/L and contact time was 30 min. The experimental equilibrium
data for Mn(II) ions adsorption on PONP were gained at the best
conditions and four different temperatures (278.15 K, 283.15 K,
293.15 K, 303.15 K).
3.3.1. Langmuir adsorption isotherm
Langmuir adsorption isotherm is based on the assumption that
the sorption of metal ions has monolayer coverage on the surface
of the adsorbent with a nite number of identical sites. There is
no migration of adsorbed ionic can take place at that sites of adsorbate when the adsorption process reaches equilibrium [15]. The
Langmuir isotherms for the adsorption of Mn(II) on PONP at different temperatures were presented in Fig. 8b.
3.3.2. Freundlich adsorption isotherm
Freundlich adsorption isotherm applies to describe the heterogeneous surface energies by multilayer adsorption. The Freundlich
isotherms for the adsorption of Mn(II) on PONP at different temperatures were presented in Fig. 8c.

Fig. 6. Effect of adsorbent dose on adsorption of Mn(II) ions (pH 6, temperature


298.15 K, contact time 180 min, initial concentration 200 mg/L).

Fig. 7. Effect of contact time and initial concentration on adsorption of Mn(II)


ions(pH 6, temperature 298.15 K, contact time 250 min, adsorbent dose
0.4 g/L).

3.3.3. Temkin isotherm model


Temkin isotherm which takes into account the heat of adsorption of all the molecules in the layer would decrease linearly with
coverage due to some indirect between adsorbent and adsorbate
on adsorption isotherms [18]. Temkin isotherm for the adsorption

Fig. 8a. Adsorption isotherm of Mn(II) ions by PONP adsorption (pH 6, contact
time 30 min, adsorbent dose 0.4 g/L).

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L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

Fig. 8b. Langmuir isotherm polts for Mn(II) ions adsorption onto PONP.

Fig. 8c. Freundlich isotherm polts for Mn(II) ions adsorption onto PONP.

The Langmuir parameters (Q, b and RL), Freundlich parameters


(KF and n) and Temkin parameters (KT and B) for the adsorption isotherms were given in Table 1.
Among these three models, Langmuir isotherm with high R2
(0.98840.9992) was the most suitable equations to describe the
adsorption equilibrium of Mn(II) ions onto PONP at different temperature values at 278.15303.15 K. For initial concentration of
Mn(II) ions from 50 to 300 mg/L used in the present study, all
the RL values are less than 1 and greater than zero indicating favorable adsorption at the conditions being studied. The value of RL
decreased with increasing of Mn(II) ions concentration. This result
showed that adsorption was more favorable at high concentration
than low initial concentration of Mn(II) ions. Referring to Table 1,
the highest mono-layer adsorption capacities of PONP for adsorbing Mn(II) ions is 103.0928 mg/g at 293.15 K. The result agreed
with the works carried out by previous researchers which reported
that the Langmuir model tted the results better than Freundlich
model on the adsorption of Mn(II) adsorbed by different adsorbents, such as granular activated carbon [34], lignite [28]. When
temperature arose from 278.15 K to 303.15 K, the adsorption
capacity of PONP can be observed with increasing the temperature.
The value of the distribution coefcient (R2) of Freundlich model is 0.90090.9688. Therefore, it came to the conclusion that the
adsorption of Mn(II) did not t Freundlich isotherm closely as well
as Langmuir model does. In addition, the n value of Freundlich
model is greater than 1 at different concentration of Mn(II) ions.
The values of n are high indicating the heterogeneity of the adsorbent is more obvious. The value for n above one indicates a normal
Langmuir isotherm while n below one is indicative of cooperative
adsorption [35,36] The results suggest that PONP is a suitable
adsorbent and benecial for the adsorption of Mn(II) ions from
solution.
At the temperature lower than 303.15 K, the experimental data
also had a good correlation with Temkin isotherm (R2 > 0.91). When
temperature exceeded 298.15 K, the higher the temperature, the
faster the motion of the metal ions, the adsorption no longer follow
Temkin isotherm. Temkin adsorption potential of PONP is
38.28375.255 kJ/mol that is greater than 8 kJ/mol, illustrating that
strong interaction between Mn(II) ions and the PONP surface
[37,38]. Based on the adsorption isotherm studies, the experimental
results indicated that a monolayer of Mn(II) ions was adsorbed on
homogeneous adsorption sites on the surface of PONP. The PONP
prepared in this work showed relatively large Mn(II) adsorption

Table 1
Modeled adsorption isotherm equation, isotherm parameters, and distribution
coefcient for the adsorption of Mn(II) on PONP at different temperatures.
5 C

Fig. 8d. Temkin isotherm polts for Mn(II) ions adsorption onto PONP.

of Mn(II) on PONP at different temperatures was presented in


Fig. 8d.

20 C

30 C

93.4579
0.1374
0.1271
0.0678
0.0463
0.0351
0.0237
0.9992

103.0928
0.1770
0.1015
0.0535
0.0363
0.0275
0.0185
0.9988

75.188
0.0405
0.3306
0.1980
0.1413
0.1099
0.0760
0.9884

Freundlich isotherm model


44.7012
KF (mg/g)
n
9.3023
2
R
0.9688

60.6913
13.3690
0.9474

76.9996
20.7469
0.9252

30.8921
7.0871
0.9009

Temkin isotherm model


KT
146.826
B
7.6731
R2
0.9681

9195.1179
6.2502
0.9431

1.4742  107
4.5592
0.9158

11.4834
8.4522
0.8804

Langmuir isotherm model


Q (mg/g)
83.3333
b (L/mg)
0.0924
RL (50 mg/L)
0.1779
RL (100 mg/L)
0.0977
RL (150 mg/L)
0.0673
RL (200 mg/L)
0.0513
RL (300 mg/L)
0.0348
R2
0.9991

10 C

66

L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

capacity, which showed application potential in the treatment of


water polluted by metal cations.

3.4. Adsorption kinetics


In order to evaluate the adsorption kinetic mechanism that
controls the adsorption process, four kinetic models including the
pseudo-rst-order, the pseudo-second-order models, intra-particle
diffusion model and Elovich model were used. Kinetic parameters
from linear plots of four kinetic models are given in Table 2.

3.4.1. Pseudo-rst-order
Pseudo-rst-order was suggested by Lagergren [19] for the
adsorption of solid and liquid systems. The adsorption of Mn(II)
from the solution to adsorbent can be considered as a reversible
process with equilibrium being established between the liquid
and solid phases.
According to the linear form of pseudo-rst-order model (Eq.
(8)), a linear t between ln(qe  qt) versus contact time (t) was
made. The rate constants (k1), the R2 and the qe values were given
in Table 2. The adsorption rate constants (k1) was calculated from
the slope of the linear plot of ln(qe  qt) versus t.
The theoretical equilibrium adsorption capacity values derived
from pseudo-rst-order kinetic model were considerably different
from the experimental values for all the three different initial concentrations of Mn(II). The values of distribution coefcient (R2) of
pseudo-rst-order model (R2 = 0.93560.9886) was low. Therefore,
the biosorption of Mn(II) onto PONP biomass does not t pseudorst-order kinetic.

3.4.2. Pseudo-second-order
Pseudo-second-order is based on the assumption that the
adsorption rate is determined by the square of the number of vacant adsorption sites on the surface of adsorbent [20].
The rate constants (k2), the R2 and the qe values were given in
Table 2. It was clear from these results that the R2 values were very
high (0.99971) for the Mn(II) biosorption. At the same time, the
theoretical equilibrium adsorption capacity values calculated from
pseudo-second-order kinetic model were very close to the experimental values for all the three different initial concentrations of
Mn(II). The results also revealed that the pseudo-second-order
model was more suitable for the process than other three models,
which had been conrmed in Fig. 9. These results implied that the
biosorption of Mn(II) onto PONP biomass adheres to the pseudo
second-order kinetics which further suggest that chemi-adsorption
is the rate controlling step [39].

Table 2
Kinetic parameters for the adsorption of Mn(II) onto PONP.

3.4.3. Intra-particle diffusion model


To highlight on the rate-limiting step of the process of adsorption, intra-particle diffusion model was applied. Intra-particle diffusion model was suggested by Weber and Morries [40,41].The
model is based on the assumption that if the plot of q versus t1/2
renders a straight line and pass through the origin, intra-particle
diffusion is the reason of rate-limiting step. If the line does not pass
through the origin, the intra-particle diffusion is not the only ratelimiting step, suggesting that the process is controlled by more
than one mechanism limiting the rate of sorption [42]. If the value
of C is higher, the effect of boundary layer on adsorption process is
greater [43]. The deviation of the plot from the linearity and the
large value of C (33.409119.27) indicated that besides of the
intra-particle diffusion, boundary layer diffusion was also the
rate-limiting step.
3.4.4. Elovich model
The Elovich model is particularly well suited for describing
adsorption behavior in aqueous systems that concur with the
nature of chemical adsorption [22].
The high value of R2 is further illustrated that chemisorption is a
major cause of adsorption. The constants depend signicantly on
the amount of adsorbent with the adsorption constant, x, being
the more sensitive than y [44]. The Elovich constants, x at different
initial concentrations have values in the ranges of 9404.3
3.8841  1014. High x value suggested that adsorption rate was
high at the initial stage of adsorption process. The result was closely associated with a large number of chemical groups exposed
at the large surface area of PONP.
4. Conclusion

Kinetic models

Parameters

Pseudo-rst-order

qe (cal) (mg/g) 5.9554


k1 (min1)
0.1276
R2
0.9356

20.2125
0.1189
0.9447

10.3481
0.0949
0.9886

Pseudo-second-order

qe (cal) (mg/g) 39.5257


K2 (min1)
0.1176
R2
1

62.5
0.0145
0.9997

131.5789
0.0206
0.9999

Elovich

x (mg/g min)
y (mg/g)
R2

Intra-particle diffusion Kid


R2
qe (exp)(mg/g)

50 mg/L

Fig. 9. Pseudo-second-order kinetic model for Mn(II) ions adsorption by PONP.

100 mg/L 200 mg/L

1.8636  107 9404.3


0.4859
0.1739
0.9282
0.9736

3.8841  1014
0.2734
0.9908

1.3310
0.9675
39.3337

1.9476
0.9401
130.625

3.7289
0.9950
61.9426

The results presented in this paper demonstrated that PONP has


the potential to be an economical and efcient nano-biosorbent for
removal of Mn(II) from wastewater. The adsorption capacity of
PONP for removal of Mn(II) from aqueous solutions was found to
decrease sharply with an increase in adsorbent dosage. On the contrary, with rising of pH and initial Mn(II) ion concentration, the
adsorption capacity showed an increasing rate. Equilibrium sorption data indicated that excellent t to Langmuir isotherm model
than Freundlich isotherm model and Temkin isotherm model. So
it was indicated a monolayer of Mn(II) ions was adsorbed on
homogeneous adsorption sites on the surface of PONP. The result
of adsorption kinetic study of Mn(II) on PONP indicated that the

L. Ma et al. / Chemical Engineering Journal 225 (2013) 5967

adsorption kinetics followed the pseudo-second-order model with


intra-particle diffusion and boundary layer diffusion as rate-limiting steps. The maximum adsorption capacity of PONP attained
within 30 min.
Acknowledgements
This study nancially supported by the Science and Technology
Project of Chengdu (No. 10GGYB472SF-023), NSFC (No. J1103518),
Science and Technology Supportive Project of Sichuan Province,
China (No. 2009SZ0204). The authors greatly appreciate Professor
Guanglei Cheng and Dong Yu from Sichuan University for their
technical assistance.
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