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pubs.acs.org/JPCC

Adsorption of Natural Organic Matter Surrogates from Aqueous


Solution by Multiwalled Carbon Nanotubes
Fei-fei Liu, Shu-guang Wang,*, Jin-lin Fan, and Guang-hui Ma

Shandong Provincial Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and
Engineering, Shandong University, Jinan 250100, P. R. China

The Agricultural Extension Station of Agriculture Bureau in Anqiu, 262100, P. R. China


S Supporting Information
*

ABSTRACT: Adsorption of two natural organic matter (NOM)


surrogates (tannic acid and gallic acid) by powdered activated carbon
(PAC) and four kinds of multiwalled carbon nanotubes (MWCNTs) with
dierent diameters was investigated in aqueous solution. The tannic acid
(TA) adsorption isotherm t the Langmuir model best, while adsorption
of gallic acid (GA) t the Freundlich model. PAC has a higher adsorption
capacity for GA due to the pore-lling eect, while TA adsorption on PAC
was lower than that on MWCNTs because of the molecule sieving eect.
Adsorption of GA and TA on MWCNTs decreased with increasing
MWCNT diameter, but neither surface area nor total pore volume alone
can fully explain adsorption of the two NOM surrogates on MWCNTs. Adsorption mechanisms including electrostatic
interaction, hydrophobic interaction, hydrogen bond, and interaction play roles in the adsorption process. This study
implies that NOM properties have a great eect on their adsorption on MWCNTs, and these properties should be further
considered when evaluating the risks of NOM-coated nanomaterials.

INTRODUCTION
Since their discovery by Iijima in 1991,1 carbon nanotubes
(CNTs) have been at the center of nanoscience and
nanotechnology research for a variety of applications such as
adsorbents, composite lters, high-ux membranes, antimicrobial agents, environmental sensors, energy storage devices, and
pollution prevention reagents due to their unique and
outstanding chemical, electronic, and mechanical
properties.26 Production and commercial use of CNTs are
now of signicant quantities, and hundreds of tons of CNTs,
especially multiwalled carbon nanotubes (MWCNTs), are
produced each year.7 As CNTs will inevitably be released
into the environment accidentally or intentionally in the
process of manufacturing and applications,8 there is serious
concern over their possible toxicity and the associated risk to
the environment.913
Natural organic matter (NOM), a complex and heterogeneous mixture of polyelectrolyte with diverse molecular
weights, derives mainly from the decay of plant and animal
residues.14 NOM is ubiquitously present in surface waters at
dissolved organic carbon (DOC) concentrations typically
ranging from 1 to 20 mg/L.15 Therefore, it is unavoidable
that CNTs will contact with NOM once released into an
aquatic environment. Thus far, several impacts of NOM on
CNTs have been reported in previous research articles. First,
NOM enhanced the stability of CNTs suspension by producing
thermodynamically favorable surfaces and inducing electrostatic
and steric repulsion between individual CNTs to overcome
their strong hydrophobicity16,17 and further aect the
2012 American Chemical Society

persistence behavior of CNTs in water. Second, NOM coating


altered the adsorption capacity of CNTs toward other
contaminants. Zhang et al. reported that the presence of
NOM suppressed the adsorption of synthetic organic chemicals
on CNTs resulting from the competition for limited adsorption
sites and physical pore blockage eect of NOM.18 However,
adsorption of heavy metals on NOM-coated CNTs could be
enhanced because of the complexation between metal ions and
functional groups on NOM.19 Third, NOM can inuence the
toxicity and bioavailability of CNTs and other pollutants. Kim
et al. found that NOM-stabilized CNTs have a low acute
ecotoxicity to Daphnia magna, while Cu toxicity increased with
increasing concentration of NOM-associated CNTs.11 Thus,
understanding the interaction between CNTs and NOM,
especially adsorption of NOM on CNTs, is the rst and
essential step for further assessing CNTs transport behavior,
bioavailability, and toxicity impacts.
To date, in the investigations focused on CNTsNOM
interactions,16,17,20,21 most of the NOM used in these studies
was extracted from river sediment or peat soil.2128 However,
NOM has an indeterminate molecular structure and molecular
weight and the composition of NOM from dierent regions
may dier, which is not favorable for determining the
adsorption mechanism accurately. Research with appropriate
small organic molecules as surrogates has provided valuable
Received: July 17, 2012
Revised: November 6, 2012
Published: November 15, 2012
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Table 1. TA and GA Properties


full name

chemical formula

molecular weight (g/mol)

pKa

solubility (mg/L)

TOC (mg/L)

max

log Kow

tannic acid

C76H52O42

1701.2

2.5 105

30.32

272

1.19

gallic acid

C7H6O5

4.9
7.4
4.3
8.7
11.4

1.2 104

39.94

256

0.70

170.12

insight into the behavior of NOM in adsorption systems.19,29


As a substitute for NOM, tannic acid (TA) is an anionic and
hydrophilic organic substance with relatively high molecular
weight, which approximates to the mean value of NOM in
surface waters.30 Another simple possible model for NOM is
gallic acid (GA).31 The molecular weight of TA is exactly 10
times that of GA, and the solubility of the former in water is 20
times higher than the latter, so these two chemicals could
represent NOM sources with a wide range of properties.
Therefore, in the present work, we used TA and GA as NOM
surrogates to systematically examine their adsorption on
dierent MWCNTs and determine the adsorption mechanisms.
In addition, adsorption of NOM on MWCNTs was also
compared with that on powdered activated carbon used in most
commercial water treatment plants. We believe the results will
shed light on the adsorption applications and environmental
fate assessment of carbon nanomaterials.

EXPERIMENTAL METHODS
Materials. TA and GA obtained from Tianjin Kemel
Chemical Reagent Co., Ltd. (Tianjin, China) were of analytical
grade and used without further purication. The physical and
chemical properties of the two compounds are summarized in
Table 1 and their chemical structures are presented in Figure 1.
The carbonaceous adsorbents used in this study were
multiwalled carbon nanotubes (MWCNTs) and powdered
activated carbon (PAC). MWCNTs were purchased from
Shenzhen Nanotech Port Co., Ltd. (Shenzhen, China) with
dierent outer diameters. All MWCNTs were synthesized by
chemical vapor deposition using the mixtures of CH4 and H2 at
700 C with Ni as a catalyst. PAC was obtained from Tianjin
Guangcheng Chemical Reagent Co., Ltd. (Tianjin, China).
MWCNTs and PAC were used without any treatment to
accurately replicate their occurrence in a commercial water
treatment system due to their application or in natural waters
resulting from released accidentally or intentionally.
Characterization of Adsorbents. A series of techniques
was employed to characterize the adsorbents. N2 adsorption
desorption isotherms were performed at 77 K with a
Quadrasorb SI-MP system (Quantachrome, U.S.). All samples
were degassed at 373 K for 8 h in a vacuum before
measurements. The BrunauerEmmettTeller (BET) equation and density functional theory (DFT) were used to
calculate their BET surface area and pore size distribution.
Transmission electron microscopy (TEM) images of
MWCNTs and PAC were observed with a microscope (JEM100CXII, Japan). Samples were prepared by dispersing
MWCNTs or PAC (<1 mg) in ethanol (50 mL) by
ultrasonication (80 kHz, 30 min), and a drop of suspension
was placed on a 200-mesh copper TEM grid. Fourier transform
infrared spectroscopy (FTIR) spectra were recorded in Avatar
370 spectrometer (Thermo Nicolet, U.S.) within the range of
4004000 cm1 with the samples prepared as KBr discs. X-ray
diraction (XRD) patterns of MWCNTs and PAC were

Figure 1. Molecular structures of TA (a) and GA (b).

obtained from a Rigaku D/max-A powder diractionmeter


(Rigaku, Japan) using Cu K radiation at a scanning ratio of
8/min ranging from 5 to 70.
Batch Adsorption Experiment. All adsorption experiments were conducted using a batch equilibration technique at
25 1 C. Briey, certain amounts of adsorbent and adsorbate
solution with a series of initial concentrations (550 mg L1)
were added into 40 mL glass tubes. Background solution
contained 10 mM NaClO4 to maintain constant ionic strength
and was purged with N2 for 15 min to prevent any degradation.
Tubes were sealed with Teon caps and placed on a rotary
shaker (200 rpm) in the dark for 48 h. Preliminary study
indicated that apparent equilibrium was reached in 24 h. After
equilibrium, the tubes were left undisturbed in the shaker
overnight to allow settling of the adsorbents. Then the
supernatants were taken out to separate the solid and solution
using 0.22 m cellulose acetate membrane lter. Finally, the
concentrations of TA or GA in the supernatants were
determined by a UVvis method. Duplicate samples were
run for all of the experiments.
Determination of Adsorbates. Concentrations of TA and
GA were quantied by an UVvis spectrophotometer (Unico
UV-2000, China) at their optimum wavelengths. Detailed max
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Figure 2. Transmission electron microscopy (TEM) images of MWCNTs 1020 (a), MWCNTs 2040 (b), MWCNTs 4060 (c), MWCNTs 60
100 (d), and PAC (e). Scale bars in all images are 100 nm.

Table 2. Selected Properties of the Multiwalled Carbon Nanotubes (MWCNTs) and Powdered Activated Carbon (PAC)
adsorbent
MWCNTs
MWCNTs
MWCNTs
MWCNTs
PAC

1020
2040
4060
60100

purity (%)

length (m)

outer diameter (nm)

SBET (m2/g)

Vmeso (cm3/g)

Vmicro (cm3/g)

Vtotal (cm3/g)

pore width (nm)

>95
>95
>95
>95

12
12
12
12

1020
2040
4060
60100

79.73
70.91
83.34
64.14
162.24

0.153
0.195
0.169
0.143
0.058

0.003
0.008
0.003
0.008
0.049

0.156
0.203
0.172
0.151
0.107

2.897
1.140
3.169
3.794
1.178

approximate energy distribution functions.32 For Freundlich


isotherm, the approximate site energy distribution is described
with the following function

are summarized in Table 1. Calibration curves were obtained


using the standard solution with known concentrations. Blank
samples were carried out for each experiment and did not
indicate any degradation or loss during the experiment process,
which was conrmed by UVvis spectra analysis.
Data Analysis. Three dierent nonlinear isotherm models
were applied to t the adsorption data.
Langmuir model (LM): qe =

F(E*) =

Freundlich model (FM): qe = KFCe

(4)

For the Langmuir isotherm, the site energy distribution is


calculated through the following equation

qmKLCe
1 + KLCe

nE*
KFn(Cs)n

exp
RT
RT

(1)

F(E*) =
(2)

qmKLCs
RT

nE*
nE*
1 + K C exp

exp
L s
RT
RT

(5)

PolanyiManes model (PMM): qe


d

Cs
0

= q exp Z RT ln

Ce

33

According to the Polanyi adsorption potential theory, the


energy of adsorption is related to the equilibrium liquid-phase
concentration by
E*

Ce = Cs exp
RT

(3)

where qe (mg g ) is the solid-phase concentration, Ce (mg


L1) is the solution concentration, qm and q0 are the adsorption
capacity for LM and PMM, KL (L mg1) is the Langmuir
adsorption anity parameter. KF and n are the Freundlich
adsorption constants. Cs (mg L1) represents the water
solubility of adsorbate at 20 C, Z and d are the PMM tting
parameters. R is the universal gas constant (8.314 103 kJ
mol1K1), and T is the absolute temperature (K).
Site Energy Distribution. To analyze the energetic
characteristics of interactions between adsorbate and adsorbent,
the condensation approximation was used to produce

(6)

where E* is the dierence of adsorption energy at Ce and Cs.

RESULTS AND DISCUSSION


Characterization of Adsorbents. TEM images of the
adsorbents are shown in Figure 2. As can be seen, a handful of
metal catalyst and amorphous carbon existed within the pristine
MWCNTs and the outer diameters were almost consistent with
the data provided by the supplier. PAC was composed by
several graphite sheets.

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N2 adsorption isotherms of MWCNTs were of identical


shape and can be divided into four sections.34 The rst section
appeared at ultralow pressures, and adsorption increased
rapidly due to the micropore lling. Adsorption of the next
section increased slowly and linearly due to surface monolayer
formation. In addition, the last two sections of N2 adsorption
were the hysteresis loops resulting from capillary condensation
in the medium and high pressures, respectively. However, the
N2 adsorption isotherm for PAC exhibited a dierent pattern
(Figure S1, Supporting Information). From BET calculation of
N2 isotherms, MWCNTs surface area was in the range of
64.1483.34 m2 g1, which was lower than the previously
reported data due to the presence of amorphous carbon and
metal catalyst.35,36 Among the four types of MWCNTs, the
surface area decreased with increasing tube diameter except
MWCNTs 4060 (Table 2). The surface area of PAC was
162.24 m2 g1, which was higher than any of the MWCNTs
used in this study.
Information about pores of PAC and MWCNTs are listed in
Table 2. As van der Waals force exists between individual tubes,
MWCNTs tend to aggregate to form bundles which possess
four possible adsorption sites including the external surface of
the outmost MWCNTs, grooves of the MWCNTs bundles,
interstitial spaces between tubes, and inner pores of the opened
tubes.37 Because of the presence of amorphous carbon and
metal catalyst in pristine MWCNTs, inner pores of MWCNTs
are not available for adsorption. Therefore, the surface area,
exible interconnected grooves region, and interstitial space are
the main adsorption sites in this study (Figure S2, Supporting
Information). Dierent from MWCNTs, the pore structure of
PAC was always xed and closed. Clearly, MWCNTs are
mesopores adsorbent, and the fraction of mesopores was about
9498%, whereas PAC possessed both mesopores and
micropores with an approximate ratio of 1.2:1 (Table 2). For
MWCNTs, the pore volumes decreased with increasing outer
diameter; however, the pore volume of MWCNTs 1020 was
the least.
Figure S3, Supporting Information, shows the XRD patterns
of MWCNTs and PAC. All of the adsorbents had a sharp
diraction peak at approximate 2 = 26 corresponding to the
(002) reection planes, which indicated that both MWCNTs
and PAC were composed by graphite sheets. It should be noted
that 2 increased but d002 (the interlayer spacing between the
adjacent graphite layers) decreased with increasing tube
diameter, which may result primarily from the low curvature
and associated strain in the higher diameter nanotubes.38,39
Higher curvature could increase attraction energies between
surfaces and adsorbed molecules40 and thus might increase
NOM adsorption on lower diameter MWCNTs. FTIR
measurements were performed to verify the functional groups
on MWCNTs and PAC (Figure S4, Supporting Information).
It was clear that all MWCNTs displayed no signicant bands,
but PAC showed some apparent bands as MWCNTs and PAC
were fundamentally dierent. MWCNTs are composed of
globally conjugated unsaturated carbons in three-dimensional
arrays, while PAC contains carbons of varying saturation degree
and oxidation state as well as functional groups formed during
the activation process.41
Adsorption Isotherms. Isotherm data for TA and GA
adsorption on the ve adsorbents are shown in Figure 3. It is
apparent that all adsorption isotherms were nonlinear when the
qe vs Ce were plotted on linear coordinates. Therefore, three
commonly used nonlinear adsorption isotherm models, LM,

Figure 3. Adsorption isotherms of GA (a) and TA (b) on PAC and


MWCNTs. Dashed lines and solid lines are the tting curves of FM
and LM, respectively.

FM, and PMM, were employed to t the experimental data


with Sigmaplot 12.0. Adsorption parameters, their probabilities
(p), and adjusted square of correction coecients (R2adj) for
GA and TA adsorption are given in Tables S1 and S2,
Supporting Information. Statistical signicance was accepted
when p was less than 0.01.
For GA adsorption isotherms, it appears that the twoparameter FM had better t to the experimental data than LM
and PMM (Figure S5, Supporting Information) with high R2adj
and low p (<0.01). The lowest R2adj and p of the tting
parameter b for MWCNTs 4060 was larger than 0.01,
suggesting that LM was not an appropriate model to describe
GA adsorption. PMM also failed to t the adsorption data with
almost all of the tting parameters signicantly unreliable (p
0.01).
For TA adsorption, lowest R2adj excluded FM as an
appropriate model for the adsorption isotherm data (Figure
S6, Supporting Information). Although PMM seemed to t TA
adsorption well with high R2adj (>0.99), the PMM tting
parameter Z for MWCNTs 60100 was signicantly unreliable
with p 0.01. LM tted TA adsorption on the ve adsorbents
quite well with high R2adj and p < 0.01. Hence, the following
discussion is based on the adsorption parameters calculated
from FM and LM tting results for GA and TA adsorption,
respectively.
Adsorption Sites Analysis. Figure 3a displays FM-tted
GA adsorption isotherms onto the ve adsorbents on the unit
mass basis. GA adsorption was markedly stronger on PAC than
that on MWCNTs, and its surface area normalized adsorption
capacity on PAC was also larger than that on MWCNTs at a
given equilibrium concentration (Figure S7, Supporting
Information). The adsorption distribution coecients (Kd, L
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g1) were calculated from the equilibrium adsorption data and


are shown in Figure S8, Supporting Information. It can be seen
that the value of Kd followed the same order as the adsorption
capacity within the tested adsorption concentrations range.
Previous studies proposed that microporous adsorbents such as
activated carbon and charcoal have higher adsorption anity to
low molecular compounds (naphthalene, benzene, and
toluene) due to the micropore lling eect resulting from the
closeness of the molecular size of the adsorbate and the pore
size of adsorbent.42,43 In the current study, PAC has the highest
micropores volume (0.049 cm3 g1) and the almost lowest
average pore diameter (1.178 nm). Moreover, the molecular
diameter of GA was approximate 0.57 nm calculated by
Gaussian software. Therefore, micropore lling was the main
contributor for the largest GA adsorption anity on PAC.
However, due to large molecular weight and thus high steric
hindrance of TA, it was very dicult for TA molecules to enter
the micropores in PAC and MWCNTs.
Figure 3b presents the adsorption isotherms of TA on PAC
and MWCNTs tted by the LM on the unit mass basis.
Compared with GA, TA exhibited apparently dierent
adsorption patterns and the adsorption anity followed an
order of MWCNTs > PAC. Besides, the surface-normalized
adsorption isotherms and the trends of Kd were all in the same
order of MWCNTs > PAC (Figures S7 and S8, Supporting
Information). The dierence of TA adsorption on MWCNTs
and PAC was probably caused by the molecular sieving eect.
TA is a bulky molecule with an average diameter of 1.6 nm.
Pelekani et al. reported that adsorption happened in pores
which were larger than 1.7 times of the adsorbate molecules
second widest dimension.44 Therefore, TA cannot access pores
smaller than 2.72 nm. Average pore width of MWCNTs except
MWCNTs 2040 exceeded 2.72 nm, and thus, TA adsorption
on MWCNTs was not aected by the sieving eect. Unlike
MWCNTs, PAC had rigid pore structures and a relatively
smaller pore width. Accordingly, PAC exhibited a more severe
molecule sieving eect than MWCNTs when encountering
bulky adsorbates. It is worth noting that although the pore
width of MWCNTs 2040 was the lowest and closest to that of
PAC, TA adsorption on MWCNTs 2040 was signicantly
higher than that on PAC. MWCNTs existed as bundles due to
aggregation of individual nanotubes and formed exible pores;
however, the aggregation behavior of MWCNTs may change
when introduced in water due to the presence of a minor
amount of functional groups. Surface functionalization with Ocontaining functional groups had a positive eect on the water
dispersibility of MWCNTs,45 which likely loosened the
MWCNTs aggregates and further enlarged the average pore
width accessible for TA.
Adsorption isotherms of GA and TA on the four types of
MWCNTs are also shown in Figure 3. It was apparent that GA
adsorption increased in the order of MWCNTs 1020 >
MWCNTs 2040 > MWCNTs 4060 > MWCNTs 60100.
In addition, adsorption of TA by MWCNTs also decreased
with increasing MWCNT diameter. Su et al. studied the
adsorption of NOM on MWCNTs and attributed the high
adsorption capacity to the large pore volume of MWCNTs.46
Yang et al. used fulvic acid (FA) as NOM to study the eect of
MWCNTs characteristics on FA adsorption and observed that
FA adsorption capacity on MWCNTs depended greatly on the
surface area of MWCNTs, thus concluding that surface area
was a major factor in the adsorption process.21 From Table 2,
total pore volume of MWCNTs followed the order MWCNTs

2040 > MWCNTs 4060 > MWCNTs 1020 > MWCNTs


60100 and BET surface area decreased with the increase of
MWCNTs diameter except MWCNTs 4060. Both of the
above orders were dierent with the order of GA and TA
adsorption on the four types of MWCNTs in the current study.
Therefore, neither MWCNTs surface area nor the total pore
volume alone can fully explain the GA and TA adsorption on
MWCNTs.
E* can be calculated according to eq 6, and variation of E* as
a function of qe is shown in Figure 4. E* decreased with

Figure 4. Variation of E* as a function of qe for GA (a) and TA (b).

increasing qe for both of GA and TA on the ve adsorbents but


exhibited dierent patterns. For GA adsorption, E* followed
the order PAC > MWCNTs 1020 > MWCNTs 2040 >
MWCNTs 4060 > MWCNTs 60100 at a certain qe (Figure
4a), which was in agreement with the order of GA adsorption
capacity on PAC and MWCNTs. E* decreased sharply at rst
but trended slowly with increasing qe, which veried the
heterogeneous sites for GA adsorption on PAC and
MWCNTs.47 For TA, E* was also in accordance with the
order of TA adsorption capacity. However, dierent from GA,
E* decreased slowly at rst but then sharply with increasing qe.
Figure 5 displays the site energy distribution of GA and TA
on the ve adsorbents. F(E*) decreased for GA with increasing
E* (Figure 5a), and the values of F(E*) for PAC were above
those for the four MWCNTs, reecting more sites on PAC for
GA adsorption. F(E*) curves for TA adsorption are illustrated
in Figure 5b. It can be seen that MWCNTs and PAC had
similar distribution shapes but dierent peaks. All of the F(E*)
values for MWCNTs were higher than that for PAC, suggesting
the presence of more sites on MWCNTs for TA adsorption.
F(E*) values for the four types of MWCNTs decreased with
increasing MWCNT diameter, which was consistent with the
decrease of TA adsorption capacity. It is worth noting that
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the surface while the surface of PAC was more hydrophilic with
O-containing functional groups. Therefore, it is believed that
hydrophobic interaction was more important for GA and TA
adsorption on MWCNTs than that on PAC. Hydrophobic
interaction can be evaluated by the octanolwater distribution
coecient (Kow) of organic chemicals, and stronger hydrophobic interaction results from higher Kow. GA is more
hydrophobic with lower solubility and higher Kow (Table 1),
but its adsorption anity on MWCNTs was obviously lower
than TA. From the above, hydrophobic interaction was not a
key mechanism for adsorption of GA and TA on the ve
adsorbents.
A hydrogen bond (H bond) has been proposed as a
mechanism for interpreting adsorption of chemicals on
carbonaceous materials.53,54 A H bond was formed between
the adsorbate OH groups and the adsorbent O-containing
groups. Similarly, GA and TA have a large amount of OH
groups and thus can form H bonds with the O-containing
functional groups of PAC. However, this mechanism might not
be important in GA and TA adsorption on MWCNTs because
the amount of oxygen on MWCNTs was very low. Though the
contribution of surface groups on MWCNTs to the H bond
was negligent, the aromatic rings on the MWCNT surface can
act as a H-bond donor and form a H bond with OH on GA
and TA molecules.55 Therefore, the H bond was one of the
mechanisms for GA and TA adsorption on the ve adsorbents,
although the source of H-bond donors was dierent for PAC
and MWCNTs.
EDA interaction was a specic, noncovalent force of
attraction between -donor and -acceptor molecules. This
interaction was usually regarded as one of the most important
driving forces for adsorption of chemicals with aromatic rings
on graphene structures.43,56,57 PAC is an organic semiconductor with delocalized electrons on its surfaces, thus
showing electrondonor properties.58 As for MWCNTs, each
carbon atom has a -electron orbit perpendicular to their
surface,59 so they can be viewed as either electrodonors or
electroacceptors. Previous studies have revealed the role of
EDA interaction in the adsorption of phenols and some
antibiotics on PAC and MWCNTs.42,53 GA and TA have a
large amount of OH, which makes aromatic rings on both of
them electrondonors due to the electron-donor ability of OH.
Therefore, EDA interaction can be responsible for the
strong adsorption between GA/TA on PAC and MWCNTs.

Figure 5. Adsorption site energy distribution curves of GA (a) and TA


(b) on the ve adsorbents.

F(E*) curves for MWCNTs 4060 and MWCNTs 60100


crossed with each other, which also can be seen from almost
overlapping of TA adsorption on MWCNTs 4060 and
MWCNTs 60100 (Figure 3b).
Adsorption Mechanisms. The adsorption behaviors of
GA and TA on the ve adsorbents were dierent, suggesting
various mechanisms occurred in the adsorption process. On the
basis of the literature, several possible mechanisms should be
considered to explain the adsorptive interactions between GA/
TA and MWCNTs/PAC including electrostatic interaction,
hydrophobic interaction, hydrogen bond, and electrondonoracceptor (EDA) interaction.
Electrostatic interaction has been widely considered one of
the major factors controlling adsorption of aromatic chemicals,
especially ionic compounds on carbon adsorbents.48,49 GA and
TA have more than one pKa (Table 1), and both of them can
be positively charged, negatively charged, or zwitterionic due to
the variation of solution pH. PAC used in this study has a large
amount of various functional groups such as OH (3400
cm1), COOH (1700 cm1), and CO (1400 cm1), and its
surface can be protonated or deprotonated at dierent pH
values. Therefore, electrostatic attraction or repulsion between
GA/TA and PAC was likely to occur in the adsorption process.
However, this mechanism was not responsible for adsorption of
GA/TA on MWCNTs. As shown in Figure S4, Supporting
Information, the as-grown MWCNTs were almost free of Ocontaining functional groups without any chemical modication, and hence, the surface of MWCNTs cannot be charged.
Both MWCNTs and PAC are heterogeneous, being
composed of hydrophobic regions due to their bare carbon
backbone. Thus, hydrophobic interaction should be considered
to understand the adsorption of some organic chemicals on
carbon adsorbents.5052 In the current investigation, MWCNTs
were completely hydrophobic with minor functional groups on

CONCLUSIONS
It is very important to understand the interaction between
NOM and CNTs as NOM has a severe eect on the fate and
possible risks of CNTs to the environment. Evaluating the
adsorption of NOM on CNTs was the rst essential step for
further assessing the potential environmental behavior of
CNTs. In this study, TA and GA were employed to investigate
the adsorption of NOM on MWCNTs. The results suggested
that MWCNTs has a higher adsorption capacity for larger
molecular weight NOM, and several mechanisms act
simultaneously in the adsorption process. Further studies are
needed to focus on the fate of NOM-coated CNTs to promote
development and application of carbon nanomaterials.

ASSOCIATED CONTENT

S Supporting Information
*

Tables of nonlinear ts of adsorption isotherms of GA on


MWCNTs and PAC and nonlinear ts of adsorption isotherms
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of TA on MWCNTs and PAC; gures of nitrogen adsorption


isotherms of MWCNTs and PAC, distribution of adsorption
sites on MWCNTs bundles, X-ray diraction (XRD) patterns
for MWCNTs and PAC, FTIR spectrum of MWCNTs and
PAC, LM and PMM isotherms of GA on MWCNTs and PAC,
FM and PMM isotherms of TA on MWCNTs and PAC,
adsorption isotherms of GA and TA on unit surface basis, and
Kd curves of GA and TA adsorption on PAC and MWCNTs.
This material is available free of charge via the Internet at
http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Phone: +86 531 88362802. Fax: +86 531 88364513. E-mail:


wsg@sdu.edu.cn.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This research was supported by the Natural Science
Foundation of Shandong Province (2009ZRB01618).

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