Beruflich Dokumente
Kultur Dokumente
pubs.acs.org/JPCC
Shandong Provincial Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and
Engineering, Shandong University, Jinan 250100, P. R. China
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
Article
chemical formula
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
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
Article
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)
SBET (m2/g)
Vmeso (cm3/g)
Vmicro (cm3/g)
Vtotal (cm3/g)
>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
F(E*) =
(4)
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)
= q exp Z RT ln
Ce
33
Ce = Cs exp
RT
(3)
(6)
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Article
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Article
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.
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
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AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENTS
This research was supported by the Natural Science
Foundation of Shandong Province (2009ZRB01618).
REFERENCES