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Page 1 of 27

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DOI: 10.1039/C5RA14748D

Facile and cost-effective synthesis of CNT@MCo2O4 (M=Ni, Mn, Cu, Zn)

core-shell hybrid nanostructures for organic dye removal

College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou

730000, P.R. China

Corresponding author. Tel./fax: +86 931 8912582

E-mail address: yansq@lzu.edu.cn (S. Yan)

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Haizhen Li, Zebin Sun, Yaxi Tian, Guijia Cui, Shiqiang Yan*

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Abstract
This study presents four hybrid materials of CNTs@MCo2O4 (M=Ni, Mn, Cu, Zn)

temperature followed by a post-annealing treatment. The resulting materials were

characterized by different techniques including SEM, EDS, XRD, FTIR, and BET
surface area measurement and were first used as adsorbents for removal of methyl
orange (MO). Experimental dates suggested that CNTs@MCo2O4 samples especially
CNTs@NiCo2O4 showed excellent adsorption properties (1188.3mg/g). The kinetic
adsorption

of

different

materials

could

be

accurately

described

by

the

pseudo-second-order model and overall rate process was apparently influenced by

external mass transfer and intraparticle diffusion. Furthermore, Langmuir and
Freundlich isotherms are employed and both of them fitted the experimental data with
good correlation coefficients. Moreover, the thermodynamic parameters indicated that
the adsorption process was spontaneous and physical adsorption mechanisms
including electrostatic interaction might play a dominant role in the adsorption
mechanism between MO and adsorbents. Results of this work are of great
significance for environmental applications of CNTs@MCo2O4 as promising
adsorbents for organic pollutant from wastewater.
Keywords: CNTs, Spinel cobaltate, removal, methyl orange
1.

Introduction
With the development of technology and industry, aqueous dye pollution,

commonly caused by the wastewater discharged from textile, leather and paper

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which were prepared via a simple chemical bath deposition method at room

Page 3 of 27

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industries, has emerged as one of most serious pollution in water especially in

developing countries.1 Unfortunately, the color wastewater is rather difficult to treat

pollutants.2 Meanwhile, the hazardous pollutants pose ecological risks and are toxic to
aquatic life and mankind if discharged directly into receiving waters, because they
may be mutagenic and carcinogenic and can cause a severe health hazard to human
beings, such as dysfunction of kidney, reproductive system, liver, brain and central
nervous system.3,

Thus, it is imperative to treat the dyes in their wastes to an

acceptable level before discharging them into the environment.

There are many physical, chemical and biological treatment techniques for
removing dyes from industrial effluent, such as chemical oxidation, photochemical
degradation, biological degradation, ultrasonic degradation, reverse osmosis, flotation
and adsorption procedures.5-10 Among those methods, adsorption is recognized to be
the most popular method because of its low cost, easy operation and high removal
efficiency.11-17
Among various available adsorbents, transition metal oxides have potential
applications in water treatment owing to their excellent characteristics such as
environmentally friendly synthesis methods and low price.18 In the large family of
metal oxides, spinel cobaltites, MCo2O4 (M=Ni, Mn, Cu, Zn) are very promising
multifunctional materials and have been widely used in several applications such as
catalysis, environmental remediation and electrochemical supercapacitors as well as
adsorption.19-21 However, the low specific area of spinel cobaltites micrometer powder

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because of the non-degradable synthetic origins and aromatic structures of the

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could greatly reduce the contact area of the materials and dye molecules, which could
significantly decrease the adsorption capacity of spinel cobaltites. In addition, the

above-mentioned problems, multi-walled CNTs are introduced due to their high

specific surface area, very high strength, chemical stability and low density.22-24 The
multi-walled CNTs could not only buffer the agglomeration of the active metal oxide
nanostructures, but also enhance the specific area of spinel cobaltites. And the active
sites of spinel cobaltites can be also further increased, which greatly increased the
adsorption capacity for dyes. Thus far, many studies focussing on CNT-supported
MCo2O4 have been reported,25-28 however, to the best of our knowledge, few of them
are selected to be adsorbents for removing dyes.
In this work, we grew MCo2O4 (M=Ni, Mn, Cu, Zn) on individual CNTs via a
simple and cost-effective chemical bath deposition method at room temperature
followed by a post-annealing treatment. The chemical co-precipitation method has
several advantages such as simplicity, low processing temperature and pressure, low
cost, high product purity and the ability to control the morphology compared with
most conventional methods. This prepared CNTs@MCo2O4 hybrids possess high
specific surface area and display a remarkable adsorption performance for removal
organic dyes. And their adsorption capability for organic pollutants were investigated
using methyl orange (MO) as a model. The CNTs@MCo2O4 were characterized by
field-emission
spectrometry

scanning electron microscopy (FESEM), X-ray energy dispersive

(EDS),

X-ray

diffraction

(XRD),

Fourier-transform

infrared

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pure spinel cobaltites are easy to agglomerate. In order to alleviate the

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spectroscopy (FTIR) analysis, Brunauer, Emmett, and Teller surface area

measurement (BET) analyses. The adsorption capacities of different materials, effects

experiments. Moreover, the adsorption kinetics, rate-controlling mechanisms, and

thermodynamics of the adsorbents were also comprehensively investigated.
2. Experimental section
2.1. Materials
MWCNTs having diameter 2030 nm and length of 520 m, were purchased
from Alpha Nano Technology Co., Ltd. (China). Polyvinylpyrrolidone (PVP),
absolute ethanol and NH3H2O (25-28 wt%) were purchased from the Sinopharm
Group Chemical Reagent Co., Ltd. CoCl26H2O, NiCl26H2O, MnCl24H2O,
CuCl22H2O and ZnCl2 were obtained from Kelong chemical company (Chengdu,
China). All chemicals are of analytical grade and used without further purification.
2.2. Preparation of CNT@MCo2O4
CNT@MCo2O4 nanomaterials were fabricated by a simple chemical bath
deposition method at room temperature followed by a post-annealing treatment. And
the detailed preparation procedure is illustrated in Scheme 1. Taking the preparation
of CNT@NiCo2O4 as an example, briefly, 35 mg MWCNT powder was uniformly
dispersed into 100ml 7 mg ml-1 PVP aqueous solution with ultrasonication for 1.5 h.
Then 0.9517g (4 mmol) of CoCl26H2O and 0.4754g (2 mmol) of NiCl26H2O were
dissolved into the MWCNT dispersion with vigorous stirring for 0.5 h to form a black
solution, followed by a drop-by-drop addition of 5% NH3H2O solution until its pH

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of pH, contact time at different initial concentrations were examined in bath

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reached 9. The mixture was kept still for 4 h at room temperature. The obtained
precipitate was filtered, washed with water and ethanol several times to remove the

obtain the CNT@NiCo2O4 nanostructure, the hybrid precursor was finally annealed in
air at 300 for 3 h with a slow heating rate of 1 min-1. With the same procedure
and amounts of CoCl26H2O and MWCNT, MnCl24H2O (0.396 g, 2mmol),
CuCl22H2O (0.341 g, 2mmol) and ZnCl2 (0.273 g, 2 mmol) were used instead of
NiCl26H2O for the syntheses of other CNT@MCo2O4 (M = Mn, Cu and Zn) hybrids,
respectively.
2.3 Material characterizations
The as-prepared CNT@MCo2O4 nanomaterials were characterized with
field-emission scanning electron microscopy (FESEM, JSM-6701F) and X-ray energy
dispersive spectrometry (EDS, Apollo40SDD). The crystallinity of the samples was
investigated by X-ray diffraction (XRD, XRD-6000, shimadzu, Japan). Fourier
transform infrared spectra (FTIR) were carried out using a NEXUS 670 FTIR
equipped with a pressed KBr pellets in wavenumber range of 400-4000 cm-1. The
BET surface area, pore volume, and pore size were characterized using nitrogen
adsorption at liquid nitrogen temperatures (Sorptomatic 1990, Thermo, USA).
2.4. Adsorption experiments
Standard solutions of methyl orange (MO) in six different concentrations
(100-600 mg L-1) were prepared by dissolving analytical grade methyl orange in
distilled water.

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surfactant and the residual ions, and dried at 60 for 12 h under vacuum. In order to

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To determine the adsorption capacities of different materials, the CNT@MCo2O4

were prepared as adsorbents for MO removal. 5 mg sample of the different adsorbents

600 mg L-1 (100 mg L-1 intervals). The mixture was sonicated for 5 minutes at room
temperature and stirred for 120 minutes and then filtered using a 0.45 m
microporous membrane filter. The filtered MO solutions were diluted and measured
by a spectrophotometric method at 465 nm.
The effect of pH on MO adsorption was studied by varying the solution pH from
3.0 to 11.0, with the initial MO concentration of 100 mg L-1. The pH of each solution
was adjusted using 1 M HCl or NaOH solution.
Adsorption kinetic experiments were conducted by adding 300 mg of different
CNT@MCo2O4 nanomaterials to each of 1500 ml MO solution, and the MO
concentration was 600 mg L-1 at 298 K. Samples were withdrawn at predetermined
time intervals and filtered through a 0.45 m filter.
The amount of MO adsorption at equilibrium qe (mg/g) was calculated using the
following equation:

 =

(  )


(1)

Where V is the volume of the MO solution (L); C0 and Ce are the initial and
equilibrium concentration (mg L-1) of MO respectively; and m is the weight of the
adsorbents (g).

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was added to each 25 mL of MO solution with initial concentration of 100 mg L-1 to

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Scheme 1 Schematic presentation of the preparation procedure of CNT@MCo2O4

3. Results and discussion
3.1 Characterization of the adsorbents
The morphology of the CNT@NiCo2O4, CNT@MnCo2O4, CNT@CuCo2O4,
CNT@ZnCo2O4 and CNT were characterized by field-emission scanning electron
microscopy (FESEM) observation and transmission electron microscope (TEM). Fig.
1(a-d) shows the representative FESEM images of the as-prepared CNT@MCo2O4
hybrids. It can be found that the surface of CNT@MCo2O4 is flake shaped and
finegrained. And the surface of CNT (Fig.1e) is relatively smooth compared with
CNT@MCo2O4. Fig.1 (f) is the TEM of CNT@NiCo2O4. It can be seen that NiCo2O4
is uniformly coated on the CNT. However, the morphology of the CNT is not easy to
distinguish. The possible reason is that CNT has only left a skeleton through
annealing process in air in the process of our material preparation. In all cases,
MCo2O4 nanomaterials were found well-grown around individual CNTs to form a

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conformal coating on the surface, showing that the method of chemical bath
deposition at room temperature followed by a post-annealing treatment could be

Fig.1. SEM images of (a) CNT@NiCo2O4, (b) CNT@MnCo2O4, (c) CNT@CuCo2O4,

(d) CNT@ZnCo2O4 and (e) CNT. TEM image of (f) CNT@NiCo2O4

Fig.2. EDS patterns of (a) CNT@NiCo2O4, (b) CNT@MnCo2O4, (c) CNT@CuCo2O4

and (d) CNT@ZnCo2O4
To confirm the composition of the hybrids, the EDS attached to the FESEM was

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generally used in the synthesis of various CNT@MCo2O4 hybrids.

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measured and the corresponding EDS spectra of the as-prepared CNT@MCo2O4

hybrids was displayed in Fig.2 (a-d). The EDS spectra of the CNT@MCo2O4 hybrids

ratio of M/Co close to 1:2. The C mainly comes from the CNTs, while O from both
MCo2O4 and some oxygen-containing functional groups of CNTs. The results of EDS
confirmed that the MCo2O4 were successfully synthesized.

Fig.3.

XRD

patterns

of

(a)

CNT@NiCo2O4,

(b)

CNT@MnCo2O4,

(c)

CNT@CuCo2O4, (d) CNT@ZnCo2O4 and (e) CNT

The

crystallographic

phase

of

CNT@NiCo2O4,

CNT@MnCo2O4,

CNT@CuCo2O4, CNT@ZnCo2O4 and CNT were identified by XRD, and the typical
wide-angle diffraction patterns are shown in Fig.3 (a-e). It can be noticed that
CNT@MCo2O4 consisted of seven well-defined diffraction peaks, which can be well
indexed to the (220), (311), (222), (400), (422), (511), and (440) crystal planes of
cubic spinel structural NiCo2O4 (JCPDS card no. 20-0781), MnCo2O4 (JCPDS card

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revealed the presence of M (Ni, Mn, Cu, and Zn), Co, C and O with the atomic ratio

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no.23-1237), CuCo2O4 (JCPDS card no. 78-2177), and ZnCo2O4 (JCPDS card no.
23-1390), respectively.29-32 It is worth mentioning that no other peaks are observed,

supported on CNTs. For CNT, two characteristic peaks can be clearly observed,
corresponding to the (002) and (100) crystal planes. However, the typical peaks (002)
of CNT are not observed in CNT@MCo2O4. The possible reason is that the typical
peaks of CNT are covered by the peaks of MCo2O4.

Fig.4. FTIR spectra of (a) CNT@NiCo2O4, (b) CNT@MnCo2O4, (c) CNT@CuCo2O4,

(d) CNT@ZnCo2O4 and (e) CNT
The FTIR spectra of CNT@NiCo2O4, CNT@MnCo2O4, CNT@CuCo2O4,
CNT@ZnCo2O4 and CNT are presented in Fig.4 (a-e). It is obvious that all spectra
exhibit adsorption bands at about 3400, and 1625 cm-1, which can be associated to the
-OH stretching and bending vibration for the free or physically absorbed water
molecules.33, 34 The corresponding metal oxide characteristic peaks positioned at 650
and 555 cm-1 for the samples (a-d) further reveals the formation of the spinel MCo2O4

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which effectively confirms the purity of the obtained MCo2O4 phase, which was

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nanostructure. These bands mainly correspond to the stretching vibrational modes of

M-O (M=Ni, Mn, Cu, Zn) in the tetrahedral positions and Co-O bands in octahedral

Fig.5.

Typical

N2

adsorptiondesorption

isotherms

of

CNT@NiCo2O4,

CNT@MnCo2O4, CNT@CuCo2O4, CNT@ZnCo2O4 and CNT

As illustrated in Fig.5, the adsorption and desorption isotherms of N2 for the
CNT@NiCo2O4, CNT@MnCo2O4, CNT@CuCo2O4, CNT@ZnCo2O4 and CNT are
clearly of type IV, according to the IUPAC classification of adsorption isotherms.35
Type IV isotherms characteristically show the simultaneous presence of micro- and
mesopores.36 And the physical properties of the CNT@NiCo2O4, CNT@MnCo2O4,
CNT@CuCo2O4, CNT@ZnCo2O4 and CNT, such as surface areas, total pore volumes,
pore size are summarized in Table 1. It can be seen that the BET surface area, total
pore volume and average pore size of CNT@NiCo2O4 are 144.0 m2 g-1, 0.8506 cm3g-1
and 23.63 nm, respectively, which were higher than that of other CNT@MCo2O4.
Generally, the BET surface area, total pore volume and average pore size have great

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positions, respectively.34

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influence on the material performance especially the adsorption capacity. Thus, the
CNT@MCo2O4 may have excellent adsorption performance, and this conclusion will

Table 1 Pore surface characteristics of different materials

Surface area (m2 g-1)

Pore volume (cm3 g-1)

Pore size (nm)

CNT@NiCo2O4

144.0

0.8506

23.63

CNT@MnCo2O4

103.64

0.5877

22.68

CNT@CuCo2O4

73.45

0.2630

14.32

CNT@ZnCo2O4

120.58

1.0156

32.99

CNT

174.48

0.8532

19.56

Materials

3.2 Adsorption experiment studies

3.2.1. Adsorption capacities of different materials
The adsorption capacities of different materials including the CNT@NiCo2O4,
CNT@MnCo2O4, CNT@CuCo2O4, CNT@ZnCo2O4 and CNT were investigated, as
shown in Fig. 6. It is obvious that the adsorption capacities of CNT@MCo2O4 were
all increased with the initial concentration of MO increased in. And all of the samples
possess relatively high adsorption performance. Compared with CNT@MCo2O4, the
adsorption capacity of CNT is markedly lower. For CNT@MCo2O4, CNT is the
skeleton and MCo2O4 is coated on the CNT, and then MCo2O4 would be the mainly
adsorbent. Sulfonate groups of MO dyes would bind with the hydroxy-groups on the
surface of metal oxides through electrostatic interaction and hydrogen bond
interaction. However, the CNT surface possesses few functional groups so that the

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be confirmed in the part 3.2.1.

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adsorption capacity of CNT for MO is much lower. In addition, CNT@NiCo2O4

shows the best adsorption capacity among the CNT@MCo2O4 nanomaterials,

with other adsorbents. It is well known that the adsorption properties for dyes depend
on the high specific surface area and the pore properties of the adsorbents.37 The
excellent adsorption capacity of CNT@NiCo2O4 may be ascribed to its large BET
surface area.

Fig.6. Adsorption capacities of different materials with regard to MO adsorption.

3.2.2. Effect of solution pH and Adsorption mechanism
The pH of the system exerts profound influence on the surface charge of the
adsorbent, the degree of ionization of different pollutants, the dissociation of
functional groups on the active sites of the adsorbent as well as the structure of the
dye.38 Thus, the adsorption experiments were performed at initial concentration of
100 mg L-1 and pH range between 3.0 and 11.0 to investigate the effect of the pH on
the adsorption capacities of the CNT@MCo2O4. As shown in Fig. 7, the adsorption

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indicating that CNT@NiCo2O4 has outstanding adsorption performance compared

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capacity of CNT@NiCo2O4, CNT@MnCo2O4, CNT@CuCo2O4 and CNT@ZnCo2O4

were all decreased with the increase in pH from 3.0 to 11.0. At acidic pH, the surfaces

be expressed as MOH2+ (M represents Ni, Mn, Cu, Zn, Co), therefore, resulting in a
higher adsorption performance for MO because of the strong electrostatic attraction
between positively charged surfaces and the anionic MO species. This is mainly the
adsorption mechanism for CNT@MCo2O4 removing MO. However, with the pH
increased, the adsorption performance of CNT@MCo2O4 decreased. The possible
reason is that a growing number of OH- caused repulsion between the negatively
charged surface and the dye molecules.

Fig.7. Effect of solution pH on MO adsorbed onto CNT@MCo2O4

3.2.3. Effect of contact time
The adsorption equilibrium time is one of the most important parameters which
influenced the design of wastewater treatment systems.39 To determine the effect of

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of CNT@MCo2O4 materials were positively charged due to protonation, which could

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contact time on the adsorption process, adsorption experiments of various materials

with initial MO concentration of 600 mg L-1 were conducted for different contact

capacity of MO onto the adsorbents drastically increase during the initial stage and
then at a slow speed, which may be ascribed to the availability of a large number of
vacant active sites on the adsorbent surface during the initial stage, and then, the
remaining vacant surface sites were difficult to occupy because of the repulsive forces
between the dye molecules on the CNT@MCo2O4 and the bulk phase. Eventually, a
plateau is reached after a certain amount of time in all curves.40

Fig.8. Effect of contact time on MO adsorbed onto different materials at 600mg/L

3.2.4. Adsorption dynamics
In order to better evaluate the adsorption kinetics, two kinetic models including
pseudo-first-order and pseudo-second-order model were applied to analyze the
experimental data. These two kinetic models can be represented by the following

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times. The results are presented in Fig. 8. It can be easily observed that the adsorption

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equations: 9, 41



log(

 ) = log
 .
,


  

(3)

Where qe and qt (mg g-1) are the amounts of MO adsorbed at equilibrium and at time t
(min), respectively, while k1 (min-1) and k2 (g mg-1 min-1) represent the observed rate
constants for pseudo first order and pseudo second order models.
Table 2 Kinetic parameters for MO adsorption onto different adsorbents at 600 mg/L
Pseudo-first-order model

Pseudo-second-order model

Adsorbents

qe,exp

k1

qe

r2

k210-4

CNT@NiCo2O4

1211

0.01621

374.7

0.9027

2.809

1206.9

0.9939

CNT@MnCo2O4

678.4

0.03871

291.6

0.9627

2.754

709.2

0.9996

CNT@CuCo2O4

804

0.01911

381.4

0.9796

2.20

819.7

0.9907

CNT@ZnCo2O4

906.9

0.02796

360.4

0.9152

2.018

925.9

0.9918

qe

r2

The values of qe and k1 for the pseudo-first-order kinetic model are determined
from the intercepts and the slopes of the plots of log (qeqt) versus t, and plots of t/qt
versus t allows calculation of the rate constant k2 and qe for the pseudo-second-order
kinetic model. The straight line plots of them are presented in Fig.S1 and Fig.S2,
respectively. The calculated kinetic parameters and correlation coefficients for the
removal of MO with CNT@MCo2O4 are tabulated in Table 2. It is obvious that all the
experimental data showed better compliance with the pseudo-second-order kinetic
model in terms of higher correlation coefficient values (r2> 0.99). Furthermore, the qe
calculated from the pseudo-second-order kinetic model are rather approximate with

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(2)

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those

from

the

experimental

results.

These

results

suggest

that

the

pseudo-second-order kinetic model is more suitable to describe the adsorption

3.2.5. WeberMorris kinetic model

As the above two kinetic models were not able to highlight the diffusion
mechanisms and rate controlling steps that affect the adsorption process, we applied
the WeberMorris kinetic model to study the steps of adsorption process. This
equation can be written as follow: 41

 =    +

(4)

Where qt is the adsorption capacity at time t, kd is the intra-particle diffusion rate

constant, C is a constant that gives idea about the thickness of the boundary layer, the
larger the value of C, the greater the boundary layer effect is. The values of kd and C
can be obtained by plotting qt against t1/2.
The multilinear plots of intra-particle diffusion process of MO adsorption onto
CNT@MCo2O4 are presented in Fig.9. It suggests that two steps have taken place
during the adsorption process. The first linear portion is related to external diffusion
which is the diffusion of MO molecules from solution to the external surface of
CNT@MCo2O4. And the second regions can be attributed to the internal diffusion of
MO from the external surface to the internal pores of the adsorbent. According to the
WeberMorris kinetic model, if the regression of qt versus t1/2 is linear and passes
through the origin, then intra-particle diffusion is the sole rate-limiting step. The
regression is linear, but the plot does not pass through the origin, suggesting that

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process.

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adsorption involve intra-particle diffusion, but that is not the only rate-controlling
step.42 From the Fig.9, it can be noticed that the plots did not pass through the origin,

Fig.9. WeberMorris plots for the kinetic modeling of MO adsorbed onto different
materials at 600mg/L
3.2.6. Adsorption isotherms
The equilibrium isotherms are very important for understanding the adsorption
systems. Adsorption isotherm provides information about the surface properties of
adsorbent, the adsorption behavior and the design of adsorption systems. It also
affords essential physiochemical data for assessing the applicability of the adsorption
process as a complete unit operation.43 In this work, two typical isotherm models,
such as Langmuir and Freundlich isotherm are applied to fit the equilibrium data. The
Langmuir model is based on the assumption that adsorption is localized on a
monolayer and all adsorption sites at the adsorbent are homogeneous.44 Whereas the

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indicating that both external diffusion and intra-particle diffusion are significant.

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Freundlich isotherm presumes that the multilayer of the adsorption process occurs on
a heterogeneous surface. These two models can be described by the following





!"

(5)

"


ln
 = ln %& + ln
'

(6)

Where qe (mg g-1) is the amount of solution adsorbed per unit mass of the adsorbent,

Ce is the solute equilibrium concentration. And qm (mg g-1) is the maximum adsorbate
amount, and b (L mg-1) is the Langmuir constant related to adsorption affinity of the
binding sites. KF and n represent the Freundlich constants related to the adsorption
capacity and adsorption intensity, respectively.
The separation factor (RL) related to Langmuir isotherm is also used to evaluate
the feasibility of adsorption on adsorbent. It can be defined as follows:


() = *!

(7)

In this equation, C0 represents the initial MO concentration (mg L-1) and b (L mg-1)
refers to the Langmuir constant. And the values of RL suggest that the types of the
isotherm which can be irreversible (RL = 0), favorable (0 < RL < 1), linear (RL = 1) or
unfavorable (RL > 1)
The Langmuir and Freundlich isotherms are shown in Fig.S3 and Fig.S4,
respectively. The parameters such as b, qm, KF, n, RL and R2 values determined from
these two isotherms are displayed in Table 3. According to the determination
parameters, both Langmuir and Freundlich models closely fitted the experimental data
with good correlation coefficients (R2). And the RL values are lying in the 0-1 range,

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equations: 10

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demonstrating that the isotherms are favorable for adsorption of MO onto

CNT@MCo2O4. The computed maximum MO adsorption capacities are 1257, 840.3,

CNT@CuCo2O4 and CNT@ZnCo2O4, respectively. It is clear that the CNT@MCo2O4

have excellent adsorption performance.
Table 3 Parameters of the Langmuir and Freundlich isotherms for MO adsorption
onto different adsorbents
Langmuir isotherm

qm

Adsorbents

r2

RL10

Freundlich isotherm

1/n

KF

r2

CNT@NiCo2O4

1257

0.0300 0.9900 0.525-2.497 0.2587

261.20

0.9954

CNT@MnCo2O4

840.3 0.0265 0.9939 0.591-2.737 0.2287

200.25

0.9823

CNT@CuCo2O4

869.6 0.0308 0.9955 0.513-2.452 0.2142

229.05

0.9949

CNT@ZnCo2O4

980.4 0.0322 0.9889 0.491-2.367 0.1794

310.7

0.9507

Thermodynamic parameters can improve our understanding regarding the

inherent energetic changes involved during the sorption process. The free energy
change (G0) was calculated from the variation of the thermodynamic equilibrium
constant (K0) to estimate the type of adsorption for the CNT@MCo2O4 toward MO,
which was determined by the following equations: 9
+

- 

% = + , = -, 

(8)

.  = (/ln%

(9)

In the equations, K0 is the thermodynamic equilibrium constant; as is the activity of

the adsorbed MO, ae is the activity of the MO in the solution at equilibrium, s is the

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869.6 and 980.4 mg g-1 at 293K for CNT@NiCo2O4, CNT@MnCo2O4,

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activity coefficient of the adsorbed MO, e is the activity coefficient of MO in solution

at equilibrium; R is the gas constant (8.314 Jmol-1K-1); T is the sorption temperature in

activity coefficient approaches unity, and reducing equation (8) to the following form:
+

% = + , = 

(10)

Therefore, the values of K0 can be acquired by plotting ln(qe/Ce) versus qe and by

extrapolating qe to zero, as shown in Fig.S5.
Table 4 Thermodynamic parameters for MO adsorption onto different adsorbents
Adsorbents

lnK0

r2

G0(kJ/mol)

CNT@NiCo2O4

5.4891

0.9724

-13.378

CNT@MnCo2O4

5.2259

0.9844

-12.737

CNT@CuCo2O4

5.7166

0.9995

-13.933

CNT@ZnCo2O4

6.5943

0.8801

-16.072

The acquired thermodynamic parameters such as lnK0, G0 and R2 are shown in

Table 4. The negative G0 values confirm the feasibility of the process and the
spontaneous nature of the adsorption. Generally G0 for physisorption is less than
that for chemisorption. The former is between -20 and 0 kJ/mol and the latter is
between 80 and -400 kJ/mol.45 Thus, the G0 results implied that physisorption
might dominate the adsorption of MO onto CNT@MCo2O4.
3.3 Comparison of adsorbent performance with literature data
Previously some researchers investigated several adsorbents for the removal of
MO from aqueous solutions. Table 5 shows a comparison of the adsorption capacities

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Kelvin. As the MO concentration in the solution decreases and approaches zero, the

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of MO onto various adsorbents. It clearly can be seen that the MO removal capacities
of CNT@MCo2O4 (M = Ni, Mn, Cu, Zn) are higher than that of other adsorbents,38, 39,
46-51

adsorbents in wastewater treatment.

Table 5 Maximum adsorption capacities of MO onto various adsorbents
adsorbates adsorbents

qmax(mg/g) Refs.

Carbon nanotubes

52.9

46

CNTs-A

149

38

Methyl

NH2-MWCNTs

185.5

47

orange

Activated carbon/Fe3O4 nanocomposites

303.0

48

Mesoporous MgO nanoplates

370

49

SiO2Al2O3 mixed oxides

381

50

Powdered activated carbon modified by HNO3

384.6

48

H--MnO2 nanoparticles

427

51

Phragmites australis activated carbon

437.9

39

CNT@NiCo2O4

1188.3

This work

CNT@MnCo2O4

790.5

This work

CNT@CuCo2O4

826.9

This work

CNT@ZnCo2O4

935.4

This work

4. Conclusions
In summary, CNT@MCo2O4 (M=Ni, Mn, Cu, Zn) nanomaterials were prepared
via a simple chemical bath deposition method at room temperature followed by a

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indicating that CNT@MCo2O4 nanomaterials have great potential as dye

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post-annealing treatment. Their adsorption properties for the removal of MO from

aqueous solution have been studied for the first time and the adsorption process were

initial MO concentrations. The CNT@MCo2O4 samples especially CNTs@NiCo2O4

showed excellent adsorption properties. And the maximum adsorption capacity for
CNT@MCo2O4 (M=Ni, Mn, Cu, Zn) are 1188.3, 790.5, 826.9 and 935.4 mg/g,
respectively. The high adsorption capacity of CNT@MCo2O4 may be ascribed to their
high BET surface area. The kinetic data of the adsorption fitted well with the
pseudo-second-order kinetic model and the results of WeberMorris kinetic model
indicated that overall process appeared to be jointly influenced by intraparticle
diffusion and external mass transfer. Moreover, Langmuir and Freundlich isotherms
are employed to describe the equilibrium adsorption and both of them fitted the
experimental data with good correlation coefficients. The adsorption mechanism was
also discussed, which could be attributed to physical adsorption including electrostatic
interactions and hydrogen bond interaction between MO and the adsorbents. The
results obtained in this work suggest that CNTs@MCo2O4 should be a promising
adsorbent for the removal of MO from wastewater.
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