Catalysis Today 282 (2017) 168173

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Catalytic activity of palladium nanocubes/multiwalled carbon

nanotubes structures for methyl orange dye removal
O. Arciniega Cano a , C.A. Rodrguez Gonzlez a, , J.F. Hernndez Paz a , P. Amezaga Madrid b ,
P.E. Garca Casillas a , A.L. Martnez Hernndez c , C.A. Martnez Prez a
a

Universidad Autnoma de Ciudad Jurez, Av. del Charro # 450 Nte, col. Partido Romero, Cd. Jurez Chihuahua, CP 32310, Mexico
Centro de Investigacin en Materiales Avanzados, S.C., Departamento de Fsica de Materiales, Miguel de Cervantes 120, Complejo Industrial Norte, Cd.
Chihuahua, Chih. Mxico, C.P. 31136, Mexico
c
Divisin de Estudios de Posgrado e Investigacin, Instituto Tecnolgico de Quertaro, Av. Tecnolgico de Quertaro, Av. Tecnolgico s/n Esq. Gral. Mariano
Escobedo, Col. Centro Histrico, 76000 Quertaro, Mexico
b

a r t i c l e

i n f o

Article history:
Received 16 March 2016
Received in revised form 3 June 2016
Accepted 28 June 2016
Available online 7 July 2016
Keywords:
Multiwalled carbon nanotubes
Palladium nanocubes
Methyl orange dye
Catalytic activity

a b s t r a c t
In this work, the synthesis and catalytic activity measurements of a nanostructured material formed by
palladium (Pd) nanocubes supported on multiwalled carbon nanotubes (MWCNTs) for removing methyl
orange as a model of organic contaminant from aqueous solution are presented. The nanocubes were
synthesized by a reduction process of H2 PdCl4 and a non-covalent method that involves a surfactant
functionalization of the carbon nanotubes was used to produce the nanostructured material. Characterization was performed by scanning electron microscopy (SEM), transmission electron microscopy
(TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UVvis. Results showed well
dispersed Pd nanocubes, in the range of 1525 nm, bonded onto the carbon nanotubes. The catalytic
experiments exhibited 81.9% methyl orange removal after 8 min and 99% after 60 min using 1 mg of the
nanostructured material per every 20 mg/L of the dye.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Textile, food, leather, plastics, dyeing, printing and cosmetic are
among the most contaminant industries due to release of hazardous
efuents containing dyes with complex and highly persistent structures, which may lead to the contamination of the ecosystem. Also,
they can cause severe health problems in human beings, since they
exhibit high biotoxicity as well as potential mutagenic and carcinogenic effects [1,2].
A wide range of technologies are applied in order to remove
dyes from colored efuents, some of them are physical (adsorption,
reverse osmosis, ultraltration), chemical (chlorination, ozonation,
precipitation, chemical oxidation processes, advanced oxidation
processes, photocatalysis) and biological (microbiological or enzymatic decomposition, biodegradation) [3].
Noble metal nanoparticles (e.g. Platinum, Palladium, Rhodium
and Ruthenium) have been successfully used as catalyst for different applications such as chemical synthesis, oil rening, storage of
hydrogen, exhaust gas treatment and wastewater treatment due to

Corresponding author.
E-mail address: claudia.rodriguez@uacj.mx (C.A. Rodrguez Gonzlez).
http://dx.doi.org/10.1016/j.cattod.2016.06.053
0920-5861/ 2016 Elsevier B.V. All rights reserved.

their high specic surface areas, high ordered structures, densely

populated unsaturated surface coordination sites, high oxidation
activity and excellent mechanical and thermal strength [4,5]. The
catalytic properties of metal nanoparticles (NPs) are determined by
shape, size and composition. Shape control of metal NPs can provide a way to adapt their catalytic activity because shape denes
the atomic disposition on the surface and it can maximize their
performance in many catalytic applications [6]. Palladium plays
an important role in a wide number of industrial applications and
these applications demand the use of Pd in a nely divided state
where the size and shape are important parameters to control in
order to maximize its properties [7]. Pd nanocubes have been used
as catalyst to enhance the properties in different studies such as
oxygen reduction [8,9] and glucose sensing [10].
Since their discovery by Sumio Iijima in 1991 [11], carbon nanotubes (CNTs) have attracted great attention in multidisciplinary
areas due to their unique mechanical, electronic and optical properties. In comparison with classical adsorbents such as activated
carbon and clay, CNTs are more attractive because of their favorable
physicochemical stability, high selectivity, and structural diversity. CNTs might be ideal sorbents for the dye removal from water
[1214]. Nanostructures made of carbon structures with noble metals NPs have been used for dye removal obtaining promissory

O. Arciniega Cano et al. / Catalysis Today 282 (2017) 168173

169

Fig. 1. SEM (a) and TEM (bd) images of MWCNTs/Pd nanostructured material.

results [15]. There are several studies where carbon nanotubes are
decorated with Pd NPs. Usually the surface of carbon nanotube
is acid treated in order to create carboxylic, and hydroxyl groups
for subsequent metal nanoparticles anchoring [16]. The principal
problem with this method is that both electrical conductivity and
corrosion resistance of carbon nanotubes would be reduced, and
also can lead to poor dispersion of metal nanoparticles [17]. Another
way to activate carbon nanotubes is by using wrapping materials (polymers, organic materials or surfactants), this non-covalent
method causes less or even no damage to the structure of carbon
nanotubes [18]. The correct organic material selection for wrapping
will result in good metal NPs dispersion on the carbon nanotubes.
In this study, a MWCNTs/Pd nanocubes material was synthetized using a non-covalent method for methyl orange (MO)
removal in aqueous solution under magnetic stirring. MO dye was
chosen as contaminant due to it is a common azo dye. Azoic dyes are
the 50% of the whole dyes used at the industry [19]. The synthesis
of the material, catalytic properties of Pd and MWCNTs adsorption
are discussed.

2. Experimental
2.1. Materials
Multiwalled carbon nanotubes produced by Chemical Vapor
Deposition (MWCNTs, length: 100 nm, diameter: 57 nm, batch #
MKBQ3087V), Cetyltrimethylammonium bromide (CTAB, 99%) and
l-ascorbic acid (AA) were purchased from Sigma-Aldrich; Palladium (II) chloride (PdCl2 , anhydrous, 59.5% as Pd) was obtained

from Alfa Aesar; Methyl orange was obtained from Matheson Coleman & Bell.
2.2. Instrumentation
Morphology and elemental chemical composition of the samples were examined with a Jeol JSM7000F scanning electron
microscope (SEM) and a Jeol JEM-2200FS transmission electron
microscope (TEM) coupled with an energy dispersive spectrometer
(EDS). The XRD patterns of samples were obtained on a Panalytical
XPert PRO powder X-Ray diffraction instrument with Cu K radiation ( = 0.15418 nm) over the range 2 = 10100 at 40 kV and
20 mA. X-ray photoelectron spectroscopy (XPS) was carried out on a
XPS Perkin Elmer spectrometer. Ultraviolet visible spectra (UVvis)
analysis was done on a StellarNet UVvis-NIR spectrometer.
2.3. Preparation of MWCNTs/Pd nanostructure
A non-covalent method using CTAB as surfactant was used to
allow the anchoring and growth of Pd nanocubes on the carbon
nanotubes. First, 1.6 mg of MWCNTs was dispersed in 20 ml of CTAB
(12.5 mM) and then sonicated for 20 min in order to allow the CTAB
adsorption on the MWCNTs. In this process the hydrophobic part of
the CTAB is adsorbed onto the MWCNTs surface by Van der Waals
interaction [17]. Afterwards, 1 ml of H2 PdCl4 (10 mM) was added
under magnetic stirring at 95 C allowing the anchoring of the CTAB
hydrophilic segment to the Pd precursor [17,20]. Lastly, after 5 min
160 l of AA (100 mM) was added to the mixture to produce a spontaneous reduction and stirred for 30 min. The mixture was then

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O. Arciniega Cano et al. / Catalysis Today 282 (2017) 168173

centrifuged at 12,000 rpm and washed two times with deionized

water in order to obtain the decorated MWCNTs.
2.4. Removal experiments
Removal experiments were performed using Methyl Orange
(MO) in order to evaluate the adsorption and catalytic activity of
the MWCNTs/Pd nanostructured material.
The experiments were carried out by adding 1 mg of nanostructures (MWCNTs/Pd, MWCNTs or Pd nanocubes) in 5 ml of MO
solution with a concentration of 20 mg/L. This mixture was maintained at room temperature and continuously stirred. Samples of
few milliliters were taken at regular intervals for UVvis analysis
and the removal efciency calculated as follows:
=

Co Ct
100%
Co

where  (%) is the removal efciency of MO at period of time t, Co

(mg/L) is the initial MO concentration and Ct (mg/L) is the concentration of MO remaining at time t. Ct was calculated:
Ct =

Fig. 2. XRD pattern of MWCNTs/Pd nanostructure.

a
k

where a is the absorbance at a period of time and k is the slope of

the calibration curve of methyl orange.
3. Results and discussion
3.1. Characterization
The functionalization of MWCNTs is essential for the attachment
of metal nanoparticles and the ultrasonic treatment of MWCNTs in
a CTAB solution is an important step for the successful fabrication
of the MWCNTs/Pd nanostructured material [17].
Fig. 1 shows SEM and TEM images where a homogeneous distribution of Pd on MWCNTs is observed. Pd nanocubes with sides the
range of 1525 nm are anchored and well dispersed on the MWCNTs. This means that Pd nanocubes nucleation and their further
growth is not only tangential to the nanotubes surface forming a
perfect cube, but also around wrapping the nanotubes.
The growth of Pd nanocubes onto MWCNTs is caused by the
difference between PdCl4 2 reduction potential and MWCNTs oxidation potential [21]. The formation of nanocubes occurs due to
the presence of bromide in the CTAB. Bromide can alter the order
of surface free energies by chemisorption onto the surface of Pd
seeds [22]. This promotes nanocrystals growth by atomic addition
onto the seeds surface resulting in Pd nanocubes through the formation of {100} facets [23]. Chemisorbed bromide layer can also
prevent the further addition of Pd atoms on the nanocube surface,
preventing the anisotropic growth of the nanocrystal [7].
The XRD analysis of MWCNTs/Pd nanostructured is presented
in Fig. 2, where a strong diffraction peak around 2 = 25.9 that
corresponds to the (002) reection of the hexagonal graphite structure is observed (JCPDS, carbon reference). The diffraction peaks
around 2 at 40.33 , 47.05 , 68.34 , 82.32 and 86.87 correspond
to the (111), (200), (220), (311) and (222) reections of metallic Pd.
The Pd diffraction peaks correspond to a face centered cubic (FCC)
structure (JCPDS, 05-0681).
EDS analysis (Fig. 3) was performed in order to corroborate the
elements in the composite. Table 1 shows the elemental analysis
of the composite where Pd, C and O are present. No evidence of
residual reagents was found determining that the washing process
was successful.
The binding energies of Pd, C and O were examined by XPS
analysis. Fig. 4a shows the Pd 3d core level spectrum in the MWCNTs/Pd nanostrucure. There are two sets of 3d peaks, one related

Fig. 3. EDS image data acquire of the composite.

Table 1
Elemental analysis of the composite.
Spectrum

Pd

1
2

100%
17.70%

77.59%

4.70%

to Pd (0) and the other to Pd (II). The rst set shows Pd5/2 at
335.6 eV and Pd3/2 at 340.5 eV, which could be assigned to Pd metal
[24,25]. Whereas the other set includes Pd5/2 at 337.5 eV and Pd3/2
at 342.5 eV which correspond to PdO2 and PdO binding energies,
respectively [25,26]. The Pd (0) and Pd (II) values are close to the
values reported in the literature.
The C 1s core level spectrum is displayed in Fig. 4b, where
the peak at 284.8 eV corresponds to carbon [27], and the peak
at 285.8 eV could be attributed to CO/Pd according to the literature [28]. It means that a bonding between the MWCNTs and Pd

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171

Fig. 4. XPS of the a) Pd 3d core level, b) C 1s core level, c) O 1s core level of the MWCNTs/Pd nanostructured material.

nanocubes is created. The peak at 287 eV is attributed to C O bond

[29] and the peak at 290.6 to O C O bond [30].
Fig. 4c shows the deconvoluted O 1s core level spectrum. The
peak observed at 531.2 eV is associated with CO/Pd as same as the
C 1s peak at 284.6 eV [28], which corroborate the binding between
Pd and C and/or O, whereas the peak at 533 eV corresponds to C O
bond [31], that union is characteristic of commercial nanotubes.
The peaks at 536 eV and 538 eV are attributed to O C O and O2 /C
bonds, respectively [32,33].
3.2. MO removal
The removal efciency of the MWCNTs/Pd nanostructured
material was evaluated by the decoloration rates of MO in aqueous solution at different time intervals. Fig. 5 shows the UVvis
spectra where the maximum peak of MO at 463 nm was decreasing
gradually and nally almost disappeared after 60 min indicating its
removal.
Decontamination efciency is illustrated in Fig. 6 where it
clearly shows the increment of the efciency when MWCNTs/Pd
nanostructured material is added instead of only MWCNTs. The
decontamination occurs when the dyes organic molecules is

adsorbed by the MWCNTs. This adsorption process is catalyzed

by the presence of Palladium nanocubes. However, Pd nanocubes
do not adsorb or decompose the organic molecules since removal
efciency is nil when only Pd nanocubes are used. Catalysis is
immediately activated when the nanostructures of MWCNTs/Pd
are placed on the MO solution and continues until MO is removed
(99.3% efciency). After 8 min a 83% efciency is reached with
the nanostructured material meanwhile only 44% is observed with
MWCNTs. The nal efciencies after 60 min were 99.31 and 84.87%
for MWCNTs/Pd and MWCNTs, respectively; these results clearly
indicate that the presence of Pd improved the efciency of the MO
removal.
The MWCNTs can adsorb the dye due to their big surface
area, which can lead to a highly efcient contact between the Pd
nanocubes and MO molecules to improve the Pd catalytic efciency
[34].
Several authors [3538] have studied the catalytic activity of Pd
to remove different organic dyes. However, in all these systems,
they use additional compounds (e.g. BH4 , H2 , bentonite, Fe3 O4 )
and the effect of pure Pd is not shown. In this case, the proposed
mechanism that involves hydrogenation and/or the formation of
secondary products cannot be applied since Pd does not remove

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Fig. 5. UVvis spectra of degradation of MO with the MWCNTs/Pd nanostructured material.

Fig. 6. Decontamination efciency of MWCNTs and MWCNTs/Pd nanostructured material.

the MO molecules by itself. However, these authors coincide that

Pd increases the electron ow in the different studied systems.
Therefore, in this case, it is possible that the electron ow in the
MWCNTs is increased in the presence of Pd improving the MO
molecules adsorption. Since it is well established that the MWCNTs
adsorption of MO occurs by Van der Waals forces and electron ow
enhances them.
4. Conclusions
In conclusion, Pd nanocubes anchored onto MWCNTs were successfully synthetized. The CTAB surfactant was the key for the

self-assembly process between the MWCNTs and Pd precursor, and

also for the formation of Pd nanocubes. Furthermore, CTAB not
only serves as functionalizing agent, but also as a stabilizing agent
that controls the size and shape of the metal nanoparticles. The
ascorbic acid combined with the proper CTAB concentration, acts
as reducing agent that favors the formation of Pd nanocubes.
The combination of the catalytic behavior of the Pd nanocubes
and the adsorption properties of MWCNTs resulted in a nanostructured material which improved the decontamination efciency
process on MO dye solutions. This material may be used on different
catalytic applications due to its observed properties.

O. Arciniega Cano et al. / Catalysis Today 282 (2017) 168173

Acknowledgments
Authors thank SEP-CONACYT for the nancial support grant No.
168039 and M.Sc. Carlos Ornelas of CIMAV Mexico for his assistance
with TEM images.
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