Nickel and cobalt nanoparticles modified hollow mesoporous carbon microsphere catalysts for efficient catalytic reduction of widely used dyes

Article abstract of DOI:10.1039/c6ra22498a

Recently, with increasing consciousness of environmental protection, Chemists are focusing on green chemistry, which allows the transformation of highly toxic organic wastes into reusable or low-toxicity compounds under mild reaction conditions. In this w

Full text of DOI:10.1039/c6ra22498a

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Nickel and Cobalt nanoparticles modified hollow mesoporous
carbon microspheres catalysts for efficiently catalytic reduction of
widely used dyes
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Meng Tian, Chunxu Dong, Xueliang Cui, Zhengping Dong*
www.rsc.org/
Recently, with increasing consciousness for environment protection, Chemists are focusing on green chemistry, which
allows the transformation of highly toxic organic wastes into reusable or low-toxicity compounds under mild reaction
conditions. In this work, hollow mesoporous carbon microspheres (h-MCM) with ultrahigh surface area were synthesized
by co-sol-emulsion-gel method and were used as supports for Ni and Co nanoparticles (NPs). The prepared nanocatalysts
(Ni/h-MCM and Co/h-MCM) have high Ni and Co NPs dispersion on the surface of the h-MCM as well as in its hollow core.
The prepared catalysts exhibit high surface area, mesoporous shell and accessible interior space. These properties benefit
for enhancing the catalytic activity of the prepared catalysts. In the catalytic reduction of methylene blue, methyl orange,
and rhodamine B, the obtained Ni/h-MCM and Co/h-MCM exhibited excellent catalytic activity as compared with other
reported catalysts. This work may promote to design non-precious metal based nanocatalysts for environmental catalysis.
TM NPs in the mesopores with desirable dispersion. Therefore,
researchers have focused their research on mesoporous carbon
materials, which meet the requirements for NP supports attribute
Introduction
In recent years, catalysts based on noble metal nanoparticles
NMNPs), especially Au, Pd, Pt and Ru NPs have attracted
to their large surface area, tunable pore structure, excellent
(
1
1, 12
1
-4 chemical and mechanical stability.
The recently reported hollow
considerable attention due to their excellent catalytic properties.
However, the scarce resources and the high cost of the noble
metals greatly limit the catalytic application of the NMNPs based
catalysts. Researchers nowadays are trying their best to develop
new types of non-noble metal catalysts that exhibit excellent
catalytic performance to replace the NMNPs based catalysts. The
widespread and low cost transition metal (TM), especially Co and Ni
have attracted considerable interest in catalysis applications
because they can catalyze the hydrogenation, reduction, oxidation
mesoporous carbon microspheres (h-MCM) has mesoporous hollow
structure, low density, high surface area, accessible interior space
1
3-15
and graphitic carbon framework.
These properties make h-
MCM ideal support for fabricating TM NPs based catalysts with high
dispersion.
On the other hand, the widely used organic dyes including
methylene blue (MB), methyl orange (MO), and rhodamine B (RhB)
1
6-18
are high toxicity, because they are carcinogenic and mutagenic.
5
-9
The discharge of organic dyes polluted water to the environment
can cause serious water pollution. Therefore, it is urgent to develop
efficient methods to treat the dye-polluted wastewater. And till
now, several methods such as adsorption, oxidation, the Fenton
reaction, as well as an electrochemical process, have been reported
for the treatment of dye-polluted wastewater. However, there are
some drawbacks of these methods, for example they are not quite
and hydrogen evolution reactions. However, because of the high
surface energy, the naked TM NPs are apt to agglomerate during
the catalytic process, and subsequently greatly reducing their
1
0
intrinsic activity. Thus it is a critical challenge to stabilize the TM
NPs on catalyst supports while retaining their nanoscale properties.
2 3 2
Although the commercially available Al O , SiO and active carbon
can be used as catalyst supports for fabrication Co and Ni based
catalysts, but their low surface area, micropore structure still can
lead the aggregation of the TM NPs and decrease the catalytic
activity of the prepared catalysts. It is well known that the
mesoporous materials with high surface area and large pore volume
can provide a large surface area as well as efficiently immobilize the
19-24
effective and cost-effective.
Compare with the above
mentioned methods, the catalytic reduction treatment method
exhibits high efficiency for reducing the toxicity of the organic dyes,
2
5, 26
attribute the C=N or N=N can be throughly hydrogenated.
Other than the NMNPs based catalysts, TM NPs based catalysts
such as Cu NPs, Co NPs and Ni NPs based catalysts have also been
2
7-30
reported for the catalytic reduction of organic dyes.
However,
a.
College of Chemistry and Chemical Engineering, Gansu Provincial Engineering
developing simple and efficient approach to prepare TM NPs
modified mesoporous carbon materials catalysts with high surface
Laboratory for Chemical Catalysis, Zhongwei High Technology Research
Institute, Lanzhou University, Lanzhou 730000, PR China.
Electronic Supplementary Information (ESI) available: [details of any area and good TM NPs dispersion is highly desired but remains a
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
challenge.
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Fig. 1. Roman spectra of the h-MCM, Ni/h-MCM and Co/h-MCM (a), XRD spectra of the h-MCM, Ni/h-MCM and Co/h-MCM (b).
Based on the above considerations, here we prepare the h-MCM the catalytic reduction process was started. The progress of the
materials with ultrahigh surface area using the co-sol-emulsion-gel reaction was monitored by UV-Vis spectroscopy.
3
1
method. Ni and Co NPs were successfully supported on the h- Characterizations
MCM with high dispersion. The novel Ni/h-MCM and Co/h-MCM
Transmission electron microscopy (TEM, Tecnai G2 F30) and
nanocatalysts exhibit excellent catalytic activity for the reduction of
the organic dyes MB, MO, and RhB. In addition, the prepared
nanocatalysts can be magnetically recycled and reused for at least
five times without obvious decrease in the catalytic activity. This
Scanning electron microscopy (SEM, JSM-6701F) were used to
characterize the morphology of the h-MCM, Ni/h-MCM and Co/h-
MCM catalysts. The powder X-ray diffraction (PXRD, Rigaku D/max-
study provides
a useful platform based on low-cost and
magnetically recyclable Ni and Co based nanocatalyst for efficient
reduction of organic dyes.
Experimental
Materials
The reagents that were used for the preparation of h-MCM
including Tetraethyl orthosilicate (TEOS), Cetyltrimethyl ammonium
bromide (CTAB), Resorcinol, and N
Tianjin Heowns Biochemical Technology Co., Ltd.. Ni(NO
Co(NO and the organic dyes MB, MO and RhB, were supplied by
2 4 2
H ·H O were purchased from
3 2
) ,
3 2
)
the Sinopharm Chemical Reagent Co. Ltd (China). Other reagents
and solvents were of analytical grade and used without further
purification.
Preparation of the h-MCM, Ni/h-MCM and Co/h-MCM
According to the similar co-sol-emulsion-gel procedure reported by
3
1
Cao et al. , the h-MCM was successfully obtained. For the
preparation of the Ni/h-MCM nanocatalyst, the procedure was
typically: 100 mg of h-MCM and 75 mg of Ni(NO
dissolved in 30 mL H O. After stirring for 6 h, the mixture was
rotary dried, and then the obtained composite was annealed from
3 2 2
) ·6H O were
2
o
o
-1
3
4
0 C to 400 C with a ramp rate of 5 °C min and held for 2 h at
o
2 2
00 C under H /N (V:V=1:2, 90 mL/min) atmosphere. Then obtain
the Ni/h-MCM nanocatalyst. The fabrication procedure for the
Co/h-MCM was the same as the Ni/h-MCM nanocatalyst.
Catalytic reduction of organic dyes MB, MO and RhB
Fig. 2. SEM (a) and TEM (b) images of the h-MCM, TEM image
of Ni/h-MCM (c), HRTEM image of the Ni NPs (d) and Ni NPs
size distribution of Ni/h-MCM (e), TEM image of Co/h-MCM (f),
HRTEM image of the Co NPs (g) and Co NPs size distribution of
Co/h-MCM (h).
Typically, 20 μL aqueous solution of the organic dye (0.01 M) was
mixed with 2.7 mL of deionized H
2
O, followed by adding 250 μL of a
(0.1 M). And then, the
freshly prepared aqueous solution of NaBH
4
-1
prepared nanocatalyst (15 mg mL ) were added (20 μL for catalytic
reduction of RhB and MO, 5 μL for catalytic reduction of MB), and
2
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2
Fig. 3. The N sorption isotherms of h-MCM, Ni/h-MCM and Co/h-MCM (a), and the pore size distribution of h-MCM, Ni/h-MCM and
Co/h-MCM (b).
o
o
o
2
400), Raman spectrometer (Jobin Yvon Lab Ram HR evolution) and three sharp peaks at 2θ=44.5 , 52 and 76.4 , respectively assigned
33
a micromeritics ASAP 2010 (USA) were used to investigate the to the Ni(111), Ni(200) and Ni(220) characteristic peaks. In the
physical properties of the samples. The magnetic measurement of Co/h-MCM, two characteristic peaks of metallic Co (Co(111) and
3
4
Ni/h-MCM and Co/h-MCM catalyst was performed using a quantum Co(220)) can also be clearly observed. Thus, the XRD results
design vibrating sample magnetometer (VSM). An Agilent Cary 5000 demonstrate that the Ni and Co exist as metallic NPs and
UV-Vis spectrophotometer was utilized for monitoring the extent of successfully been supported on the h-MCM support.
the catalytic reduction of MB, MO and RhB.
To investigate the morphology of the prepared samples, SEM and
TEM characterizations have been performed (Fig. 2). As can be seen
in Fig. 2a that the spherical h-MCM NPs have an average diameter
of about 150 nm. The TEM image displayed in Fig. 2b confirms that,
the h-MCM has a hollow core and mesoporous shell. The shell
thickness is about 20-30 nm. When adsorbed with Ni(NO ) and
Results and Discussion
Materials Characterizations
3
2
The h-MCM was prepared through the co-sol-emulsion-gel
Co(NO ) , and respectively reduced under H atmosphere, the Ni/h-
31
3 2
2
process, carbonization and HF etching process. And then the Ni/h-
MCM and Co/h-MCM were obtained by the reduction of the
MCM and Co/h-MCM nanocatalysts were obtained. Fig. 2c and f
show the TEM image of the Ni/h-MCM and Co/h-MCM
nanocatalysts, respectively. The Ni and Co NPs were successfully
modified on the h-MCM as well as in the hollow core. There is
almost no NPs aggregation, indicating the Ni and Co NPs were
highly dispersed. Furthermore, the h-MCM support almost
maintained its original structure after the modification process,
indicating the adsorption and reduction process did not damage the
h-MCM structure. In the HRTEM image of the Ni/h-MCM, the
Ni(111) lattice d= 0.204 nm can be clearly observed (Fig. 2d). Fig. 2g
shows the Co(111) lattice of d= 0.205 nm. In addition, the average
particle size of the Ni NPs is about 5 nm (Fig. 2e), and the Co NPs
have an average particle size of 7 nm (Fig. 2h), as measured from
the TEM images. The EDS spectra displayed in Fig. S1 indicate the
composition of the Ni/h-MCM and Co/h-MCM nanocatalysts.
3 2 3 2
Ni(NO ) and Co(NO ) adsorbed h-MCM respectively. Fig. 1a shows
the Raman spectra of the h-MCM, Ni/h-MCM and Co/h-MCM, two
characteristic peaks named D band and G band can be clearly
−
1
observed. The D band located at 1317 cm can be assigned to the
defect sites in the hexagonal framework of graphite materials, while
the G band can be assigned to sp2 hybridized carbon atoms of the
3
2
D G
graphite structure. The relative I /I values for h-MCM, Ni/h-MCM
and Co/h-MCM are 1.08, 1.08,and 1.06, these values reveal that the
h-MCM, Ni/h-MCM and Co/h-MCM graphite framework have
comparatively defect sites, should mainly exist as C=O and COOH.
These functional groups in the h-MCM, Ni/h-MCM and Co/h-MCM
may act as the condensation centers, and beneficial for the
2
+
2+
D G
adsorption of the Ni and Co ions. From the I /I values, it can be
seen that after being supported with Ni and Co NPs, the framework
of h-MCM has almost not been changed. The XRD patterns of the
prepared samples were displayed in Fig. 1b. The broad peak located
The N adsorption-desorption isotherms of the h-MCM, Ni/h-MCM
2
and Co/h-MCM nanocatalysts were shown in Fig. 3a. The three
samples all exhibit type-IV isotherms. From the loops, it can be seen
o
between 20-30 is assigned to the graphitic interlayer (002) peak of
that at relatively high pressure (P/P
0 2
>0.6), steep increase of N
the h-MCM support. Compared to the h-MCM, the Ni/h-MCM has
absorption was observed, indicating that all the samples exhibit
Table 1. Textual parameters of the h-MCM, Ni/h-MCM and Co/h-MCM.
2
-1
3
-1
Entry
Sample
h-MCM
S
BET (m g )
1058.9
921.5
Pore Volume (cm g )
Pore Size (nm)
1
2
3
1.8
1.3
6.7
5.9
5.6
Ni/h-MCM
Co/h-MCM
666.1
1.15
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prepared nanocatalyst because it can be simply separated from the
reaction mixture by using an external magnet. Fig. 4 inset shows the
separation procedure of the Ni/h-MCM and Co/h-MCM
nanocatalysts.
Reduction of MB, MO and RhB
Organic dyes including MB, MO and RhB that are widely used in
manufacturing industries are well-known environmental pollutants.
Various noble metals such as Pd, Au, Ag and Pt based catalysts have
been developed for the purpose of disposing these environmental
36, 37
pollutants.
While the current work utilizes the cost-effective
and widespread metallic Ni and Co to prepare Ni/h-MCM and Co/h-
MCM nanocatalysts to catalytic reduction the MB, MO and RhB
organic dyes pollutants.
Fig. 4. Room temperature magnetization curves of the Ni/h-
MCM and Co/h-MCM. Inset is the magnetic manipulation of
the nanocatalysts.
Initially, the selected organic dyes, bule colored MB, yellow colored
MO and pink colored RhB have the absorption peak at λMB=663nm,
λMO=465nm, λRhB=554nm. When only the reductant NaBH4 was
introduced into the dyes solution, the color of the dyes solution can
maintain a long time, indicating that without an effective catalyst
the reduction reaction cannot be occurred. When the Ni/h-MCM
nanocatalyst was added into the dyes solutions containing excess
3
5
mesoporous structure. The Brunauer-Emmett-Teller (BET) surface
2
-1
areas are 1059.8, 921.5 and 666.1 m g , respectively for h-MCM,
Ni/h-MCM and Co/h-MCM; and the pore volumes for the three
3
-1
samples were found to be 1.8, 1.3, 1.15 m g , respectively. The
results indicated that the obtained Ni/h-MCM and Co/h-MCM
nanocatalysts exhibit ultrahigh surface areas and large pore
volumes. The decrease of the BET surface areas and the pore
volumes for the Ni/h-MCM and Co/h-MCM nanocatalysts compared
with h-MCM was probably attributed to the modification of the Ni
and Co NPs on the support. Moreover, the pore size distribution of
the h-MCM, Ni/h-MCM and Co/h-MCM nanocatalysts were
described in Fig. 3b. Slightly decrease of the pore size in Ni/h-MCM
and Co/h-MCM nanocatalysts compared with h-MCM can be
observed, mainly due to the Ni and Co NPs that grafted in the
mesopore of the h-MCM support. In addition, the textual
parameters of the prepared samples were presented in Table 1, and
the changing trends in BET surface areas, pore volumes and pore
size of the prepared samples before and after modifying Ni and Co
NPs can be clearly seen.
NaBH , the reaction started as observed through the UV-vis spectra
4
(
Figs. 5a-c). Fig. 5a shows that the maximum absorption peak of MB
at 663 nm gradually decreased and finally disappeared in 537 s. And
also the blue color mixture changed to a colourless solution,
indicating the completion of the reduction reaction. Figs. 5b,c show
the absorption peaks change trend of the catalytic reduction of the
MO and RhB respectively. From which it can be observed that, the
reduction of the MO and RhB can be completed in 550 s and 335 s,
respectively. These results reveal that the Ni/h-MCM nanocatalyst
can effectively catalyze reduction the organic dyes. Like the Ni/h-
MCM, the Co/h-MCM nanocatalyst can also effectively catalyze
reduction the above mentioned organic dyes. The UV-vis spectra
displayed in Figs. S2a-c clearly demonstrated that the Co/h-MCM
nanocatalyst can completely catalytic reduction of the MB, MO and
As is well known that, metallic Ni and Co NPs exhibit magnetism.
Thus, the prepared Ni/h-MCM and Co/h-MCM nanocatalysts also
have the magnetism property as confirmed by the magnetization
curves (Fig. 4). The magnetism property is very useful for a
Fig. 5. Successive UV-vis spectra for the reduction of MB (a),
4
MO (b) and RhB (c) by NaBH with Ni/h-MCM nanocatalyst. (d)
Kinetic curve for the reduction of MB, MO and RhB catalyzed
by Ni/h-MCM nanocatalyst.
Scheme 1. The mechanism of the catalytic reduction of organic
dyes (MB, MO, RhB).
4
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reduction reactions could be considered as the pseudo-first order
kinetics. The linear relationship between the the ln(C /C ) vs the
reaction time also confirms the pseudo-first order reaction kinetics
Fig. 5d and Fig. S2d). Using the equation (1), all the rate constants
t
0
(
K estimated from the slopes of the linear rela-tionship are given in
Table 2. Furthermore, the catalytic activity comparation of the Ni/h-
MCM and Co/h-MCM nanocatalysts with the other reported noble
metal catalysts and non-precious metal catalysts are also listed in
Table 2. The Ni/h-MCM and Co/h-MCM nanocatalysts have higher
catalytic activity than other non-precious metal based catalysts in
the catalytic reduction of organic dyes, and also comparatively
2
5,
catalytic activity with other reported noble metal based catalysts.
3
8-42
The excellent catalytic activity of the Ni/h-MCM and Co/h-MCM
Fig. 6. The reusability of the Ni/h-MCM and Co/h-MCM
nanocatalysts for thecatalytic reduction of MB.
nanocatalysts was mainly attributed its unique structures: ultrahigh
surface area, mesoporous shell, hollow core and the highly
dispersed active sites, these factors may enhance the ease
accessibility of the active sites and enhance the mass transfer
effect, thus enhance the catalytic activity of the prepared
nanocatalysts.
RhB organic dyes in 353 s, 338 s and 185 s, respectively.
The reaction mechanism invoked for catalytic reduction of MB, MO
and RhB organic dyes over the Ni/h-MCM and Co/h-MCM
nanocatalysts was detailed illustrated in Sheme 1, which invoked a
Furthermore, the reuseability and stability of the Ni/h-MCM and
Co/h-MCM nanocatalysts were also investigated. As the prepared
nanocatalysts exhibit magnetism property, they were easily
recovered from the reaction mixture by using an external magnet.
Using the catalytic reduction of MB as the probe reaction, both of
the Ni/h-MCM and Co/h-MCM nanocatalysts can be reused for at
least 5 runs without an obvious decrease in the catalytic activity (Fig.
1
6, 26, 27
-
two-electron transfer process.
4
Firstly, BH was absorbed on
the metal NPs (Ni or Co NPs), and transferred a hydride to the
surface of the metal NPs to form the Ni-H or Co-H bonds; Secondly,
the organic dye molecules (MB, MO and RhB) were absorbed onto
the surfaces of the Ni/h-MCM or Co/h-MCM nanocatalyst, and two
active H atoms on the surface of the metal NPs tend to be captured
by the organic dye molecule. Finally, the C=N or N=N bonds were
hydrogenated and the reduction products were desorbed from the
metal NPs and reactivated the Ni/h-MCM and Co/h-MCM
nanocatalysts.
6
). And from the TEM images of the reused Ni/h-MCM and Co/h-
MCM nanocatalysts (Fig. S3), it can be seen that the morphology of
the reused nanocatalysts was well maintained.

Ê
Ÿ
Ê
Conclusions
Ǝ ÂÄ ʠ ʡ Ɣ Ǝ ÂÄ ʠŸ ʡ Ɣ §Ê (1)
̉
̉
In summary, we have successfully prepared the novel Ni and Co
modified mesoporous carbon microspheres catalysts, named Ni/h-
MCM and Co/h-MCM. The obtained nanocatalysts have been
carefully characterized and their catalytic activity in the catalytic
reduction of organic dyes MB, MO and RhB have been detailed
investigated. The prepared Ni/h-MCM and Co/h-MCM
nanocatalysts can also be recovered easily using an external magnet
from the reaction mixture and reused without obvious decrease in
catalytic activity, indicative of its reusability and stability.
4
In the organic dyes catalytic reduction reaction, the NaBH used was
excess as compared with the dyes, thus it should maintain constant
during the reduction reaction. Therefore, the organic dyes catalytic
Table. 2. Compare catalytic activity for the reduction of MB,
MO, and RhB between the current work and some other
catalysts reported in the literatures.
-
1
Samples
Dyes
MB
MO
RhB
MB
MO
RhB
MB
MO
MB
MO
RhB
MB
RhB
MB
MB
K
(s )
Ref.
The conclusions section should come in this section at the end
of the article, before the acknowledgements.
0.011
0.003
0.005
0.023
0.003
0.006
0.017
0.002
0.006
0.04
This
work
Ni/h-MCM
Acknowledgements
This
work
Co/h-MCM
We thank the financial support from the Fundamental Research
Funds for the Central Universities (lzujbky-2015-14 and lzujbky-
Crystalline palladium
nanoparticle
38
2
015-21).
Fe
3
O
4
@C@Au
39
25
References
MnFe
2
O
4
@SiO @AgMRC
2
0.02
1
Y. Hartadi, D. Widmann and R. J. Behm, ChemSusChem, 2015, 8,
56-465.
0.002
0.0003
0.006
0.037
4
Au–CNx
Cu microsphere
Ni nanotube arrays
40
41
42
2
M. Martin-Martinez, L. M. Gómez-Sainero, J. Bedia, A. Arevalo-
Bastante and J. J. Rodriguez, Appl. Catal. B: Environ., 2016, 184,
55-63.
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
3
4
5
6
K. Ghosh, R. A. Molla, M. A. Iqubal and S. M. Islam, Green.
Chem., 2015, 17, 3540-3551.
Ciambelli and J. A. Navio, Appl. Catal. B: Environ., 2016, 188,
134-146.
R. Fang, H. Liu, R. Luque and Y. Li, Green. Chem., 2015, 17, 4183- 38 V. Vilas, D. Philip and J. Mathew, Mater. Chem. Phys., 2016, 170,
188. 1-11.
S. Rosler, J. Obenauf and R. Kempe, J. Am. Chem. Soc., 2015, 137, 39 Z. Gan, A. Zhao, M. Zhang, W. Tao, H. Guo, Q. Gao, R. Mao and E.
998-8001. Liu, Dalton Trans., 2013, 42, 8597-8605.
X. Jin, M. Zhao, C. Zeng, W. Yan, Z. Song, P. S. Thapa, B. 40 T. Bhowmik, M. K. Kundu and S. Barman, Rsc Adv., 2015, 5,
4
7
Subramaniam and R. V. Chaudhari, ACS Catal., 2016, 6, 4576-
583.
V. Polshettiwar, B. Baruwati and R. S. Varma, Green. Chem., 2009,
1, 127-131.
C. van der Wijst, X. Duan, I. Skeie Liland, J. C. Walmsley, J. Zhu, A.
Wang, T. Zhang and D. Chen, Chemcatchem, 2015, 7, 2991-2999.
M. R. Nabid, Y. Bide and Z. Habibi, Rsc Adv., 2015, 5, 2258-2265.
0 X. Li, C. Zeng, J. Jiang and L. Ai, J. Mater. Chem. A, 2016, 4, 7476-
38760-38773.
4
41 Y. Zhang, P. Zhu, L. Chen, G. Li, F. Zhou, D. Lu, R. Sun, F. Zhou and
C.-p. Wong, J. Mater. Chem. A, 2014, 2, 11966-11973.
42 X.-Z. Li, K.-L. Wu, Y. Ye and X.-W. Wei, Crystengcomm, 2014, 16,
4406-4413.
7
8
1
9
1
7482.
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
1 H. Zhang, O. Noonan, X. Huang, Y. Yang, C. Xu, L. Zhou and C. Yu,
Acs Nano, 2016, 10, 4579-4586.
2 S. Mohapatra, S. R. Rout, R. K. Das, S. Nayak and S. K. Ghosh,
Langmuir, 2016, 32, 1611-1620.
3 D.-S. Yang, C. Kim, M. Y. Song, H.-Y. Park, J. C. Kim, J.-J. Lee, M. J.
Ju and J.-S. Yu, J. Phys. Chem. C, 2014, 118, 16694-16702.
4 Y. Dai, H. Jiang, Y. Hu, Y. Fu and C. Li, Ind. Eng. Chem. Res., 2014,
53, 3125-3130.
5 L. Chen, X. Cui, M. Wang, Y. Du, X. Zhang, G. Wan, L. Zhang, F.
Cui, C. Wei and J. Shi, Langmuir, 2015, 31, 7644-7651.
6 M. Atarod, M. Nasrollahzadeh and S. M. Sajadi, J. Coll. Interf. Sci.,
2
016, 462, 272-279.
7 U. Kurtan, M. Amir and A. Baykal, Appl. Surf. Sci., 2016, 363, 66-
3.
7
8 X. S. Wang, J. Liang, L. Li, Z. J. Lin, P. P. Bag, S. Y. Gao, Y. B. Huang
and R. Cao, Inorg. Chem., 2016, 55, 2641-2649.
9 E. M. Yusni and S. Tanaka, Electrochimica Acta, 2015, 181, 130-
1
38.
0 M. S. Tehrani and R. Zare-Dorabei, Rsc Adv., 2016, 6, 27416-
7425.
1 D. Tao, Y. Higaki, W. Ma and A. Takahara, Chem Lett, 2015, 44,
572-1574.
2 S. Ou, J.-P. Zheng, G.-Q. Kong and C.-D. Wu, Dalton Trans., 2015,
4, 7862-7869.
2
1
4
3 H. S. Oliveira, L. D. Almeida, V. A. A. de Freitas, F. C. C. Moura, P.
P. Souza and L. C. A. Oliveira, Catal. Today, 2015, 240, 176-181.
4 A. Mizrahi and I. M. Litaor, Desalin. Water Treat., 2014, 52,
5
264-5275.
5 U. Kurtan, M. Amir, A. Yildiz and A. Baykal, Appl. Surf. Sci., 2016,
76, 16-25.
3
6 P. Veerakumar, S. M. Chen, R. Madhu, V. Veeramani, C. T. Hung
and S. B. Liu, ACS Appl. Mater. Interf., 2015, 7, 24810-24821.
7 Z.-Z. Wang, S.-R. Zhai, B. Zhai and Q.-D. An, Eur. J. Inorg. Chem.,
2
015, 2015, 1692-1699.
8 T. Kamal, S. B. Khan and A. M. Asiri, Cellulose, 2016, 23, 1911-
923.
1
9 A. Chinnappan, A. H. Tamboli, W.-J. Chung and H. Kim, Chem.
Eng. J., 2016, 285, 554-561.
0 Y. Yang, Y. Ren, C. Sun and S. Hao, Green. Chem., 2014, 16, 2273-
2280.
3
3
1 J. Hou, T. Cao, F. Idrees and C. Cao, Nanoscale, 2016, 8, 451-457.
2 Z. Dong, C. Dong, Y. Liu, X. Le, Z. Jin and J. Ma, Chem. Eng. J.,
2
015, 270, 215-222.
3 W. L. Zhen, J. T. Ma and G. X. Lu, Appl. Catal. B: Environ., 2016,
90, 12-25.
4 X. Z. Li, Y. Y. Fang, L. X. Wen, F. Li, G. L. Yin, W. M. Chen, X. C. An,
J. Jin and J. T. Ma, Dalton Trans., 2016, 45, 5575-5582.
5 Z. Shi, W. Jiao, L. Chen, P. Wu, Y. Wang and M. He, Micropor.
Mesopor. Mater., 2016, 224, 253-261.
3
3
3
3
3
1
6 W. Zuo, G. Chen, F. Chen, S. Li and B. Wang, Rsc Adv., 2016, 6,
28774-28780.
7 V. Vaiano, G. Iervolino, D. Sannino, J. J. Murcia, M. C. Hidalgo, P.
6
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