CoFe2O4-decorated carbon nanotubes for the dehydration of glucose and fructose

Article abstract of DOI:10.1039/c6nj00501b

Multi-walled carbon nanotubes (CNTs) decorated with different ferrites have been synthesized and successfully used under heterogeneous conditions in the dehydration of fructose. In addition, inverse spinels, such as cobalt ferrite (CoFe₂O₄) and magnetite (Fe₃O₄), decorated on CNTs showed better performance than normal spinel such as zinc ferrite (ZnFe₂O₄)-decorated CNTs. The catalyst could be easily recycled and the protocol was simple. Moreover, functionalized CNTs were characterized using various methods, including Raman spectroscopy, X-ray diffraction and Transmission Electron Microscope analysis. The crystallite size of CoFe₂O₄-decorated CNTs was nearly 20 nm.

Full text of DOI:10.1039/c6nj00501b

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CoFe O Decorated Carbon Nanotubes for Dehydration of
2
4
Glucose and Fructose
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
Kalluri V S Ranganath*, Mahendra Sahu, Melad Shaikh, Pramd Kumar Gavel,
b
c
a
DOI: 10.1039/x0xx00000x
Kiran Kumar Atyam , Santimoy Khilari, Pradip Das
www.rsc.org/
Multi-walled carbon nanotubes (CNTs) decorated with different ferrites have been synthesized and
successfully used under heterogeneous conditions in the dehydration of fructose. In addition inverse
spinels like cobalt ferrite (CoFe
2
O
4 3 4
) , magnetite (Fe O ) decorated on CNTs showed better performance
than normal spinel like zinc ferrite (ZnFe
2
4
O ) decorated CNTs. The catalyst could be easily recycled
and make the protocol simple. Moreover, functionalized CNTs were characterized by using various
methods including Raman Spectroscopy, X-ray Diffreaction (XRD) and Transmission Electron
Microscope (TEM) analysis. The crystallite size of CoFe
2
O
4
decorated CNTs shows nearly 20 nm.
7
Industry favours a heterogeneous catalysis over homogeneous catalysis due to ease of separation of the catalyst. Surface
due to the advantage of recovery and recycling. Heterogeneous functionalization of carbon materials with carboxyl group,
catalysis has been around for a long time, but has still much to amino group or hydroxyl group provides an efficient way of
groom. Due to their high thermal conductivity, high surface significantly improved performance of CNTs due to the
area, carbon nanotubes (CNTs) have evoked high interest not enhanced compatibility and surface reactivity. All such
only for heterogeneous catalytic applications, but also in many functionalized groups of finds vital role in many catalytic
8
important field such as fuel cell, lithium battery, composite reactions of homogeneous and heterogeneous type. Besides,
1
-3
materials and electric device. While most of the CNTs can be especially both carboxylic and sulfonic groups containing CNT
used in various applications, there has been increasing demand groups finds applications extensively for phenol oxidation
9
a
for the functionalization of CNTs and consequently reactions , and also in agar conversion, oxygen reduction
9
b
functionalized CNTs find a use in wide range of applications reactions.
4
including catalysis. In addition, CNTs distinguish themselves The hydroxymethylfurfural (HMF) which has been used in
from other carbon materials such as activated carbon and plastics, pharmaceuticals, and fine chemicals is mainly derived
carbon nanofibers because of well defined tubular structure from petrochemicals at present, but it also could be obtained by
5
,6
10
formed by graphene layers. CNTs decorated with magnetite the dehydration of various monosaccharides.
Recently,
nanoparticles are attractive particularly in heterogeneous
several remarkable catalytic systems have been explored,
remarkably using acid catalysts in the dehydration of
1
1-12
sacharadies.
In addition heterogeneous catalytic systems
a
Guru Ghasidas University (A Central University), Department of Chemistry, Koni,
Bilaspur 495009 (India)
have also been developed for the dehydration of sugar
b
13-15
Dept. Of Materials Sciences, Indian Institute of Technology, Kharagpur
moieties.
However, in most of the cases, along with HMF,
c
Dept. Of Metallurgical and Materials Science, RGUKT-Basar-504101
other products like levulinic acid are also producing.
Nevertheless, only a few catalytic systems have been realized to
display only HMF as a sole product.
.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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J. Name., 2013, 00, 1-3 | 1
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Table 1 Ferrite-CNTs Catalyzed Dehydration of Fructose and Glucose
In the present communication, we are reporting the synthesis of
HMF with high selectivity (up to 99%) using ferrite decorated
CNTs form fructose (Scheme 1).
Entry
Catalyst
Reactant
Time(h) Conversion Selectivity
(%)
(%)
1
2
3
4
5
6
7
8
9
CNT
Fructose
Fructose
Fructose
Fructose
Glucose
Fructose
Glucose
Fructose
Fructose
Fructose
Glucose
Fructose
24
15
15
6
N.R
28
-
-
CNT-COOH
CNT-NH2
32
-
Fe
3
3
O
O
4
10
-
Fe
4
10
8
N.R
34
-
CoFe
2
O
4
4
4
78
-
Scheme 1 Ferrite Decorated CNTs Catalyzed Dehydration of Fructose
CoFe
2
O
12
24
6
N.R
N.R
22
2
ZnFe O
-
The multi walled CNTs and (CNT), amino functionalized
CNT-Fe
3
O
4
98
a
b
a
b
1
1
0
1
CNT-CoFe
CNT-CoFe
2
O
4
4
4
8
75, 74 , 75
99,98 ,99
CNTs (CNT-NH
2
) were purchased from (diameter 12.9 nm
m) from nanoshell laboratories, Haryana.
2
O
10
8
64
98
-
and length 3-12
ꢀ
12
CNT-ZnFe O
N.R
2
The carboxylic acid functionalized CNTs (CNT-COOH),
Reactions were performed using 20.0 mg of catalyst, 180.0 mg of fructose, DMF:
.0 mL at 80 °C. The reaction mixture was analyzed by using UV spectroscopy
ferrite decorated CNTs were prepared according to the
3
1
6,17
b
nd
c
rd
literature procedure.
with Carrez solutions. II cycle. III cycle.
Initially, the unfunctionalized CNTs was employed as
versatile heterogeneous catalyst for the dehydration of the
fructose to HMF at 80 °C in DMF and the results are shown in
the Table 1. The dehydration of fructose could not takes place
(
Table 1, entries 8 & 12). Substantial increase in catalytic
power of CoFe -CNT is highly remarkable in the
dehydration of fructose up to 75% conversion with 99%
selectivity to HMF. The low activity of ZnFe is attributed
2
O
4
2
O
4
1
8
with unfunctionalized CNTs (Table 1, Entry 1). Very little
conversion was observed with acid and base functionalized
CNTs without HMF formation (Table 1, entrys 2& 3). Later the
dehydration of fructose and glucose has been carried with
different ferrites like Fe O , CoFe O and ZnFe O4 and the
due to the diamagnetic property of the material and also may be
electro negativity difference between the cobalt, iron and zinc.
The higher activity of CoFe O -CNT and Fe O -CNT facile
2
4
3
4
3
+
2+
2+
3+
redox reaction Fe to Fe and Co to Co in an easier way
because of the synergetic effect of CNT and ferrites and thus
reaction proceeds in a smooth way. In the present study CNTs
not only acts as a simple support but also promoting the
reaction along with ferrites because of having extreme
conducting properties. Moreover easy removal of the catalyst
from the reaction mixture makes the procedure very simple for
heterogeneous catalytic reactions (Table 1, entry 10). Although
the rate of reaction is slow with glucose, however the
selectivity towards HMF, up to 98% is highly remarkable
3
4
2
4
2
results are shown in the table 1 (entries 4-7). The inverse
spinels like Fe and CoFe promotes the dehydration of
fructose than normal spinel ZnFe . Notably, less conversion
of fructose using magnetite as a catalyst in the dehydration of
fructose at 80 C (10%) without HMF production whereas with
CoFe O 34% conversion with 78% selectivity of HMF was
3
O
4
2 4
O
2
O
4
°
2
4
obtained. Of particular note is that no catalytic conversion of
glucose was observed using Fe and CoFe . Since ferrite
decorated CNTs have been using as an attractive materials
3
O
4
2 4
O
(
Table 1, entry 11). The significant increase in the activity of
CoFe on CNT is due to its quite stability towards acidic and
environmental conditions whereas Fe O is quite reactive. The
1
9
20
towards electro catalysis , adsorbents
and also as
2
O
4
2
1
electrochemical sensor are motivated to synthesize ferrite
decorated CNTs. Therefore, CNTs were decorated with various
ferrites which possess different magnetic properties like
paramagnetic Fe O , diamagnetic ZnFe O and electromagnetic
3
4
acidic hydroxyl groups of sugar molecule and also product
HMF, might be having strong interaction with Fe , which
3
O
4
3
4
2
4
may lead to the reactivity in the dehydration reaction compared
CoFe
2
O
4
were explored as recyclable catalysts in the
to CoFe O4
2
dehydration of fructose (Table 1, entries 9 & 12). However, in
the presence of magnetite-CNT, the rate of fructose dehydration
increases significantly up to 22% conversion with 98%
The ferrite decorate CNTs were characterized by using Raman
spectroscopy (Fig. 1). The Raman spectra exhibit the D and G
bands typical of MWCNT. The two main typical graphite bands
are present in the Raman Spectrum of MWCNTs bundles: the
selectivity, Table 1, entry 9). Remarkably, neither ZnFe O4
2
2 4
alone nor ZnFe O -CNT catalyzed the dehydration of fructose.
-1
band at 1573 cm (G band) assisted to the in-plane vibration of
2
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the C — C bond, typical of defective graphite-like materials respective ferrites. It was found that average crystallite size of
-1
and the band at 1343 cm (D band) activated by the presence of Fe O , CoFe O and ZnFe O4 is 16.4nm, 20.0 and 18.6 nm
3
4
2
4
2
disorder in carbon systems. The Raman spectrum also exhibits respectively (Fig. S3-S6). The magnetite has been conformed to
-1
a band at 2677 cm called the G’ band and attributed to the mix phase in the crystal phase of cubic Fe
overtone of the D band. The ID/IG ratio of the Fe , CoFe Goethite (Fe . H O) because of transformation of little
and ZnFe O on CNT are 0.74, 0.81, 0.72 respectively. The magnetite to goethite under washing with CNTs, whereas
3 4
O along with
3
O
4
2
O
4
2
O
3
2
2
4
orientation of the octahedral and tetrahedral sites of ferrites on cobalt ferrite exhibits cubic crystal structure.
CNTs might have caused the change in defective sites. In Besides, the ferrite decorated CNTs were also characterized by
addition to that, some of the nanoparticles of ferrites can adopt using Scanning Electron Microscope (SEM) analysis.
the internal shape of the CNTs and accommodate them along Agglomerations of metal oxide particles along the wall of CNT
the tube axis leading to enhancement of the magnetic were observed (Fig. 2). The SEM images indicating-metal
anisotropy, which affects the increase the defective sites and oxide particles (with some agglomerated state) set at open
hence the ratio. Further, the Raman spectra indicate that the surface of lump MWCNTs which may be for catalysis
radial breathing mode (RBM) of ferrite decorated CNTs below applications.
-1
5
00 cm and broadened “G” line shows the presence of
2
2
metallic character.
2 4
Fig.2. SEM of CoFe O decorated CNT
Apart from other methods, the all the ferrites on CNTs were
also characterized by TEM, which indicates the crystallite size
2 4 3 4 2 4
is around 20 nm (Fig.2). The CoFe O , Fe O , ZnFe O
decorated CNTs are having the average diameter of 8.5 nm, 12
and 11.6 nm respectively.
3 4 2 4 2 4
Fig.1. Raman Spectra of a) CNTs b) Fe O on CNT c) ZnFe O on CNT d) CoFe O on CNT
In addition, the catalysts were also characterized by using X-
ray diffraction (XRD). The crystallinity and structure of three
spinels are confirmed by powder XRD. The peak position and
relative intensity of all diffraction peaks for all the three samples are
in close approximations with their respective reference pattern
matched. In addition theta is equal to 26.2 indicates the presence of
carbon nanotubes. The presence of (220), (311), (422), (511)
revealed the cubic spinel phase of ferrites. The (002), (100), (101),
(
004), and (110) peaks are related to the presence of the CNTs. The
004) and (101) reflections are also due to flat graphitic layers,
(
residual carbon particles, and the defect of the CNTs. The
crystallite size was calculated using Scherer equation
2 4 3 4 2 4
Fig.3. HR-TEM of (a) CoFe O on (b) Fe O (c) ZnFe O on CNT
D=0.89λ/Bcosθ by taking maximum intensity peak FWHM for
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1
0
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In conclusion, ferrite decorated CNTs have been successfully in
the dehydration of sugar moieties. Moreover decoration of
CNTs with ferrites acts as versatile heterogeneous catalysts
with recyclability in the dehydration of fructose. Further work
will try to understand the mechanism and possibility of
asymmetric reactions will be of great interest.
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To a suspension of functionalized CNT (20.0 mg) in DMF (3.0
mL) was added fructose (180.0 mg). The reaction mixture was
2
b
c
heated to 80
°
C with vigorous stirring. After completion of the
,
reaction monitored by UV and HPLC (C-18 column,
water:DMF/methanol 9.5:0.5:1, 1.0 mL/min flow rate), the
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New Journal of Chemistry
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DOI: 10.1039/C6NJ00501B
CoFe O Decorated Carbon Nanotubes for Dehydration of Glucose and
2
4
Fructose
Kalluri VS Ranganath*, Mahendra Sahu, Melad Shaikh, Pramd Kumar Gavel, A. Kiran Kumar ,
Santimoy Khilari, Pradip Das
Carbon nanotubes have been decorated with various ferrites of normal and inverse spinels
were characterized by using XRD, Raman, SEM and TEM analysis. The inverse spinel
decorated CNTs were successfully evaluated in the dehydration reactions.