Synthesis of mesoporous cerium oxide (CeO2) nanoparticles and effect of cerium precursors on transamidation of acetamide with N-octylamine under solvent-free conditions

Article abstract of DOI:10.1166/jnn.2017.13744

Mesoporous cerium oxide (CeO₂) nanoparticles act as an effective heterogeneous catalyst for the transamidation reaction of amides with amines. The mesoporous CeO₂ nanoparticles were prepared by hydrothermal method using different cerium precursor such as: cerium(III) chloride heptahydrate [CeCl₃? 7H₂O], cerium nitrate hexahydrate [Ce(NO₃)₃ ? 6H₂O], ceric ammonium nitrate [(NH₄) 2Ce(NO₃)₆], and cerium(III) acetate [Ce(C₂H₃O₂)₃ ?_1.5H₂O]. It shows highest catalytic activity for transamidation of acetamide with N-octylamine under solvent free conditions. This is the first example of a heterogeneous catalyst for transamidation using aliphatic amines as substrates. The X-ray diffraction, BET surface area analysis, and FT-IR characterizations of CeO₂ suggested its excellent catalytic activity for transamidation reaction.

Full text of DOI:10.1166/jnn.2017.13744

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Nanoscience and Nanotechnology
Vol. 17, 4983–4988, 2017
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Synthesis of Mesoporous Cerium Oxide (CeO2)
Nanoparticles and Effect of Cerium Precursors on
Transamidation of Acetamide with N-Octylamine
Under Solvent-Free Conditions
Ashish Kumar1ꢀ∗, Manu Sharma2, Rajeev K. Gautam3, Pooja Agarwala4, and Soumen Basu1
1School of Chemistry and Biochemistry, Thapar University, Patiala 147004, India
2Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
3Sustainable Environergy Research Laboratory, Department of Chemical Engineering, Indian Institute of Technology Delhi,
Hauz Khas, New Delhi 110016, India
4Organic Electronics Laboratory, Department of Physics, Indian Institute of Technology Bombay, Powai,
Mumbai 400076, Maharashtra, India
Mesoporous cerium oxide (CeO2ꢀ nanoparticles act as an effective heterogeneous catalyst for the
transamidation reaction of amides with amines. The mesoporous CeO2 nanoparticles were pre-
pared by hydrothermal method using different cerium precursor such as: cerium(III) chloride hep-
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tahydrate [CeCl · 7H O], cerium nitrate hexahydrate [Ce(NO ꢀ · 6H O], ceric ammonium nitrate
IP: 95.181.177.69 On: Wed, 12 Apr 20317 10:23:00
3
2
2
Copyright: American Scientific P3ublishers
[(NH4ꢀ2Ce(NO3ꢀ6], and cerium(III) acetate [Ce(C2H3O2ꢀ3 ·1.5H2O]. It shows highest catalytic activity
for transamidation of acetamide with N-octylamine under solvent free conditions. This is the first
example of a heterogeneous catalyst for transamidation using aliphatic amines as substrates. The
X-ray diffraction, BET surface area analysis, and FT-IR characterizations of CeO2 suggested its
excellent catalytic activity for transamidation reaction.
Keywords: Nanostructures, Transamidation Reaction, Hydrothermal Synthesis, Mesoporous
CeO2, One-Pot Synthesis.
1. INTRODUCTION
primary amides (acetamide) and amines (N -octylamine),
as a transamidation reaction. However, most of them suffer
from low activity, low selectivity or limited scope. Herein,
we report such a procedure utilizing catalytic quantities of
lab made mesoporous ceria to activate the primary amide
and promote a transamidation reaction. During the course
of our on-going effort into developing catalytic synthesis
of amide bonds,4 we envisioned that a catalytic method of
primary amide activation would not only be an exception-
ally atom efficient and clean reaction but it also need to be
highly synthetically useful due to the primary amide group
inertness in presence of many other catalysts and common
organic reagents.
The amide bond is a fundamental part of biological and
synthetic polymers (i.e., proteins and nylons) and also the
most important linkages in industrial and medicinal chem-
istry nowadays. Synthesis of N -alkyl amides have been a
great interest of study because they are synthetic interme-
diates of numerous natural products, pesticides, pharma-
ceuticals, and polymers.1 The most common way to make
an amide bond by using a stoichiometric amount of a cou-
pling reagent with growing focus on green chemistry is
still an expensive and wasteful procedure.2 In the view of
green chemistry, there has been high interest in developing
catalytic methods of amide bond formation, which avoid
using these coupling reagents.3
Transamidation generally requires harsh conditions
(>250 ꢀC), long reaction times and stoichiometric reagents
to cleave the chemically robust amide bond. CeO2 has
acid–base and redox properties and has been used as
an effective catalyst for various organic reactions5ꢀ6
Clearly, there is a lack of an efficient catalytic procedure
for selective synthesis of the secondary amide from simple
∗Author to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2017, Vol. 17, No. 7
1533-4880/2017/17/4983/006
doi:10.1166/jnn.2017.13744
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Transamidation Reaction Over CeO2 NPs Under Solvent-Free Conditions
Kumar et al.
Mesoporous CeO2
[Ce(C2H3O2ꢁ3 · 1.5H2O], tetraethylorthosilicate (TEOS),
cetyl trimethyl ammonium bromide (CTAB), ethanol, were
purchased from Sigma-Aldrich and ammonia solution was
purchased from Fisher scientific were used in synthesis
catalyst. The solutions were made in deionized water.
R=8
O
O
O
O
O
O
R
Ce
Ce
Ce
Ce
Ce
Ce
Ce
Ce
N
H
R=8
R
O
O
NH
N-octyl acetamide
NH2
route 1
N-octyl amine
acetamide
H
R
N
2.1.1. Synthesis of Mesoporous CeO2
NH2
H
H
R
H
O
In a typical synthesis procedure,21 2.0 mmol CeCl3 ·7H2O
was slowly added to the solution containing 4.1 mmol of
L-glycine and 10 mL of H2O under stirring. After that,
10 mL of 0.15 M Na2(CO2ꢁ2 solution was added into
the above solution to obtain white precipitate of cerium
oxalate. Finally, the solution along with precipitate was
transferred into an autoclave, which was tightly sealed and
O
O
N
NH3
O
O
O
O
O
Ce
Ce
Ce
Ce
Ce
Ce
Ce
Ce
Scheme 1. Reaction mechanism of transamidation reaction over meso-
porous CeO2 nanoparticles.
such as; dehydration of alcohols,7–10 alkylation of aro-
matic compounds,11ꢀ12 dimerization of alcohols, aldehydes,
esters13 and carboxylic acids14ꢀ15 to ketones, cyclazation of
diols,16 and reduction of benzoic acid.17
ꢀ
hydrothermally treated at 160 C for 24 h in an oven.
The as-synthesized sample was collected through filtration,
washed successively 3 times with water and ethanol and
ꢀ
then dried at 60 C for 12 h. The sample was finally cal-
In this study we report lab made mesoporous CeO2
acts as a recyclable heterogeneous catalyst for one-
pot N -alkyl amides (N -octyl acetamide) formation from
amides (acetamide) and amines (N -octylamine) at 160 ꢀC,
which provides a new and green catalytic system for
N -alkyl amides synthesis with high yields (75% to 94%)
under solvent-free conditions. Catalytic studies show that
our method is particularly effective for the transamida-
tion reaction. The possible reaction mechanism is proposed
in Scheme 1, which supports the transamidation of pri-
ꢀ
cined at 360 C in air for 1 h, to yield yellowish ceria
powder and named as C1.
In this case as the hydrated acetate (Ce(C2H3O2ꢁ3 ·
1.5H2O) used as cerium precursor.22 6 g hexadecylamine
as a surfactant was added to 35 ml of a 50% aque-
ous ethanol solution. Inorganic precursor: surfactant molar
ratio of 2 was achieved by adding the required quantity of
cerium precursor. The mixture was stirred for 1 h at room
ꢀ
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temperature and placed in an oven at 60 C for 2 days
(ambient atmospheric conditions). The precipitate formed
IP: 95.181.177.69 On: Wed, 12 Apr 2017 10:23:00
mary amide with amine as rate-limiting step. This reaction
mechanism provides a reason why the present catalytic
system gives high selectivity.
Copyright: American Scientific Publishers
was washed with ethanol–water mixture and harvested by
filtration. The solid product was again washed with deion-
ized water and dried in air at 120 ꢀC for 6 h. Subsequently
described as the as-synthesiꢀzed material and then calcined
at temperatures from 360 C in air for 4 h and named
as C2.
The high-surface area mesoporous CeO2 was prepared
by using Ce(NO3ꢁ3 ·6H2O as cerium precursor19 with sur-
factant cetyltrimethyl ammonium bromide (CTAB) as tem-
plating agent. A solution of NaOH (2 g) in 300 mL dis-
tilled water was added to a stirred solution of Ce(NO3ꢁ3 ·
6H2O (4.3 g) and CTAB (2.2 g) in 200 mL distilled water.
The pH of the resulting mixture is approximately 12. The
As prepared high surface area mesoporous ceria can be
used in various important applications such as; catalysis,
sensors, and fuel cells. Hence, cerium oxide (CeO2ꢁ is an
important rare earth oxide and has the potential of becom-
ing a very useful material.18–20 The rare earth oxide mate-
rials are of interest as designing catalysts since they are
less expensive in comparison to precious metal catalysts
like platinum and palladium.
In view of organic synthesis and green chemistry, it is
important to study CeO2-catalyzed ꢀorganic reactions fur-
ther at lower temperatures (<200 C). In this work we
reported that mesoporous CeO2, synthesized by different
precursors of cerium, as a effectively catalyzes transamida-
tion of acetamide with N -octylamine to yield correspond-
ing N -octyl acetamide in high yields at 160 ꢀC under
solvent-free conditions.
ꢀ
mixture was then allowed to react at 90 C, aꢀnd the pre-
cipitate obtained was filtered after aging at 60 C for 12 h
and washed with ꢀhot water. The resultant yellow powder
ꢀ
was dried at 110 C for 10 h and then calcined at 360 C
in air for 4 h and named as C3.
Mesoporous ceria with high specific surface area has
been prepared using ceric ammonium nitrate as cerium
precursor23 and non-surfactants organic compounds glu-
cose, acryl amide via hydrothermal method. In a typical
experiment, glucose (0.005 mol), acryl amide (0.0075 mol)
and ceric ammonium nitrate (2.5 mmol) were dissolved
into deionized water (40 mL) one by one with magnetic
stirring. Then ammonia solution (25 wt%) was added drop-
wise to the solution until the pH value was about 10. After
2. EXPERIMENTAL DETAILS
2.1. Materials
All the chemicals were used of analytical grade with-
out any further purification. All the cerium precur-
sor viz cerium(III) chloride heptahydrate [CeCl3 · 7H2O],
cerium nitrate hexahydrate [Ce(NO3ꢁ3 · 6H2O], ceric
ammonium nitrate [(NH4ꢁ2Ce(NO3ꢁ6], cerium(III) acetate
4984
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Kumar et al.
Transamidation Reaction Over CeO2 NPs Under Solvent-Free Conditions
stirring for 5 h, the mixture was transferred into a teflon-
lined autoclave and kept at 150 ꢀC for 48 h, then the auto-
clave was allowed to cool to room temperature. After that
the solution was filtered and the precipitate was washed
with deionized water and alcohol three times. Finally, the
obtaineꢀd sample was dried at 80 ꢀC overnight and calcined
at 360 C for 4 h in air and named as C4.
for the organic reactions were of analytical grades and
purchased commercially and were used without further
purification.
3. RESULTS AND DISCUSSION
3.1. Characterization of Catalysts
3.1.1. X-ray Diffraction (XRD)
It can be seen from Figure 1, the XRD patterns of
the calcined mesoporous CeO2 samples as-prepared by
hydrothermal methods using different cerium precursor.
The presence of several narrow and intensive diffraction
peaks indicates that the precursor is well crystallized. All
diffraction peaks can be indexed to a face-centered cubic
phase ceria (JCPDS 34-0394) and no signals of impurities
are detected. XRD shows main peaks at 2ꢅ values of 28.4ꢀ,
32.9ꢀ, 47.3ꢀ, and 56.2ꢀ corresponding to planes of (111),
(200), (220) and (311) with interplanar spacing of 3.12,
2.72, 1.91 and 1.63 Å, respectively. The intensities and
positions of the diffraction peaks are in good agreement
with the literature data. Extremely broad reflections for the
as-prepared sample indicating that the crystallite sizes are
very small. On the basis of the width of the (111) diffrac-
tion peak, the mean crystallite size of the mesoporous ceria
samples were calculated by the Scherrer equation to be
about 4–10 nm and shown in Table I.
2.2. Catalyst Characterizations
X-ray diffraction (XRD) patterns of the catalysts were
recorded on a Rigaku Miniflex (M/s. Rigaku Corpo-
ration, Japan) using Ni filtered Cu-Kꢂ radiation (ꢃ =
0ꢄ15406 nm). The crystallite size of gold was calculated
by using Debye–Scherrer equation and the phase iden-
tification was done with the help of the JCPDS files.
Fourier transform infrared (FT-IR) spectra of the cata-
lysts were taken on the IR (Model: GC-FT-IR Nicolet
670) spectrometer by KBr disc method under ambient
condition. Scanning electron microscopy (SEM) analysis
was observed in Hitachi S-520 SEM unit. The BET sur-
face area were obtained from N2 adsorption–desorption
isotherm (Autosorb I/Quantachrome instruments, USA at
−196 ꢀC), where the samples were first out gassed at
ꢀ
300 C to ensure a clean surface prior to the construc-
tion of adsorption isotherms. The Barrett–Joyner–Halenda
(BJH) method was used to calculate the pore–size distribu-
tion from the desorption branch of the isotherm (Autosorb
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3.1.2. Fourier Transform Infrared (FT-IR)
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I/Quantachrome, USA).
The FT-IR spectra of the as-synthesized calcined sam-
Copyright: American Scientific Publishers
ple are displayed in Figure 2. The one near 3410 cm−1
is due to the physically adsorbed water (−OH features
at 3400 cm−1ꢁ and carbonate (adsorbed bidentate car-
bonate signals at 1500 and 1280 cm−1ꢁ features are
observed. There appears a broad adsorption peak at around
400 cm−1, which can be attributed to the Ce–O stretching
band, according to the literature.24
2.3. Catalytic Experiments
A typical procedure for transamidation of acetamide with
N -octylamine is as follows: mesoporous CeO2 (25 mg,
5.8 mol% Ce with respect to acetamide) was added to
the mixture of acetamide (2.5 mmol) and N -octylamine
(5.0 mmol) in a reaction vessel equipped with a condenser
under N2 atmosphere. The resulting mixture was vigor-
ously stirred at 160 ꢀC. The reaction mixture was analyzed
by GC. Conversion and yield of the products were deter-
mined based on acetamide and N -octyl acetamide using
pentadecane as an internal standard. Once the reaction was
completed, the CeO2 catalyst was separated by centrifuga-
tion. In the catalyst recycling experiments, the separated
catalyst was washed with acetone three times and calcined
ꢀ
in air at 300 C for 1 h. For measurement of the iso-
lated yields, the reaction of amine (2.6 mmol) and primary
amide (2.5 mmol) was carried out. After full conversion
of the primary amide was confirmed by GC, the catalyst
was separated by filtration. The crude product was purified
ꢀ
by evaporating the filtrate at 70 C to remove the unre-
acted amine. The resulting products were identified by GC,
GC-MS.
The GC (Shimadzu GC-2014) and GC-MS (HP-5973
quadruple) analysis were carried out with a DB-wax
123-7033 (Agilent) capillary column (0.32 mm i.d., 30 m
long) using nitrogen as the carrier gas. All chemicals used
Figure 1. XRD patterns of mesoporous CeO2 samples as-prepared by
hydrothermal method using different cerium precursor.
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Transamidation Reaction Over CeO2 NPs Under Solvent-Free Conditions
Kumar et al.
Table I. BET surface area and pore size distribution data of mesoporous
ceria samples prepared by hydrothermal method using different cerium
precursor.
C1
C2
CeO2
samples
BET surface
area (m2/g)
Total pore
Pore
Crystallite
volume (cc/g) diameter (nm) size (nm)a
C1
C2
C3
C4
235
205
195
162
0.35
0.41
0.46
0.48
4.4
4.1
3.3
3.2
4ꢄ60
9ꢄ37
9ꢄ36
10ꢄ21
C3
C4
Note: aCrystallite size determined from XRD.
3.1.3. Scanning Electron Microscopy (SEM)
The morphologies and architectures of mesoporous CeO2
samples as-prepared by hydrothermal methods using dif-
ferent cerium precursor were investigated by SEM (Fig. 3).
Figure 3. SEM images of mesoporous CeO2 samples as-prepared by
hydrothermal method using different cerium precursor.
3.1.4. BET Surface Area and Pore Size
Distribution Measurements
To characterize the porosity of the mesoporous CeO2
samples (Table I), N2 adsorption analysis was carried
out. Figure 4(a) displays the N2 adsorption–desorption
isotherms and the corresponding pore size distribution
curve (Fig. 4(b)) calculated from the adsorption branch by
the BJH method. The obtained ceria sample exhibits the
isotherm of type IV, and the adsorption branch shows an
uptake of adsorbed volume at low relative pressure (P/P0ꢁ
The results show that mesoporous CeO2 (C1) has the high-
est conversion and yield of N -octyl acetamide, indicating
that mesoporous CeO2 is the most effective catalyst for
transamidation compared to other CeO2.
(a)
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of 0.1–0.4, which indicates the existence of mesopores.
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The BJH pore size distribution curve displays a wide pore
Copyright: American Scientific Publishers
diameter distribution from 3 to 5 nm. The pore volume and
the specific surface area of the obtained ceria for sample
C1 are 0.35 cm3/g, and 235 m2/g, respectively.
3.2. Catalytic Properties for Transamidation Reaction
Transamidation hardly proceeded without a catalyst. Using
different cerium precursor of metal oxides, conversion and
yield for transamidation reaction were reported in Table II.
(b)
Figure 2. FT-IR spectra for mesoporous CeO2 samples as-prepared by
Figure 4. (a) N2 adsorption–desorption isotherms and (b) BJH pore size
hydrothermal method using different cerium precursor.
distribution for mesoporous CeO2 (C1) sample.
4986
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Kumar et al.
Transamidation Reaction Over CeO2 NPs Under Solvent-Free Conditions
Table II. Transamidation of acetamide with N-octylamine to N-octyl acetamide catalyzed by mesoporous CeO2 with different cerium precursor.
O
O
Mesoporous CeO2
-NH3
NH2
NH2
N
H
acetamide
N-octylamine
N-octylacetamide
Synthesis methods
Catalyst (Mesoporous CeO2ꢁ
Time (h)
Conversion (%)
Selectivity (%)
Yield (%)
C1
C2
C3
C4
1
1
1
1
98
95
85
83
96
92
96
90
94
87
82
75
160 ꢀC, Hydrothermal, [CeCl3 ·7H2O]
60 ꢀC, Hydrothermal, [Ce(C2H3O2ꢁ3 ·1.5H2O]
90 ꢀC, Hydrothermal, [Ce(NO3ꢁ3 ·6H2O]
160 ꢀC, Hydrothermal, [(NH4ꢁ2Ce(NO3ꢁ6]
Notes: Reaction conditions: acetamide (2.5 mmol), N-octylamine (5.0 mmol), mesoporous CeO2 (25 mg), T = 160 ꢀC in N2. Yield of N-octyl acetamide was determined
by GC.
mesoporous CeO2 (Table II). The reaction by mesoporous
CeO2 (C1) for 1 h resulted in 98% conversion and the
yields of N -octyl acetamide was 94% with 96% selec-
tivity compared to other CeO2 catalysts. Among all the
catalysts, mesoporous CeO2 (C1) showed the highest cat-
alytic reactivity for the direct amidation of acetamide with
N -octylamine to N -octyl acetamide, hence; found to be
the best catalyst for this reaction in terms of activity and
selectivity.
As shown in Figure 5, it is suggested that CeO2 cat-
alyzed reaction proceeds via route 1 (Scheme 1) and the
secondary amide formation from primary amide, where
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amine (transamidation) is the rate-limiting step. Note that
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this reaction mechanism is different from that of the
Copyright: American Scientific Publishers
homogenous catalysts reported by Murahashi et al.25 and
Figure 5. Plots of conversion/selectivity/yield versus mesoporous CeO2
catalysts for transamidation of acetamide. Reaction conditions: acetamide
(2.5 mmol), N-octylamine (5.0 mmol), mesoporous CeO2 (25 mg),
T = 160 ꢀC in N2.
Williams et al.,3ꢀ26 in which they have proposed that one-
pot alkylamidation of nitrile. In contrast, the reaction by
CeO2 proceeds by route 1 (Scheme 1) avails high selec-
tivity to N -octyl acetamide.
3.2.1. Comparison of Different Cerium Precursors Over
Transamidation Reaction
3.2.2. Reaction Mechanism
First, one-pot synthesis of N -octyl acetamide from
acetamide with N -octylamine at 160 ꢀC under solvent
free condition was chosen as a test reaction to compare
the catalytic activity of different cerium precursors of
The effect of reaction time on the mesoporous CeO2
catalyzed one-pot secondary amidation of acetamide
with N -octylamine was investigated as shown in
Figure 6. At the initial stage, acetamide was immediately
Figure 6. Plots of conversion and yield versus reaction time for transamidation of acetamide. Reaction conditions: acetamide (2.5 mmol),
N-octylamine (5.0 mmol), mesoporous CeO2 (25 mg), T = 160 ꢀC in N2.
J. Nanosci. Nanotechnol. 17, 4983–4988, 2017
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Transamidation Reaction Over CeO2 NPs Under Solvent-Free Conditions
Kumar et al.
consumed to produce the corresponding N -octyl acetamide
(94% yield at t = 1 h). Then, the yield of N -octyl
acetamide decreased with time. After 5 h, the yield of
N -octyl acetamide reached >88%, and any by-products
were detected by GC. These results indicate the one-pot
secondary amide formation proceeds by following consec-
utive steps (in Scheme 1); the secondary amide formation
from primary amide and amine. Note there are no other
products formed for transamidation reaction catalysed by
mesoporous CeO2.
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We have demonstrated that mesoporous CeO2 acts as
an effective heterogeneous catalyst for the transamida-
tion reaction of amides with amines. This novel catalysis
provides a clean, convenient and practical route for the
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50, 4262 (2009).
Conflict of Interests
The authors declare that there is no conflict of interests
regarding the publication of this.
Acknowledgments: Authors are thankful to DST
(Grant No: SB/FT/CS-178/2013), New Delhi for financial
assistance.
Received: 1 March 2016. Accepted: 23 June 2016.
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J. Nanosci. Nanotechnol. 17, 4983–4988, 2017