La–Sn oxide nanocatalyst: Efficient materials for the synthesis of cyclohexanones

Article abstract of DOI:10.1016/j.molliq.2016.09.050

A series of La–Sn oxide catalysts were synthesized by facile low temperature hydrothermal procedure. La–Sn oxide nanoparticles were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM) coupled with energy di

Full text of DOI:10.1016/j.molliq.2016.09.050

La-Sn nanocatalysts: Efficient materials for the synthesis of cyclohexanones
Ikram Ahmad, Sher Bahadar Khan, Abdullah M. Asiri, Muhammad
Nadeem Arshad, Shahid Ali Khan
PII:
DOI:
Reference:
S0167-7322(16)31526-4
doi:10.1016/j.molliq.2016.09.050
MOLLIQ 6327
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
12 June 2016
24 August 2016
18 September 2016
Please cite this article as: Ikram Ahmad, Sher Bahadar Khan, Abdullah M.
Asiri, Muhammad Nadeem Arshad, Shahid Ali Khan, La-Sn nanocatalysts: Effi-
cient materials for the synthesis of cyclohexanones, Journal of Molecular Liquids (2016),
doi:10.1016/j.molliq.2016.09.050
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La-Sn nanocatalysts: Efficient materials for the synthesis of
cyclohexanones
Ikram Ahmada,b, Sher Bahadar Khana,b*, Abdullah M. Asiria,b, Muhammad Nadeem
Arshada,b, Shahid Ali Khana,b
aCenter of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz
University, Jeddah, Saudi Arabia
bChemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah 21589,
Saudi Arabia
* Correspondence address: E-mail: sbkhan@kau.edu.sa
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Abstract
A series of La and Sn catalysts were synthesized by facile low temperature hydrothermal
procedure La-Sn nanoparticles and characterized by x-ray powder diffraction (XRD), field
emission scanning electron microscopy (FESEM) coupled with energy dispersive
spectroscopy (EDS), Fourier transform infrared (FTIR) and UV-visible spectroscopy. The
FESEM and XRD analysis revealed the growth of nanoparticles with homogeneous
morphology, high crystallinity and particle size of ˂ 20 nm. The synthesized nanoparticles
showed excellent catalytic activity for the synthesis of cyclohexanones. The effect of
variations in La and Sn contents on the progress of reaction was estimated by yield of the
products. The recovery of the catalysts after the completion of reactions was also assessed.
Key words: La-Sn nanoparticles; Nano-catalyst; Cyclohexanone; Efficient catalyst
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1. Introduction
Conventional heterogeneous catalysts usually consist of less active or “inert” solid carriers’
and active metal phases in order to enhance available working area and material
consumption. In these catalysts the metals usually show the dimensions of numerous to a
few tens of nanometers,1-3 their further processing may proceed by ion-exchange,
impregnation, activation , pulverization ,coating, , drying, heat-treatment, reduction,
precipitation and rewashing,4. This protocol can disperse the active nanoparticles or metal
clusters on the carriers. But the classical procedure for catalyst mainly depends on the
proficiency of process implementers. The effective catalyst is generally formed through
conscientious trial-and-error experiments. Insufficient materials analysis and complicated
procedures of developed routes for active catalysts are secrets of the developers for viable
interests.4, 5 The topography, facet, defect, size, shape, and compositional distinction play
vital role on the efficiency of heterogeneous catalysts.1-3
The excellent catalytic efficiency of tin and palladium catalysts for dehydrogenation of
alkanes fascinated most of the researchers in last decades.4-6 Considerable improvements
have been done experimentally and theoretically.7-10 The bimetallic catalysts as Sn-Pt rely
generally on the Pt and Sn interactions, and especially on the state of Sn.5 It is recommended
that electronic density of Pt is altered by tin by transfer of positive charge from Sn+ or to the
other electronic structure in Sn-Pt alloys.11 It is also reported that tin decreases the surface
dimensions of Pt which helps to inhibit the isomerization, coke formation and hydro-
cracking by keeping the Pt sites clean from coke.12 However, the stabilities of the catalysts
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still demand more attention. Consequently, it is vital to enhance the stability of Sn-Pt
catalysts for short chain paraffin conversion.
About stability issues, developments were made and investigators reported that catalytic
performance of Sn-Pt based catalysts can be improved by adding rare earth metals as they
can augment thermal stabilization and reinforce metal-rare earth oxide interaction
efficiently.13-15 It has been observed that the catalytic stability of Sn-Pt/Al2O3 can
significantly improve by adding lanthanum in propane dehydrogenation reaction because of
the reticence of coke formation and reduction of Sn oxidation in the existence of La.16
Catalytic properties selectivity and stability of Sn-Pt, Na/ZSM-5 in propane dehydrogenation
process was improved by induction of La.17 The performance of La addition illustrates that it
could amend the characteristics of acid and metal function and as a consequence, the
examination of La advertiser on catalyst is very crucial. Cyclohexanone derivatives play a
vital role in many systems in organic synthesis and in industry.18-20 Besides the important
organic precursor, these have good antimicrobial activities such as anti-convulsant, anti-
implantation, anti-asthmone, anti-bacteria, anti-fungal, and herbicidal.21-26
The preparation of cyclohexanone has been investigated in the presence of different
catalysts.22-24 The cascade process of ethyl acetoacetate and benzaldehyde in the presence of
sodium carbonate,23,24 piperidine,25 triethyl amine,26 potassium carbonate polyethylene
glycol,27 bismuth trichloride.25 The same process in the presence of sodium hydride-butyl
lithium14 and another group studied similar reaction in the presence of potassium
tetracarbonyl-hydridoferrate.28 In recent methods cyclohexanone were reported by
Knoevenagel condensation followed by Michael addition28. But the use of high temperatures,
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expensive metal precursors, catalysts that are harmful to environment and longer reaction
times limit the use of these methods. Therefore, the search for a better catalyst for the
synthesis of cyclohexanone derivatives is of prime importance. Too many reactions are
reported which give good yield in the presence of catalyst and also affect the reaction
kinetics and mechanism.
In present investigation, we report the synthesis, characterization and catalytic effect
of La-Sn nanoparticles (La-Sn/i, La-Sn/ii and La-Sn/iii) in one-pot tandem-sequence. These
nanoparticles were prepared in large quantity possessing a spherical shape. La-Sn/i, La-Sn/ii
and La-Sn/iii have average diameter of ~38 ± 10 nm. These catalyst were employed for the
synthesis of cyclohexanones. Reaction kinetics, yield of respective products and activity
factor of catalysts were determined. La-Sn nanoparticles showed efficient result with good
recovery of catalyst.
2. Experimental
2.1. Reagents and Chemicals
Lanthanum carbonate, tin carbonate, ethylacetoacetate, ammonium acetate,
piperidine, ethanol, and aldehydes and all other chemicals were purchased form Sigma-
Aldrich. All the reagents were of analytical grade and were used without further purification.
2.2. Synthesis of La-Sn nanoparticles
The aqueous solutions of lanthanum carbonate (0.1 M) and tin carbonate (0.3 M)
were mixed together and titrated by NaOH (0.5 M) solution to increase the pH above 10.0.
This high basic solution was then kept for stirring at 60.0 °C for 12 hours. Finally the product
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was obtained by washing the precipitate several times with ethanol. The precipitate was dried
°
and named as La-Sn/i. The La-Sn/I was calcined at 450.0 C for 6 hours and named as La-
Sn/ii. For the preparation of La-Sn/iii, the same amounts of precursor materials were mixed
with 5 wt% of carbon black and follow the same procedure which was used for the synthesis
of La-Sn/i.
2.3. Physical Characterization of La-Sn nanomaterial
JEOL Scanning Electron Microscope (JSM-7600F, Japan) was used to analyze the
morphology of the prepared material while the crystallography was studied by Thermo
Scientific, ARLservice X-ray diffractometer. For compositional and optical studies of the
nanoparticles, FT-IR and UV spectrum were record by a Nicolet (iS50 FT-IR) FT-IR
spectrometer and UV (Evolution 300 UV-VIS) spectrometer.
2.4. Catalytic activity
The catalytic activity of the prepared nanomaterial was determined by applying in the
tandem Knoevenagel condensation followed by aldol condensation reaction of aromatic
aldehyde with ethyl acetoacetate in the presence of piperidine as base (Scheme 1) and
proposed mechanism showed in scheme 2. The reaction was carried out at room temperature
and pressure (RTP), monitored by thin layer chromatography (TLC) and product was
purified by column chromatography. As the two of main product were crystalline so the
confirmation was done by single crystal XRD technique and non-crystalline were confirmed
by NMR. The reaction was repeated, monitored by TLC and determined the reaction kinetics
by UV (Evolution 300 UV-VIS). Same protocol was applied for different catalysts and
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determined the catalytic activity by calculating slope. Activity factor of catalysts was
compared and yield of product was calculated to sort out the best catalyst.
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O
R
O
O
O
O
O
Sn-La,/i,ii&iii
Pipyridine, r.t.
O
O
O
R
H
OH
Scheme 1: Catalyzed tandem Knoevenagel condensation followed by Aldol condensation
reaction.
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H
O
O
O
O
O
O
O
O
O
R
O
H
H
H
O
H
O
O
-H2O
Knovengeal
Condensation
O
O
R*
H
R
H
O
OH
H
O
O
H
H
O
R
O
O
H
O
O
O
O
O
O
O
R
Sn-La,/i,ii&iii
H
O
O
H
CH2
O
R
O
Sn-La,/i,ii&iii
O
O
O
O
Aldol condensation
O
O
O
R
O
H
H+
H
O
O
O
O
O
O
R
H
O
H
O
CH3
H
O
N
R* =
Cl
O
and
,
,
CH3
,
O
H
Scheme 2: Proposed Mechanism for the synthesis of cyclohexanones.
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3. Results and Discussion
3.1 \Physical characterization of La-Sn nanoparticles
The FESEM images of the synthesized La-Sn nanoparticles are presented in Fig. 1
were utilized to explore the morphology and size of all La-Sn nanoparticles. It is evident
from the FESEM images that La-Sn/i, La-Sn/ii and La-Sn/iii are grown in the form of
particles. These nanoparticles are grown in large quantity possessing a spherical shape. La-
Sn/i, La-Sn/ii and La-Sn/iii nanoparticles are grown in the size of ˂ 20 nm.
Figure: 1. Typical FESEM images of Ln-Sn/i, Ln-Sn/ii and Ln-Sn/iii.
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Figure: 2.Typical EDS spectrum of Ln-Sn/i, Ln-Sn/ii and Ln-Sn/iii.
The elemental composition was determined from the EDS spectrum. The EDS analysis
indicating the presence of O, Ln and Sn elements as showing in Fig. 2.
The crystallographic information of the all La-Sn based nanoparticles was
corroborated by X-ray diffraction (Fig. 3 (a)). All the characteristic diffraction peaks
coincided with those for well-crystalline hexagonal La2O3 as well as tetragonal SnO2.34,35 The
SnO2 peaks at 2θ values of 26.6°, 33.9°, 38.0°, 51.7°, and 65.9° can be associated with (110),
(101), (200), (211) and (112) respectively. The La2O3 peaks at 2θ values of 27.3°, 31.6°,
45.5°, and 56.6° can be associated with (100), (101), (110), and (112) respectively.
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Figure: 3.Typical (a) XRD pattern and (b) FTIR spectrum of Ln-Sn/i, Ln-Sn/ii and Ln-Sn/iii.
The chemical structure of La-Sn/i, La-Sn/ii and La-Sn/iii nanoparticles was also
examined by FTIR analysis which was recorded in the range of 400 ~ 4000 cm−1 and shown
in Fig. 3 (b). An intense broad peak exhibited at 3350 cm-1 recommended the presence of OH
stretching vibration. The very intense bands observed at 525 and 621 cm−1 were attributed to
M–O (M = Sn, La) and M-O-M bonds, respectively. Supplementary peaks centered at 1369,
-
1636 and 3412 cm−1 were assigned to CO2, CO3 , H2O absorbed from the environment,
respectively36,37
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2
Figure: 4.Typical UV spectrum of (a) Ln-Sn/i (b) Ln-Sn/ii, (c) Ln-Sn/iii and (αhν) vs. hν plots
of (d) Ln-Sn/I, (e) Ln-Sn/ii, (f) Ln-Sn/iii.
The band gap was determined from UV-Vis data. The catalyst Ln-Sn (i, ii and iii) indicating a
band gap at 4.2, 4.15 and 4.2 eV as depicted in Fig. 4d-4f respectively.
3.2. Catalytic activity
The catalytic efficiency of La-Sn/i, La-Sn/ii and La-Sn/iii nanoparticles were evaluated in
tandem reaction for the synthesis of cyclohexanone derivatives at room temperature using
different aromatic aldehydes, ethyl acetoacetate and piperidine in ethanol as the starting
materials. The experiment was carried out at room temperature. The aromatic aldehyde (3
mmol), piperidine (3 mmol), ethylacetoacetate (6 mmol) and 10 mol% of La-Sn/i or La-Sn/ii
or La-Sn/iii nanoparticles were taken in reaction flask having 2ml ethanol and stirred for a
certain period of time. The reaction was monitored by collecting the sample after each
periodically to observe reaction kinetics through UV/VIS spectrophotometer. The product
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was also confirmed by TLC. When the reaction completed, the contents were filtered and
washed with ethanol to recover the catalyst, the components of filtrate were purified by
column chromatography. The main fraction of column crystallized out after 24 hrs in 5%
ethyl acetate ethanol solvent system and the structure was examined by single crystal XRD
and NMR. The % yields were calculated which are given in Table 1. The formation of
product was also monitored by UV/vis analysis. After treating the reactants in the presence
of catalyst, the UV absorbance was gradually increased with the passage of time. Figure 5 is
showing the UV analysis of the products for catalysts La-Sn/i,La-Sn/ii and La-Sn/iii,
respectively.
4
3
2
1
0
4
3
2
1
0
0
min
La-Sn/ii
0
min
10 min
25 min
40 min
55 min
70 min
85 min
100 min
125 min
150 min
175 min
200 min
10 min
25 min
40 min
55 min
70 min
85 min
100 min
125 min
150 min
175 min
200 min
La-Sn/i
a
b
300
400
500
300
400
500
Wave length (nm)
Wave length (nm)
1.0
0.5
0.0
4
0 min
La-Sn/iii
10 min
25 min
40 min
55 min
70 min
85 min
100 min
125 min
150 min
175 min
200 min
3
2
1
0
c
Product
300
400
500
300
400
500
Wave length (nm)
Wave length (nm)
Figure: 5. Absorbance spectra of the synthesis of Cyclohexanone derivatives through tandem
Knoevenagel condensation followed by aldol condensation in the presence of a) Sn-La/i
nanoparticles. b) Sn-La/ii nanoparticles. c) Sn-La/iii nanoparticles. d) 2-(4-Chloro-phenyl)-4-
hydroxy-4-methyl-6-oxo-cyclohexane-1,3-dicarboxylic acid diethyl ester).
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The results showed that La-Sn/ii is the most efficient catalyst and it also gave no side product
i.e. cyclohexanone derivative which was purified by column chromatography, as the product
was crystalline, single crystal XRD technique was used for their structure analysis. The %
yield of crystalline product was calculated which was extra ordinary good. Table 2, 3, 4 and
5 is showing the excellent results of the catalysts. . (not clear)
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Table: 2. % yield of Molecule 1 by using Sn-La/i, Sn-La/ii and Sn-La/iii nanomaterial.
Literature Time28
Literature Yield28
Sr# Catalysts Reaction Time ( +5 min.)
% Yield
91%*
84%
1
2
3
Sn-La/ii
Sn-La/iii
Sn-La/i
200*
230
2 days
2 days
2 days
66%
66%
66%
300
76%
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Table: 3. % yield of Molecule 2 by using Sn-La/i, Sn-La/ii and Sn-La/iii nanomaterial.
Literature Time28
Literature Yield28
Sr# Catalysts Reaction Time (+5 min.)
% Yield
96%*
91%
1
2
3
Sn-La/ii
Sn-La/iii
Sn-La/i
70*
75
2 days
2 days
2 days
86%
86%
86%
100
76%
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Table: 4. % yield of Molecule 3 by using Sn-La/i, Sn-La/ii and Sn-La/iii nanomaterial.
Sr# Catalysts Reaction Time (+5 min.)
Literature Time
% Yield
92%
Literature Yield
1
2
3
Sn-La/ii
Sn-La/iii
Sn-La/i
110
150
180
--
--
--
--
--
--
81%
72%
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Table: 5. % yield of Molecule 4 by using Sn-La/i, Sn-La/ii and Sn-La/iii nanomaterial.
Sr# Catalysts Reaction Time (+5 min.)
Literature Time
% Yield
87%
Literature Yield
1
2
3
Sn-La/ii
Sn-La/iii
Sn-La/i
120
165
200
--
--
--
--
--
--
71%
66%
4. Conclusions
In conclusion efficient La-Sn/i, La-Sn/ii and La-Sn/iii nanoparticles catalysts were
developed, characterized and determined their catalytic activity towards synthesis of
cyclohexanone derivatives through tandem Knoevenagel condensation followed by aldol
route. The catalyst helped to increase the yield, reduce time, decrease the side products and
gave a different route than classical mechanism by which cyclohexanone derivative
compounds were prepared more conveniently and were easy to purify. The yield and time of
tandem Knoevenagel condensation followed by aldol route by these catalysts is strong
evidence that the traditional catalysts could be replaced by nanocatalysts to improve the
shortcomings in organic synthesis of vital compounds by which standards of health and food
can be increased because of their versatile applications of products.
Acknowledgment
The authors are grateful to the center of excellence advance material research King
Abdulaziz University, Saudi Arabia for providing research facility.
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Authors’ contributions
Ikram design and carried out all experiments and write the manuscript. Sher and Nadeem
help in experiment and revised the manuscript Abdullah also revised the manuscript and
provide experimental facilities while Shahid help in experiment. All the authors read and
approved the final manuscript.
Conflict of interest
The authors confirms that this article content has no conflict of interest.
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Graphical abstract
O
R
O
O
O
O
O
O
O
O
R
H
OH
Sn-La,/i,ii&iii
Nanoparticles
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Highlights
 Low temperature synthesis of La-Sn nanoparticles
 La-Sn nanoparticles as efficient nano-catalyst
 Synthesis of cyclohexanone
 High yield
25