PII: S1026-9185(16)30080-4
DOI: 10.1016/j.sajce.2017.11.006
Reference: SAJCE 58
Please cite this article as: Samsonu, D., Brahmayya, M., Govindh, B, Murthy, Y.L.N., Green Synthesis
& Catalytic study of Sucrose Stabilized Pd Nanoparticles in Reduction of Nitro Compounds to Useful
Amines, South African Journal of Chemical Engineering (2018), doi: 10.1016/j.sajce.2017.11.006.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
PT
b
Department of Environmental Engineering Safety and Health, Hung Kuang University, Shalu, Taichung, Taiwan
c
Department of H & S, Raghu Institute of Technology, Visakhapatnam, Andhra Pradesh, India
RI
*Corresponding author: Dasi Samsonu, manurichinna_07@yahoo.co.in, Phone +918121210889,
The authors (co-first authors) contributed equally to this work
U SC
AN
M
D
TE
C EP
AC
ACCEPTED MANUSCRIPT
Green Synthesis & Catalytic study of Sucrose Stabilized Pd Nanoparticles in Reduction
of Nitro Compounds to Useful Amines
PT
Department of H & S, Raghu Institute of Technology, Visakhapatnam, Andhra Pradesh, India
*Corresponding author: Dasi Samsonu, manurichinna_07@yahoo.co.in, Phone +918121210889,
The authors (co-first authors) contributed equally to this work
RI
Abstract:
An efficient chemoselective reduction of aromatic nitro compounds to corresponding amino
SC
analogues was achived using palladium/sucrose (Pd/S) nanoparticles as an eco friendly catalyst, a
green approach formate in ethanol at RT. The reductions are fruitfully carried out in presence of
U
various other reducible functional groups such as halo, alkoxy, carbonyl, and cyanide etc. The
reactions are worthy and high yielding (100%).
AN
Key words: pd/sucrose nano particles, eco friendly, reduction, amine formation, methodolgy,
M
characterizations
___________________________________________________________________________
D
dimensional materials are like an interlinked among bulk and atomic materials which have been
shown to display a diversity of distinctive physical, chemical and electronic properties. 1 Nowadays
Pd/Sucrose nanoparticles (Pd/S) are broadly used in organic synthesis due to great catalytic activity
EP
The benefit of these type of catalysts is the absence of ligands, easy separation from the product and
AC
the chance of their reuse. The compensations are accomplished upon control of PdS on organic or
1, 3
inorganic media that permits one to escape aggregation of nano particles (Nano Particles) and to
use modest separation approaches, such as filtration or centrifugation. Nevertheless, the
4
immobilization procedure is frequently backbreaking. Additionally, the support is occasionally not
inert, together to Pd/S and to the substrate.
Reduction of nitro compounds always a significant reaction in industry and is often employed
as an ideal procedure for studies on catalyst effectiveness and recyclability. Earlier, a number of
[1]
ACCEPTED MANUSCRIPT
procedures based on PdS fixed on solid support of Fe2O3, Al2O3, SiO2, and CeO2 and several other
5, 6, 7
metal oxides were recommended for hydrogenation of nitro arenes. In general, anilines were
achieved in increased yields and with notable selectivity.
Sometimes, the nano particles (from 1 to 2 nm) had the maximum catalytic activity. 8-10 In
1-12
some other cases, 6–9 nm sized particles were the most active as well, and in some other
3-7
classifications, the selectivity of the reaction was influenced by the choosen solvent. Most
PT
preferably, the catalytic activity always depends on the procedures of their synthesis and capping onto
13-15
the support, but the existence of oxide and hydroxy groups affect the creation of branched azo
compounds. 16
RI
Presently, environmental ideologies and demand of chemical industry need selective catalyst
SC
17-18
to be prepared eco friendly, low-price, simply utilized, and positively well recyclable.
Consequently, we paid an attention on activated palladium sucrose nano particles (APSNP), an
inexpensive and commonly obtainable inert support. 16-18 Distinctive features of this support contain
U
an immense large surface, polymodal size spreading of pores, capability to adsorb organic
AN
compounds.
All chemicals, reagents and solvents were obtained from commercial suppliers and used
without further purification. All experiments were conducted in 50-100 mL round-bottomed Pyrex
D
glass flasks with nonstop and constant stirring at 700 rpm. Thin layer chromatography was carried on
TE
silica gel plates. Flash column chromatography was made using various 300–400 mesh silica gel.
Visualization of TLC was achieved by illumination under a UV lamp (254 nm). 1H-NMR spectra were
13
recorded on a 200 MHz spectrometer and C-NMR was recorded on a 100 MHz spectrometer,
EP
tetramethylsilane (TMS) served as an internal standard. Infrared (IR) spectra were recorded with a
Perkin-Elmer Spectrum One FT-IR spectrometer. Samples were prepared as potassium bromide
C
pellets for IR characterization. The mass spectra were analyzed on a Finnigan LTQ-Orbitrap XL
instrument (ESI source) and UV-vis spectroscopy was recorded by using an UV-vis spectrophotometer
AC
(UV-1601, Shimadzu).
[2]
ACCEPTED MANUSCRIPT
formation of Pd nanoparticles. Then the reaction mixture was transferred into a sealed tube and
reaction was further preceded for 4 hrs at 1800 C. The reaction mixture was allowed to cool at room
temperature. The resulting mixture was centrifuged and washed with distilled water and finally dried
at 60oC for 12 h. The prepared sucrose stabilized Pd nanoparticles were characterized by X-ray
diffraction patterns (XRD), UV-Visible spectroscopy, scanning electron microscopy (SEM),
transmission electron microscopy (TEM) and Energy dispersive X-ray (EDX) spectra.
PT
General procedure for hydrogenation of nitrobenzene & substituted nitrobenzenes:
The study of catalytic reaction of Pd/ carbohydrate (sucrose) (Pd/S) in the formation of
RI
amines was evaluated using the catalyst (1 mol%), 1mmol of nitro benzene and 20 ml of ethanol at
room temperature in hydrogen atmosphere for 1hour under stirring condition. The completion of the
SC
reaction was monitored by TLC and after completion, the catalyst was separated by centrifugation and
subsequently washed with dichloromethane. The reaction mixture was diluted with water and product
U
was extracted with dichloromethane (2 X 10 mL). The organic layer was dried over anhydrous sodium
sulphate and evaporated under reduced pressure to afford the crude product. The crude product was
AN
purified by column chromatography and characterized by advanced spectroscopic techniques. All the
spectral data was explored from the supporting material.
M
X-ray diffraction patterns (XRD) were carried out using a MINI FLEX RIGAKU MODEL
X-ray diffractometer, at 2 degree per minute with Cu-Kα radiation (1.5418 A°) with scan ranging
from 10o to 80o. The XRD patterns of sucrose stabilized Pd nanoparticles are presented in Fig 1. XRD
EP
structure respectively. From the data, it was found that the prepared Pd nanoparticles show good
crystalline nature. The average crystallite size was calculated for Pd NPs for its {111}, reflection from
AC
the line broadening using the Debye– Scherrer’s formula given by:
D = k λ / β Cos θ
where D is the average grain size, λ is the wavelength of the X-ray used (λ = 1.54Å for Cu
Kα), θ is the Bragg angle (in degrees), β is the full width at half maximum after making the correction
due to instrumental broadening and k is the shape factor. The value of k depends on several factors,
including the Miller index of the reflecting plane and the shape of the crystals. If the shape is
unknown, k is often assigned a value of 0.89. Calculated crystallite size for the prepared Pd/S NPs
was around 6 nm.
[3]
ACCEPTED MANUSCRIPT
PT
RI
Figure 1: Powder XRD pattern of sucrose stabilized Pd nanoparticles.
UV-Visible spectroscopy:
SC
The Pd2+ ion solution displays gradual color change from transparent yellow to dark brown
for over time on addition of varying quantity of sucrose. The observed intense brown color
U
recommends the formation of palladium nanoparticles and the reduction procedure is monitored using
AN
UV-visible spectroscopy. Fig. 2 shows the broad continuous UV-visible spectra recorded for the
samples prepared at room temperature (P1-P5) compared with the absorbance peak of bulk palladium
acetate solution. As depicted in Fig. 2, the characteristic absorption peak of Palladium acetate at 300
M
nm vanished in the reaction progress, which revealed that bivalent palladium was reduced to zero
valent palladium completely in the end and the formation of the Pd/S nanoparticles. Thus, the
D
obtained spectra comparable with the earlier reports and reveal that the complete reduction of bulk
TE
Figure 2: UV-visible spectra of Palladium acetate and Pd NP using different amount of sucrose.
[4]
ACCEPTED MANUSCRIPT
TEM of sucrose stabilized Pd nanoparticles:
The surface morphology and particle size of Pd/S nanoparticles was investigated by
scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Transmission
electron microscopy images were obtained [TEM model FEI TECNAI G2 S-Twin] at an accelerating
voltages of 120 and 200 kV.
PT
TEM micrographs of prepared Pd/S nanoparticles are presented in Fig. 3. TEM micrograph
depicted in Fig. 3 clearly shows the spherical like morphology with average diameter ranging from 4
-5 nm. The particle size of Pd/S nanoparticles obtained from TEM was in good agreement with the
RI
average crystallite size calculated from the XRD data.
U SC
AN
M
D
TE
C EP
AC
Surface morphology was observed by scanning electron microscopy (SEM) using Field
Emission Gun-Scanning Electron Microscope (FEG-SEM) JSM-7100F model, operating at
accelerating voltage 0.1 to 30 kV, Magnification x25 to 1,000,000 and resolution of 1.0 nm - 1.5 nm
[5]
ACCEPTED MANUSCRIPT
(15kV) equipped with an electron probe- micro analyzer. SEM image of Pd/S nanoparticles is showed
in Fig. 4. From the SEM images Fig. 4, it can be seen that spherical morphology of Pd nanoparticles.
SEM image Fig. 4 reveals that Pd NPs are not aggregated. This is due to the Pd NPs were stabilized
by sucrose.
PT
RI
U SC
AN
Figure 4: SEM images of sucrose stabilized Pd nanoparticles
M
The energy dispersive X-ray (EDX) analysis of Pd/S nanoparticles presented in Fig. 5. EDX
analysis reveals the presence of carbon, oxygen and Pd in sucrose stabilized Pd nanoparticles, which
D
in turn confirms the formation of sucrose stabilized Pd nanoparticles. The EDX revealed the
formation of a strong signal for palladium and confirmed the formation of palladium nanoparticles.
TE
C EP
AC
[6]
ACCEPTED MANUSCRIPT
Results & Discussion:
In this study, we reported Pd/S as inexpensive and mostly accessible catalyst for nitro
reduction reactions. In the synthesis of catalyst, we improved the method of avoiding impurities by
19-20
the adsorption of activated sucrose. The preparation and characterizations (XRD as Fig-1 in 4a,
UV as Fig-2 in 4b, TEM as Fig-3 in 4c, SEM as Fig-4 & EDAX as Fig-5 in 4d) of sucrose stabilized
palladium NPs was presented.
PT
The XRD patterns of Pd/S nanoparticles are presented in Fig 1. XRD pattern revealed the
21
planes of Pd metal with face centered-cubic (fcc) structure. The particle size calculated by the
RI
22
Debye–Scherrer technique based on XRD data was rather enough size, namely 6 nm. Even the
distinguished UV spectrum of substrate materials and prepared materials provided as Fig. 2. Also,
SC
prepared palladium clusters up to 6 nm in size were noticed by means of SEM Fig. 4. Thus we tuned
to test them for hydrogenation of nitrobenzene. 23 Such Pd clusters maintained stable throughout the
reaction. 1–3 nm nanoparticles that undergo leaking or coalescence with time. Moreover, small scale
U
nanoparticles i.e., 5-6 nm nanoparticles are safe for selectivity of the reaction since they accurately
AN
lead reaction at aimed function.
From Table 1, the initial efforts to use the palladium based catalysts 24 such as Pd/C, Pd/ZnO,
M
Pd/CeO2 catalyst (5 mg) in nitrobenzene, hydrogenation displayed lower efficiency. From Table 2, the
yield of aniline after 1h was only 34% and 19% respectively for the Pd/C and Pd/ZnO (entry 1 and 2).
D
We flourished in raising the yield fairly (90%) by altering the catalyst like Pd/CeO2 (5mg) and
hydrogen pressure, reaction time (1.5 h) and temperature 800C (entry 3). Finally, optimum conditions
TE
the catalyst is examined, once the completion of the reaction occurred. The catalyst was separated by
centrifugation, washed with water and then with diethyl ether for 3 times. The catalyst was
subsequently dried at 120o C and reused for the next cycles. It was found that, the catalyst showed
C
[7]
ACCEPTED MANUSCRIPT
Table 1: Optimization conditions for the reduction of nitro benzene with molecular hydrogen a
Sl.no A B C Solvent
1 Pd/C 40 80 Ethanol
2 Pd/ZnO 40 70-80 Ethanol
3 Pd/CeO2 40 80 Ethanol
4 Pd/Sucrose 40 RT Ethanol
PT
5 Pd/Sucrose 40 RT Hexane
6 Pd/Sucrose 20 RT Water
7 Pd/Sucrose 20 RT Ethanol
RI
8 Pd/Sucrose 20 RT Ethanol
A: APSNP/Support (mole %); B : P/Atm; C : T/0C;
SC
Table 2: Yields obtained/cycle
U
1 2 3 4
AN
1 34
1 19
M
1 90 86
1 98
2 1 80 80 80
D
a
Reaction conditions: 1 mmol of nitrobenzene, 1 mol% of the APSNP catalyst, 2 ml of EtOH, H2.
b
The yield of aniline was determined by NMR spectroscopy.
EP
As shown in Table 3, reduction with 1 mol% of the catalyst happens rather efficiently
together in the case of non-substituted nitrobenzene (entry 1) and in the case of compounds having an
C
electron-donating substituent, (entries 5, 6, 7, 8). In the case of electron withdrawing groups like
halogen or highly electronegative elements like nitrogen functionality nitro compounds requires the
AC
catalyst amount to be increased to 2 mole %. 27-28 Hydrogen pressure had to be furthermore enhanced
to 40 atm (entries 2, 3, 4, 9). However, we found that the selectivity was 100 % in all case studies.
[8]
ACCEPTED MANUSCRIPT
Table 3: Hydrogenation of nitrobenzene by using APSNP
PT
8 1h 2h 1 100
9 1i 2i 2 86
RI
a
The yield was determined by NMR spectroscopy. The yield ties the conversion of the initial nitro
compound in all circumstances; b40 atm H2.
SC
Thus, we presented a modest variation of low-cost and recyclable APSNP catalyst and for
discriminated hydrogenation of aromatic nitro compounds by catalytic transfer of hydrogenation by
using hydrogen gas as hydrogen donor. The given procedure can also be useful at room temperature.
U
This recyclable catalyst offers advantages like simple work-up and high yields. The developed
AN
thought is predictable to be broader and easily applicable. The APSNP is ecologically benign and can
be used for reduction of nitro aryls to corresponding amines. Hence the protocol fits into various
green chemistry concepts such as use of nontoxic solvent, atom economy, ambient reaction
M
NO2 NH2
D
R1 R5 R1 R5
APSNP (1 mole%), 20 atm H2
TE
R2 R4 Ethanol / RT, 2h R2 R4
R3 R3
1a R1,R2,R3,R4,R5 = H 2a R1,R2,R3,R4,R5 = H
EP
Scheme–1
AC
Acknowledgements:
The author D S thankful to Prof. Y L N Murthy, and departmental support to carry out this
work.
[9]
ACCEPTED MANUSCRIPT
References:
PT
5 S. Cheong, J. D. Watt, R. D. Tilley, Nanoscale 2010, 2, 2045.
6 S. Horinouchi, Y. Yamanoi, T. Yonezawa, T. Mouri, H. Nishihara, Langmuir 2006, 22, 1880.
7 H. Kobayashi, M. Yamauchi, H. Kitagawa, Y. Kubota, K. Kato, M. Takata, Journal of the
RI
American Chemical Society 2010, 132, 5576.
8 S. Mubeen, T. Zhang, B. Yoo, M. A. Deshusses, N. V. Myung, The Journal of Physical Chemistry
SC
C 2007, 111, 6321.
9 C. P. Mehnert, D. W. Weaver, J. Y. Ying, Journal of the American Chemical Society 1998, 120,
12289.
U
10 M. T. Reetz, E. Westermann, Angewandte Chemie International Edition 2000, 39, 165.
AN
11 S. Klingelhöfer, W. Heitz, A. Greiner, S. Oestreich, S. Förster, M. Antonietti, Journal of the
American Chemical Society 1997, 119, 10116.
12 S. Pathak, M. T. Greci, R. C. Kwong, K. Mercado, G. S. Prakash, G. A. Olah, M. E. Thompson,
M
467.
18 Q. Shi, R. Lu, K. Jin, Z. Zhang, D. Zhao, Green Chemistry 2006, 8, 868-870.
AC
[10]
10]
ACCEPTED MANUSCRIPT
25 F. Harraz, S. El-Hout, H. Killa, I. Ibrahim, Journal of Catalysis 2012, 286, 184-192.
26 H. D. Burge, D. J. Collins, B. H. Davis, Industrial & Engineering Chemistry Product Research
and Development 1980, 19, 389.
27 N. Mahata, A. Cunha, J. Orfao, J. Figueiredo, Applied Catalysis A: General 2008, 351, 204.
28 E. A. Gelder, S. D. Jackson, C. M. Lok, Chemical communications 2005, 522.
PT
RI
U SC
AN
M
D
TE
C EP
AC
[11]
11]
ACCEPTED MANUSCRIPT
Supporting Information
PT
a
Department of organic chemistry and FDW, Andhra University, China waltair Road, Visakhapatnam-530003,
India.
RI
b
Department of Environmental Engineering Safety and Health, Hung Kuang University, Shalu, Taichung, Taiwan
c
Department of H & S, Raghu Institute of Technology, Visakhapatnam, Andhra Pradesh, India
SC
*Corresponding author: Dasi Samsonu, manurichinna_07@yahoo.co.in, Phone +918121210889,
U
AN
Spectroscopic Data for Products:
13
J=7.88 Hz), 3.50 (2H, br., s). C NMR (100
MHz/CDCl3) δ ppm: 190.0, 150.0, 129.5, 125.0, 115.5.
AC
CHO
Mass-ESI: 122 (M+H).
[12]
12]
ACCEPTED MANUSCRIPT
PT
4-methoxybenzenamine (2e) IR (KBr pellet) cm-1: (Fig S9) 3423.05, 2964.53,
RI
2839.53, 1506.26, 1234.24, 1129.64, 826.06. 1H NMR
(400 MHz/ CDCl3) δ ppm: (Fig S10) 6.70 (2H, d, J=8.20
SC
Hz), 6.63 (2H, d, J=7.64 Hz), 3.75 (2H, br., s), 3.31 (3H,
s). 13C NMR (100 MHz/CDCl3) δ ppm: (Fig S11) 152.7,
140.0, 116.2, 114.5, 55.8. Mass-ESI: (Fig S12) 124.07
U
(M+H).
AN
O-Toluidine (2g). IR (KBr pellet) cm-1: 3420.45, 2930.54, 2860.28,
1542.70, 1200.50, 1168.32, 750.30. 1H NMR (400 MHz/
M
Benz ene- 1, 4- diamine (2i): IR (KBr pellet) cm-1: 3410.54, 3075.80, 1526.80,
1096.43, 828.54., 1H NMR (400 MHz/ CDCl3) δ ppm:
13
6.50 (4H, s), 3.95 (2H, br., s). C NMR (100
MHz/CDCl3) δ ppm: 136.5, 138.0, 115.5. Mass-ESI: 109
(M+H).
[13]
13]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[14]
14]
ACCEPTED MANUSCRIPT
Spectral charts
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[15]
15]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[16]
16]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[17]
17]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[18]
18]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[19]
19]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[20]
20]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[21]
21]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[22]
22]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[23]
23]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
C EP
AC
[24]
24]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
C EP
AC
[25]
25]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[26]
26]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[27]
27]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[28]
28]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[29]
29]
ACCEPTED MANUSCRIPT
PT
RI
U SC
AN
M
D
TE
EP
C
AC
[30]
30]
ACCEPTED MANUSCRIPT
Simple impressive chemoselective reduction of aromatic nitro compounds to the corresponding amino analogues
at RT conditions.
Cost viable Palladium/Sucrose (Pd/S) nanoparticles acted as efficient catalyst for the above conversions.
The reusability of catalysts are easy & acted for more cycles.
The reductions are fruitfully carried out in presence of other reducible functional groups in the molecule, such as
halo, alkoxy, carbonyl, and cyanide etc.
PT
The reactions are very keen with high yielding (100%).
RI
U SC
AN
M
D
TE
C EP
AC