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Green synthesis of palladium nanoparticles using fenugreek tea and their cata-
lytic applications in organic reactions
PII: S0167-577X(17)30980-1
DOI: http://dx.doi.org/10.1016/j.matlet.2017.06.081
Reference: MLBLUE 22793
Please cite this article as: K. Mallikarjuna, C. Bathula, K. Buruga, N.K. Shrestha, Y-Y. Noh, H. Kim, Green synthesis
of palladium nanoparticles using fenugreek tea and their catalytic applications in organic reactions, Materials
Letters (2017), doi: http://dx.doi.org/10.1016/j.matlet.2017.06.081
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Green synthesis of palladium nanoparticles using fenugreek tea and
Abstract
spectroscopy, scanning electron microscopy (SEM), small area electron diffraction (SAED),
fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). FT-IR
menifested that polyol and amide groups present in fenugreek may have participated in the
coupling reaction between bromobenzene and phenyl boronic acid gave desired biphenyl in
excellent yield.
Admirable research has been progressed on the utilization of phytochemicals in the field of
green nanoscience and nanotechnology [1-3]. Tea extracted from natural sources are basically
fabrication of nanoparticles [4-7]. Noble and transition metal nanoparticles such as Pt, Pd, Ru,
Au, Ag, Fe, Ni, Co and Cu are widely employed as active catalysts in various synthetic and
industrial processes. Some of the conventional routes for synthesis of metal nanoparticles
method, template method, and microwave-assisted synthesis using hazardous reducing agents
friendly protocols, for metal nanoparticles has emerged out over the last decade [10]. For
leaves, fruits, roots, honey, coffee, tea, and peel extracts has been reported [11-13]. These
natural products are expected to play efficient role in reduction of metal ions, and formation
seed, as it contains very high concentrations of the proteins, vitamins and dietary fibers [18].
fenugreek seeds as green reducing agent. As an example of the functional properties, the
PdNPs were prepared by stirring 30 ml of 0.01 M PdCl2 with 3 ml of aqueous extract at room
temperature. The reaction mixture gradually turned in to a black indicating the formation of
PdNPs@FT. The progress of the reaction was monitored via UV-Vis absorption spectroscopy.
bromobenzene, benzeneboronic acid, PEG-400 and K2CO3 in water were mixed with
PdNPs@FT catalyst in a round bottomed flask, and the mixture was refluxed for 6 hours.
After completion of reaction, the filtrate containing the product was evaporated to obtain
desired biphenyl in excellent yield (96%). The 1H NMR data of the recrystallized product
The formation of PdNPs@FT was studied by UV-Vis absorption spectroscopy Fig. 1. The
reaction media showed a transition in color from dark yellow to black, which indicates the
confirmed by the disappearance of d-d transition band of Pd 2+ (i.e., PdCl2) exhibited by the
reaction mixture at about 480 nm, which suggests the reduction of Pd2+ (d 8 electron
FE-SEM images of the synthesized biogenic PdNPs@FT are presented in Fig. 2 (a)
and (b). These images illustrate spherical nanoparticles with diameter ranging 20 to 50 nm.
We also examined particles carefully at the edges by lowering the accelerator voltage. In all
cases, the brighter edges of the PdNPs@FT was observed. The observed phenomenon of
color contrast between edge and central part of the PdNPs@FT indicates the capping of
PdNPs by phyto-chemical moieties. The capping was further confirmed using FT-IR analysis,
which will be discussed in later part. The formation of PdNPs by bioreduction of Pd ions and
their crystal structure was confirmed using powder X-ray diffraction (XRD) technique. The
XRD pattern of the PdNPs@FT is displayed in Fig. 2(c), showing the peaks at 2-Theta of
40.2º, 46.6º, 68.6º, 81.8º and 86.8º, which correspond to the diffraction from (111), (200),
(220) (311) and (222) planes, respectively. Based on the XRD patterns (JCPDS 05-0681 PDF
file), PdNPs can be indexed to the face centered cubic (fcc). The comparatively highly
intense diffraction peak from (111) planes suggests that the biogenic PdNPs@FT inclined to
develop into particles with planes bound by the lowest energy (111) lattice plane. This
growth indicates that crystals grown on the (111) planes were bottled-up by the selective
adsorption of bioorganic moieties onto the (111) facet [20, 21]. Further, SAED pattern (Fig.
2(d)) shows the characteristic diffraction ring patterns, which are in good aggrement with the
XRD patterns.
FT-IR spectroscopy is used to elucidate the role of fenugreek tea in the surface adsorbed
biomolecules on PdNPs@FT (Fig. 3a). Peak at 3418 cm−1 is attributed to N–H stretching, H
bonded O-H vibrations of amides and polyphenol groups. Peaks at 2922 and 2848 cm−1
represents asymmetric and symmetric streching C-H vibrations. The band at 2348 cm-1 is due
to the coordination of C-N groups of proteins with the metal atoms at the surface of the
PdNPs@FT. The peaks between 1738-1170 cm−1 arises from the N-H bending, C=O and C-
fenugreek tea [22]. This FT-IR spectrum looks more or less simlar to that of the tea extract
(Fig. 3b), suggesting the encapsulation of PdNPs by phyto-chemical moieties of the tea
PdNPs.
monitored using UV-Vis absorption spectroscopy. When NaBH4 was added to 4-nitrophenol,
the solution turned yellow and produced an absorption peak at 400 nm in the UV-Vis spectra
(Fig. 4a), suggesting the formation of 4-nitrophenolate anion. The addition of nanoparticles
new peaks at 300 nm and 230 nm [22, 23]. The results revealed that the PdNPs@FT
decrease in the peak intensity at 400 nm illustrates the utilization of 4-nitrophenol, and the
progress of the reaction. However, no proportional increase in the aminophenol peak intensity
hydrogen transport shuttle between the NaBH4 and 4-nitrophenol. In this shuttling,
PdNPs@FT adsorbs hydrogen from the NaBH4, and release it efficiently during the reduction
reaction.
On the other hand, Suzuki–Miyaura coupling reaction is most widely used protocol in
most challenging C-C bond formation reaction, and has significance in organic synthesis.
Traditionally, Pd(PPh3)4 is used as catalyst in this coupling reaction. However, owing to the
high cost and complex procedure in catalysis, PdNPs obtained from various techniques have
been explored as an alternative (see Table S1 in SI section). In this work, the coupling
reaction between bromobenzene and phenyl boronic acid was catalyzed by the PdNPs@FT
(Fig. 4b), which yielded desired biphenyl in excellent yield. The catalytic performance is
highly competitive to the previously reported PdNPs, and found even better in some cases
(Table S1).
4. Conclusion
PdNPs@FT as a green catalyst. Phyto-chemical moieties within fenugreek tea not only
contributes to effective reduction of Pd(II) to PdNPs, but also aids in capping in order to
provide excellent stabilizing against agglomeration. The PdNPs@FT grew with their surfaces
inclined by the lowest energy (111) facets. PdNPs@FT displayed high catalytic activity in
nitrophenol reduction, and in Suzuki-Miyaura coupling reactions. The green synthetic route
References
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Figure captions
Fig. 1. (a) UV-Vis absorption spectroscopy of during synthesis of PdNPs@FT. The spectrum
of PdNPs@FT (PdCl2 + Fenugreek seed extract) was recorded after 3 hours of reaction.
Fig. 2. (a) and (b) Different magnification of SEM images of PdNPs@FT, (c) XRD patterns
Fig. 3. (a) FTIR spectrum of PdNPs@FT, and (b) FTIR spectrum of Fenugreek seed extract.
of NaBH4 by PdNPs@FT (Inset is the scheme for reduction reaction). (b) Schematic
presentation of Suzuki cross coupling reaction between bromobenzene and phenyl boronic
Graphical abstract