Characterization of next-generation Materials Research Summary

Characterization of Copper
nanoparticles Synthesized by a
novel Microbiological Method
Ratnika Varshney, Seema Bhadauria, M.S. Gaur, and Renu Pasricha

The exploitation of various biomateri- in fields of lubricants, polymers/plastic, dures have been shown to be a powerful
als for the biosynthesis of nanoparticles metallic coating and ink. Cu sulfide has tool for preparing stable nanoparticles
is considered as green technology as it potential applications in solar cells, IR composed of a wide range of metals
does not involve any harmful chemicals. detectors and lubrication.11 and compounds.13–18 The most varied
The present study reports the synthesis There are several reports available and versatile preparation route appears
of copper nanoparticles which involves of physical and chemical synthesis to be the so-called “sacrificial anode”
non-pathogenic bacterial strain Pseu- of Cu and Cu based nanomaterials. electrolysis that is usually carried out
domonas stutzeri, isolated from soil. Chuncheng Hao et al. have reported the in the presence of cationic surfactants
These copper nanoparticles are further preparation of Cu nanoparticles encap- such as tetra-alkyl-ammonium salts. In
characterized for size and shape distri- sulated in graphitic carbon shells using a seminal paper based on the combined
butions by ultraviolet-visible spectros- modified arc plasma method.12 Surfac- use of transmission electron and scan-
copy, x-ray diffraction, and high resolu- tant-assisted electrochemical proce- ning tunneling microscopies, the group
tion transmission electron microscopy of M. Reetz demonstrated that these
techniques. The results showed that the How would you… metal nanoparticles possess a core-shell
particles are spherical and quite stable …describe the overall significance
structure in which the metallic core is
in nature and shows surface plasmon of this paper? stabilized by a monolayer of tetra alkyl-
resonance clearly featured in the opti- This paper reports a bacterial ammonium species, and the thickness
cal spectra in visible region. strain for the synthesis of copper of this shell is linearly correlated with
nanoparticles. This is a novel the length of the alkyl chains.19 In the
InTROdUCTIOn method as it doesn’t involve any
harmful and environmentally last decade, the electrolytic production
Low-dimensional nanoscale materi- toxic chemicals used previously in of nanoparticles and nanocomposites
als are currently of great interest due to conventional chemical reduction containing platinum group elements
their unique electronic, optical, and me- methods for the preparation of has been extensively studied, due to
copper nanoparticles.
chanical properties.1–4 Among the coin- the strong catalytic properties of these
…describe this work to a products.13,20–25 The electro-synthesis of
age metals, Ag and Au have been stud-
materials science and engineering
ied the most because of their stability professional with no experience in Cu and Ag colloids, on the other hand,
and their intense absorption band in the your technical specialty? has been the subject of only a few re-
visible region, often called surface plas- Copper nanoparticles synthesized ports.14,26–28 But no reports are avail-
mon absorption. Cu, in turn, is the least with this method are spherical and able on the biological synthesis of Cu
well dispersed. They have organic
studied out of the coinage metals due coating on the surface which is
nanomaterials. It is, therefore, impor-
to its high instability for oxidation, and reducing and not only acts as tant to develop synthetic strategies that
most of the time it forms complexes with capping agent but also prevents them are simple, cost-effective, environment
water molecules in aqueous media.5,6 from oxidation, which seems to be friendly, easily scalable and at the same
a major problem with the previous
Particularly in transition metal oxides, methods involved in the copper time with parameters to control size and
Cu-based nanoparticles and nanowires nanoparticles synthesis. shape of the materials. Hence the devel-
have been synthesized by a variety of …describe this work to a opment of a novel method for the prepa-
methods, and because of a reduction layperson? ration of Cu nanoparticles is inevitable.
in dimensionality, their ferromagnetic This method reports use of a non- With these ideas in mind, an attempt has
polarizations are quite different from pathogenic bacterial strain and been made in this investigation to syn-
those observed in transition metals.7–9 spherical nanoparticles of copper thesize Cu nanoparticles by a novel bio-
are synthesized which are very useful
Cu nanoparticles were widely used as in the field of catalysis. It is a simple, logical method using non-pathogenic
alternative catalysts,10 such as selective rapid, cost efficient and green bacterial strain Pseudomonas stutzeri
hydrogenation and methanol synthesis method which is free from using isolated from soil and characterize them
any toxic reducing chemicals. This
reactions, which make them suitable provides a platform for new metallic
for their properties by methods of ab-
for application in the field of catalysis. nanoparticles synthesis. sorption optical spectroscopy and trans-
Nano-sized Cu particles are widely used mission electron microscopy (HRTEM).

102 [Link]/[Link] JOM • December 2010

 can be made for the absorption spectra Figure 2a illustrates the crystallized par-
of Cu nanoparticles. In this case, the ticles immediately after the preparation
broad and low absorption peak can be
Absorbance (a.u.)
consisted of Cu and in Figure 2b, crys-
related to the small particle size due to tallized particles of Cu after one month
a reduced mean free path for conduction illustrates an insignificant change in
electrons. At very small sizes, limitation intensity. Since it is clear from Figure
of the mean free path by the particle 2 that Cu nanoparticles have not been
boundary broadens and decreases peak oxidized in over one month, it was dem-
absorption.31 The spectra of nanopar- onstrated that the organic coating on the
0 400 600 800
Wavelength (nm) ticles obtained by biological synthesis metal nanoparticles is effective in pre-
Figure 1. UV-Visible spectra recorded gives the better band than the traditional venting them from oxidation.
from solution of Cu nanoparticles; inset chemical methods, proves the less share To confirm the spectra analysis find-
shows the appearance of yellow color of impurity, and also, probably, the less ings and identify the existence of Cu
indicating the synthesis of nanoparticles.
dispersion in the size of particles. nanoparticles structure, HRTEM analy-
The XRD pattern of the sample is sis was performed for the sample. Typi-
The size and shape distributions of Cu shown in Figure 2. Diffraction peaks cal HRTEM images and SAED pattern
nanoparticles are determined from the can be indexed to those of pure face- of the Cu nanoparticles synthesized are
data of TEM and optical spectroscopy. centered cubic (f.c.c.) Cu (JCPDS, presented in Figure 3. In the HRTEM
X-ray diffraction (XRD) analysis was File No. 04-0836), corresponding to images, the dark spots and light features
performed to identify the crystalline na- the (111), (200), and (220) planes. The corresponds to Cu nanoparticles and
ture of Cu nanoparticles. crystallite size can be found by apply- carbon matrix, respectively. HRTEM
See the sidebar for experimental pro- ing Sherrer’s equation and the average study shows that particles produced
cedures. crystallite size is found to be 11 nm. The were almost spherical and 8–15 nm in
observation of diffraction peaks for the size range (Figure 3a). In Figure 3b, a
RESULTS and dISCUSSIOn
Cu nanoparticles indicates that these are thin coating layer can be observed on
Nanosized Cu together with other crystalline in nature. all particles and the thickness is a few
noble metals such as Au and Ag are Previous studies found that Cu nanometers. This indicates that the bac-
the most studied metallic nanoparticles nanoparticles without the coating oxi- terial surface acts both as reducing as
as the surface plasmon resonances are dize gradually.32 To confirm the stability well as capping agent. The micrograph
clearly featured in the optical spectra, of nanoparticles, we performed diffrac- also demonstrates that as-synthesized
and are located in visible region.29 Cu tion analysis of Cu nanoparticles as pre- Cu nanoparticles are well-dispersed
nanoparticles were first indicated by the pared and after one month. The graph in with no conspicuous agglomeration and
appearance of a yellow color solution
(Figure 1 inset). This is due to Plasmon EXPERIMEnTaL PROCEdURES
resonance, with a significant contribu- Bacterial strains were enumerated from soil around the sewage outfall of the small
tion from inter-band transition which scale electroplating industry from Dhakran, Agra by Serial dilution-agar plating method
produces yellow hydrosol having Imax (Nigam 1965). 1 × 10–3 dm3 inoculum was transferred into 50 × 10–3 dm3 medium contain-
at 570 nm (Figure 2). The yellow color ing (g/l) Peptone, 5; Beef extract, 3; Sodium chloride, 5; Agar, 15; pH 7.2 in Erlenmeyer
of the colloidal solution remains stable flasks. Cells were grown at 37°C for 24 h and then harvested by centrifugation (8,000 r
after one month of synthesis. The posi- min.–1, 10 min. at room temperature). The cell pellet was resuspended and centrifuged
three times in deionized water. Copper sulfate was purchased from Hi-media, and was
tion and shape of the plasmon absorp-
used as received. In a typical synthesis for nanoparticles using Pseudomonas stutzeri, the
tion peaks are dependent on the particle carefully weighted 0.1 g biomass was added to 100 ml of 1 mM aqueous CuSO4 solution,
morphology, dielectric functions of the in conical flasks of 250 ml content. The flasks were thereafter incubated in incubator-
metal and the surrounding medium as shaker at 150 rpm at room temperature.
well as surface-absorbed species.29 The To confirm the synthesis of nanoparticles, characterization was done by UV-Vis spec-
presence of the single surface-plasmon troscopy, x-ray diffraction, high-resolution transmission electron microscopy and se-
peaks implied that the formed nanopar- lected area electron diffraction techniques. The bioreduction of Copper ions in aqueous
solution was monitored by periodic sampling of aliquots (0.2 ml) of the suspension, then
ticles were nearly spherical attributed
diluting the samples with 2 ml deionized water and subsequently measuring ultra vio-
to the coherent oscillation of the con- let visible (UV-vis) spectra of the resulting diluents. UV–vis spectroscopy analyses of
duction electrons caused by oscillating copper nanoparticles produced were carried out on ELICO UV spectrophotometers at
electric field when they are irradiated by a resolution of 1 nm. X-ray diffraction measurements of the bioreduced solution, drop-
light.30 coated onto glass substrate, were done by an X’Pert Pro x-ray diffractometer instrument
According to Mie theory, spec- operating at a voltage of 45 kV and a current of 40 mA with Cu Ka radiation. Samples for
tra of the particles with radii between HR-TEM analysis were prepared on carbon- coated copper grids. The films on the copper
about 2 and 10 nm are independent of grids were allowed to stand for 2 min following which the extra solution was removed
using a blotting paper and the grid was allowed to dry prior to measurement and analysis
the particle size. For particles with di-
was carried out on Tecnai G2 F30 S-Twin (FEI; Super Twin lens with Cs =1.2 mm) instru-
mensions beyond 10 nm the absorp- ment operated at an accelerating voltage at 300 kV (field emission gun), having a point
tion peak broadens and shifts to longer resolution of 0.2 nm and lattice resolution of 0.14 nm.
wavelength. Analogous considerations

Vol. 62 No. 12 • JOM [Link]/[Link] 103

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(2004), pp. 2417–2419. Bhadauria are with the Microbiology and Nano-
molecules present in the biomass not 27. L. Rodriguez-Sanchez, M.C. Blanco, and M.A. technology Research Lab, Department of Botany,
only reduce the metal ions and but also Lopez-Quintela, J. Phys. Chem. B, 104 (2000), pp. Raja Balwant Singh College, Khandari, Agra-
stabilize the metal nanoparticles by 9683–9688. 282004, India; M.S. Gaur, associate professor,
28. A. Dierstein, H. Natter, F. Meyer, H.O. Stephan, is with the Department of Physics, Hindustan
preventing them from being oxidized C. Kropf, and R. Hempelmann, Scripta Materialia, 44 College of Science & Technology, Farah, Mathura,
after the preparation. To the best of our (2001), pp. 2209–2212. India; and Renu Pasricha, scientist, is with the
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104 [Link]/[Link] JOM • December 2010