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Green synthesis of zinc oxide nanoparticles by aloe barbadensis miller leaf extract:
Structure and optical properties
Gunalan Sangeetha a, Sivaraj Rajeshwari a,*, Rajendran Venckatesh b
a
Department of Biotechnology, School of Life Sciences, Karpagam University, Eachanari Post, Coimbatore 641 021, Tamilnadu, India
b
Faculty of Chemistry, Government Arts College, Udumalpet 642 126, Tamilnadu, India
A R T I C L E I N F O A B S T R A C T
Article history: Biological methods for nanoparticle synthesis using microorganisms, enzymes, and plants or plant
Received 29 January 2011 extracts have been suggested as possible ecofriendly alternatives to chemical and physical methods. In
Received in revised form 17 June 2011 this paper, we report on the synthesis of nanostructured zinc oxide particles by both chemical and
Accepted 29 July 2011
biological method. Highly stable and spherical zinc oxide nanoparticles are produced by using zinc
Available online 26 August 2011
nitrate and Aloe vera leaf extract. Greater than 95% conversion to nanoparticles has been achieved with
aloe leaf broth concentration greater than 25%. Structural, morphological and optical properties of the
Keywords:
synthesized nanoparticles have been characterized by using UV–Vis spectrophotometer, FTIR,
A. Nanostructures
Photoluminescence, SEM, TEM and XRD analysis. SEM and TEM analysis shows that the zinc oxide
B. Chemical synthesis
C. Optical properties nanoparticles prepared were poly dispersed and the average size ranged from 25 to 40 nm. The particles
D. X-ray diffraction obtained have been found to be predominantly spherical and the particle size could be controlled by
E. Electron microscope varying the concentrations of leaf broth solution.
ß 2011 Elsevier Ltd. All rights reserved.
0025-5408/$ – see front matter ß 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2011.07.046
G. Sangeetha et al. / Materials Research Bulletin 46 (2011) 2560–2566 2561
Fig. 4. PL spectra for ZnO nanoparticle. (A) Chemical method, (B) biological method.
Fig. 2. Effect of various concentration of Aloe leaf extract (ALE) on the time course of
ZnO nanoparticle synthesis. Fig. 5. FTIR spectra for ZnO nanoparticle with 0–50% ALE.
G. Sangeetha et al. / Materials Research Bulletin 46 (2011) 2560–2566 2563
the shape of the particles. The number of SPR peaks increases as the The particles obtained from both the synthesis show an
symmetry of the nanoparticle decreases [68–70]. excitation wavelength at 325 nm which is in accordance with
Fig. 4 represents the Photoluminescence (PL) spectra of ZnO results in the literature [50,51]. A relatively sharp, weak UV
particles obtained from synthesis I and II. All the samples with emission band at 3.23 eV (384 nm) and a broad stronger emission
different concentrations of ALE show similar excitation and band in the green part of the visible spectrum with a maximum
emission spectra but their luminescence intensities are different. intensity at 2.4 eV (520 nm) is observed and studied extensively.
The emission intensity decreases gradually and may be likely due ZnO nanoparticles synthesized without ALE (Fig. 4a) show the
to concentration quenching. The UV luminescence of ZnO lowest emission while nanoparticles synthesized with ALE
nanomaterials is commonly attributed to the direct recombination (Fig. 4b–f) show decreasing intensity with increasing concentra-
of excitons through an Exciton–excition scattering [71]. The visible tion ranging from 5 to 50%. The highest peak may correspond to the
luminescence originates from the radioactive recombination of a absorption peaks in the UV–Vis measurement and the band gap of
photo-generated hole with an electron occupying the oxygen ZnO nanoparticles. The broad green band at 2.38 eV is attributed to
vacancy [72]. the radioactive recombination of photogenerated hole with an
Fig. 6. SEM photographs for ZnO nanoparticles with (a) 0% ALE, (b) 5% ALE, (c) 10% ALE, (d) 15% ALE, (e) 25% ALE, (f) 50% ALE.
2564 G. Sangeetha et al. / Materials Research Bulletin 46 (2011) 2560–2566
electron belonging to a singly ionized vacancy in the surface and been assigned to stretching vibrations of the primary and
subsurface [52,53]. The emission shifts from green to red by secondary amines, O–H stretching of alcohols and C–H stretching
increasing the concentration of ALE which reflects the change in of alkanes. The corresponding bending vibration for primary and
the excition energy in the absorption spectra and increase in the secondary amines is also noticed. The peaks around 1640 and
particle size of ZnO nanoparticles. These PL signals are attributed to 1540 cm 1 are due to the amide I and amide II regions that are
band-edge free excitons and bound excitons, respectively [54]. characteristic of proteins/enzymes [57]. The intense bands
Fig. 5 shows the FTIR spectra of zinc oxide nanoparticles observed at 924, 1020, 1150 and 1380 cm 1 have been assigned
synthesized by chemical and biological method. The spectrum to alcohols and phenolic groups, C–N stretching vibrations of
obtained for synthesis I (Fig. 5a) clearly shows ZnO absorption aliphatic and aromatic amines [56], respectively. The peaks in the
band near 528 cm 1. The peaks at 3451, 1552, 1393 and 922 cm 1 region between 600 and 400 cm 1 are allotted to Zn–O [55,58] are
indicate the presence of –OH stretching of intramolecular clearly represented in the Fig. 5.
hydrogen bond, C5 5O stretching and C–C stretching of alkanes The mechanism by which nanoparticles are formed in the
[55,56]. Similar spectra are obtained for the nanomaterials biosynthesis procedures is still not clear. The overall observation
produced via synthesis II (Fig. 5b–e). The amide linkages between proves the existence of some phenolic compounds, terpenoids or
the amino acid residues in the proteins give rise to additional peaks proteins that are bound to the surface of ZnO nanoparticles that
in the infrared region (2900–3700 cm 1) of the electromagnetic remained despite repeated washing. The stability of ZnO nanopar-
spectrum. The bands observed at 3450, 3266 and 2932 cm 1 have ticle may be due to the free amino and carboxylic groups that have
Fig. 7. TEM images for ZnO nanoparticles with (a) 0% ALE, (b) 5% ALE, (c) 10% ALE, (d) 15% ALE, (e) 25% ALE, (f) 50% ALE.
G. Sangeetha et al. / Materials Research Bulletin 46 (2011) 2560–2566 2565
interacted with the zinc surface. The bonds of functional groups precursors have been completely decomposed and no other crystal
such as –CO–C–, –C–O– and –C5 5C– are derived from heterocyclic products have been retained after the decomposition process. All
compounds and the amide bands derived from the proteins are samples with aloe extract had preferred orientation along the
present in the leaf extract and are the capping ligands of the (1 0 1) plane. It has been observed that the preferred orientation of
nanoparticle [56,59,60]. Moreover the proteins present in the (1 0 1) for the ZnO nanoparticles slightly shifted to the left when
medium prevent agglomeration and aids in the stabilization by aloe extract was used when compared to ZnO prepared without
forming a coat, covering the metal nanoparticles. aloe extract (Fig. 8). As the concentration increased, the typical
The SEM and TEM monographs in Figs. 6a–f and 7a–f clearly tendency of increasing intensity of samples was determined using
shows the distribution of ZnO nanoparticles prepared with or the Scherrer’s formula, D = 0.9l/(B cos u) [65,66], where D is the
without aloe broth extract. The powders obtained were homoge- crystal size, l the X-ray wavelength, u the Bragg’s angle in radians,
neous and agglomerated with a particle size ranging from below 25 and B the full width at half maximum of the (1 0 1) peak in radians.
to 55 nm with some deviations. The images show spherical shape The average particle size of the products was around 35 nm, a trend
and hexagonal nanoparticles, which are in accord with the XRD. that generally matched the tendency shown in the TEM and SEM
Owing to the uniform distribution of oxidized metal anions in the images.
three-dimensional polymeric network structure, the agglomera-
tion could be induced by densification resulting in the narrow 4. Conclusions
space between particles [61,62]. Addition of aloe vera extract to the
zinc nitrate did not change ZnO nanoparticles shape, but it caused The secrets gleaned from nature have led to the development of
an increase in nanoparticle size especially for higher concentration biomimetic approaches for the growth of advanced nanomaterials.
(50%) of aloe vera extract. Only a small difference is observed A simple, rapid biological procedure has been developed to
between nanoparticle size measured by XRD and TEM. The synthesize zinc oxide nanoparticles with tunable optical properties
difference in the obtained values of the particle size of the directed by particle size using varying concentration of Aloe vera
produced ZnO nanoparticle is due to the fact that TEM measure- leaf broth extracted solution. The zinc oxide nanoparticle shows
ments are based on the difference between the visible grain distinct poly dispersity and the particle size ranges from 25 to
boundaries, while XRD calculations measure the extended 45 nm with an average size of 35 nm. Maximum nanoparticles
crystalline region that diffracts X-rays coherently. So, the XRD show particle size of 30 nm with distinct cap, which may be due to
method has a more stringent criterion and leads to smaller sizes the flavonoids, proteins and other functional groups present in the
[63]. leaf broth of aloe vera and are likely to be responsible for the
The TEM images at higher resolution also reveal that formation of zinc oxide nanoparticles. The explored eco-friendly,
nanoparticles are not in physical contact but are separated by high efficient zinc oxide nanoparticles prepared from Aloe vera leaf
uniform inter-particle distance. The images clearly show the broth are expected to have more extensive applications in
presence of secondary material capping with a thickness of biomedical fields and in cosmetic industries.
10 nm which may be assigned to bioorganic compounds present
in the leaf broth [49–60]. This can be further confirmed by
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