ZnO Biosinteza
ZnO Biosinteza
ZnO Biosinteza
Materials Letters
journal homepage: www.elsevier.com/locate/matlet
art ic l e i nf o a b s t r a c t
Article history: This contribution reports on the synthesis and the main physical properties of ZnO nanoparticles syn-
Received 20 July 2015 thesized for the first time by a completely green process using Agathosma betulina plant extract as an
Received in revised form effective chelating agent. The surface/interface and volume room temperature properties of these quasi-
9 August 2015
spherical 15.8 nm in size ZnO nanoparticle by transmission electron microscopy, energy dispersive X-Ray
Accepted 10 August 2015
Available online 10 August 2015
Spectroscopy, X-rays diffraction, attenuated total reflection IR and Raman spectroscopy are reported.
Likewise, a spark sintered pellet made of such nanoparticles exhibited a significant nonlinear current–
Keywords: voltage exponential response characteristic of a varistor.
Green synthesis & 2015 Elsevier B.V. All rights reserved.
Zinc oxide
Nanoparticles
Agathosma betulina’s extract
http://dx.doi.org/10.1016/j.matlet.2015.08.052
0167-577X/& 2015 Elsevier B.V. All rights reserved.
F.T. Thema et al. / Materials Letters 161 (2015) 124–127 125
dye extract solution (pH 5) was filtered twice to eliminate residual nanoparticles. Fig. 2b reports a typical X-Rays Diffraction (XRD)
solids. Analytical grade hydrated zinc nitrate Zn(NO3)2 6H2O was profile of the optimized nanoparticles (λCukα1 ¼1.5406 Å). The
considered as a zinc precursor. 6.0 g of zinc nitrate was homo- 8 observed Bragg peaks match entirely with the single phase ZnO
geneously mixed with 100 ml of A. betulina solution and heated at wurtzite pattern (JCP 00-036-1451). The deduced lattice constants
100 °C for 2 h. Following such a phase, a precipitate was observed. are 〈aexp.〉 ¼3.24 and 〈cexp.〉 ¼5.93 Å. Relatively to bulk ZnO, there is
This precipitate was washed with dH2O repeatedly and centrifuged a significant difference in the clattice value indicating that the [001]
at 1000 rps for 10 min and subsequently dried in an oven at direction is under elongation conditions. Likewise, the ratio Δd/
100 °C. The dried precipitate was annealed in an open furnace at dbulk (Δd ¼[dexp dbulk]) is negative except for the [002] reticular
various temperatures within the range 100–500 °C for 2 h. The direction sustaining the fact that the c-direction is under stretch-
annealing at 500 °C was the optimized condition to obtain highly ing conditions. The Debye-Scherrer approximation 〈Ø〉∼0.9λ/ ΔΘ1/
crystalline ZnO nanoparticles. 2 cos(ΘB) gives an average size of the optimized ZnO nanoparticles
of ∼19.4 nm in line with the TEM results.
3.1. Morphology & microscopy observations To validate again the zincite nature of the synthesized nano-
particles and their purity, Attenuated Total Reflection-Fourier
Fig. 1 reports a typical a High Resolution Transmission Electron Transform Infrared spectroscopy (ATR-FTIR) studies were per-
Microscopy (HRTEM) image of the optimized sample (Annealed at formed. Fig. 3a reports the typical ATR-FTIR spectrum of the
500 °C). It consists of quasi-spherical agglomerated nano-scaled pressed powder in the spectral range of 400–4000 cm 1). The IR
particles. The digitization phase of various images indicates that transmission is plotted so to single out the major absorptions
the nanoparticles' diameter Ø ranges from 12 to 26 nm. By fitting observed at lower wavenumbers. One can distinguish a broad
the histogram data with a Gaussian distribution, 〈Ø〉 was found to band observed at 3437.5 cm 1 attributed to the O–H stretching
be 15.8 70.2 nm (Fig. 1b). The Selected Area Electron Diffraction mode of hydroxyl group. The characteristic bands corresponding
(SAED) profile of Fig. 1c indicates via its combined spotty ring to the Zn–O stretching mode are observed at 493.8 and
patterns the highly crystallized structure of the synthesized na- 846.2 cm 1[25]. In view of the relative intensity of the Zn–O
noparticles. Fig. 1d reports an HRTEM image of single nano- modes to the adsorbed OH compounds, one can pre-conclude on
particles revealing a series of distinguishable reticular plans with the high crystallinity and purity of the synthesized ZnO nano-
reticular distances dhkl of 0.25 nm and 0.28 nm. These values fit particles. Like most wurtzite crystal structure materials, ZnO be-
with the (101) and (100) reticular distances of the ZnO hexagonal longs to the hexagonal system with C6v4(P63mc) with two formula
wurtzite structure (JCP 00-036-1451). units per primitive cell where all atoms occupy C3v sites. Ac-
cording to the group theory, ZnO has active photon modes of A1, E1
3.2. Elemental & structural analysis and 2 E2 type and inactive photon B1[26]. Fig. 3b displays the
Raman spectrum using the 473 nm excitation laser line with an
Fig. 2a reports a typical Energy Dispersive X-Ray Spectroscopy average excitation power of 2.48 mW in the spectral range of 200–
(EDS) spectrum. The spectrum of the optimized sample confirmed 1000 cm 1. It consists of a dominant peak centered at 439.6 cm 1
the presence of zinc and oxygen in the powder. The appearance of attributed to E2(high) mode of wurtzite ZnO [27]. The band at
C (0.26 keV) and Cu (8.09 keV) are attributed to the C coated Cu 505 cm 1 maybe associated with oxygen deficiency or oxygen
grid support. Consequentially, there are no other elements except vacancies in ZnO [28]. The mode at 332.8 cm 1 is generally asso-
Zn and O sustaining the pure chemical form of the formed ZnOy ciated to the second order structure of 2E2(M). The disorder–
Fig. 1. TEM image of the optimized ZnO particles (a) with their size distribution (b), their SAED pattern (c) and HRTEM image (d).
126 F.T. Thema et al. / Materials Letters 161 (2015) 124–127
Fig. 3. (a) ATR-FTIR spectrum of the optimized ZnO nanoparticles and (b) their
Raman spectrum.
Fig. 2. (a) EDS spectrum of the optimized ZnO nanoparticles and (b) their XRD
pattern.
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