Materials Letters 259 (2020) 126853

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Green synthesis of ZnO nanoparticles using whey as an effective

chelating agent
V.A. Soares a, M.J.S. Xavier a, E.S. Rodrigues a,b, C.A. de Oliveira a, P.M.A. Farias b, A. Stingl c, N.S. Ferreira d,
M.S. Silva a,⇑
a
Physics Department, Federal Institute of Education, Science and Technology of Sertão Pernambucano, 56000-000 Salgueiro, PE, Brazil
b
Postgraduate Program in Materials Science, Federal University of Pernambuco, 50670-901 Recife, PE, Brazil
c
Phornano Holding GmbH, Korneuburg, Austria
d
Physics Department, Federal University of Sergipe, 49100-000 São Cristóvão, SE, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Zinc oxide (ZnO) nanoparticles were successfully synthesized using a whey-assisted sol-gel method. X-
Received 16 September 2019 ray diffraction (XRD) and Raman spectroscopy analysis revealed a wurtzite crystalline structure for
Received in revised form 16 October 2019 ZnO nanoparticles with no impurities present. Transmission electron microscopy (TEM), (XRD) observa-
Accepted 20 October 2019
tions, and UV–Vis absorption spectroscopy results showed that with an increase in calcination tempera-
Available online 24 October 2019
ture from 400 to 1000 °C, the size of nanoparticles increases from 18.3 to 88.6 nm, while their optical
band gap energy decreases to ~3.25 eV. The whey-assisted sol-gel method proved to be highly efficient
Keywords:
for the synthesis of crystalline ZnO nanoparticles whose applications are of great interest in material
Green synthesis
Whey
science technology.
ZnO Ó 2019 Elsevier B.V. All rights reserved.
Nanoparticles

1. Introduction thermore, it is a highly harmful waste to the environment (soil,

Zinc oxide (ZnO) is a wide band-gap II-VI semiconductor with
high binding energy [1,2]. For past decades, considerable attention
has been given to ZnO nanoparticles due to their great potential as
solar cell windows [3,4], transparent electrodes [5], gas sensors,
varistors [6], and photocatalysts for the purification and decompo-
sition of pollutants. Many investigations have shown that distinc-
tive synthesis routes have used to obtain nanosized ZnO particles
[1,2]. However, new strategies have been advanced for low-cost
nanoparticle synthesis with the use of a diverse array of material
types—organic, inorganic, and biological—in search of improve-
ments that aims to control the size, shape, structure, morphology,
and material properties [1–11]. In search of an even more eco-
friendly, economical and reliable process, we sought to develop a
green synthesis route using salts (nitrates, chlorates, and sulfates)
as the starting material and whey as an effective chelating agent
instead of conventional analytical reagents.
Whey is a by-product of milk fats and casein precipitate formed
during cheese making. It accounts for 85–90% of milk volume and
is considered one of the main pollutants of the dairy industry. Fur-
springs, etc.) because of its biochemical oxygen demand approxi-
mately one hundred times the value generated by domestic sew-
age [12]. However, whey retains most of the milk’s nutrients,
such as lactose soluble proteins, minerals, vitamins, and non-
soluble nitrogen. The proteins present in whey are of great interest
in many aspects for several applications prior to their high biolog-
ical value. They are rich in branched-chain essential amino acids
(leucine, isoleucine, and valine) and have a certain affinity for
metal ions which may control the size and morphology of the
nanostructured ZnO [12–13].
The present work reports on the synthesis and characterization
of ZnO nanoparticles obtained by using whey as a novel, inexpen-
sive, and eco-friendly chelating agent that to the best of our knowl-
edge has not been reported so far. The results obtained by X-ray
diffraction, transmission electron microscopy, selected area elec-
tron diffraction, Raman spectroscopy, and UV–vis absorbance anal-
ysis were discussed.
2. Experimental

All reactants were purchased from Merck KGaA, Darmstadt,

⇑ Corresponding author. Germany and used without additional purification unless other-
E-mail address: torrex2003@yahoo.com.br (M.S. Silva). wise specified. The typical procedures used in preparing ZnO
nanoparticles are described as follows: Firstly, zinc citrate was

https://doi.org/10.1016/j.matlet.2019.126853
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
2 V.A. Soares et al. / Materials Letters 259 (2020) 126853

Fig. 2. (a) Raman spectra for the ZnO nanoparticles calcined at different temper-
atures. (b) UV–vis absorption spectra of ZnO nanoparticles.

Fig. 1. (a) XRD patterns of ZnO Nanoparticles. (b) Typical Rietveld refined X-ray
pattern for sample calcined at 800 °C.
obtained by Zn(NO3)2.6H2O, mixed with citric acid (CA), previously
dissolved in distilled water (0.1 g/ml), at the molar ratio of 1:3.
Whey (W) was subsequently added to these solutions at the mass
ratio of CA:W = 60:40 to promote citrate polymerization. The
resultant mixture was homogenized and maintained under mag-
netic stirring for 1 h at 80 °C to complete gelatinization. The
obtained brown colored and transparent stable resin (xerogel)
aspect was heated to 100 °C in order to eliminate excess water.
Then, the xerogel was calcined at temperatures ranging from 200
to 1000 °C for one hour to obtain the resultant ZnO nanoparticles.
The as-prepared ZnO nanoparticles were then accurately charac-
terized regarding their optical and structural properties. Raman
spectra of ZnO nanoparticles were recorded using a Raman spec-
trometer (SENTERRA, Bruker). X-ray diffraction (XRD) analysis
(Rigaku RINT 2000/PC) was further performed using a Cu-Ka-
radiation tube operated at 40 kV and 40 mA. XRD data were col-
lected in a scan range of 20–70° (2h), a step size of 0.02°, and a scan
rate of 0.25° (2h min 1). Rietveld refinement procedures were
applied to XRD patterns using the Full Proof software [14]. The
crystallite size of the samples was calculated using the Scherrer
equation [11,15]. The particle size and morphology were observed
by transmission electron microscopy (TEM, JEOL-100F). The dis-
persed optical absorption spectra of ZnO nanoparticles in ethylene
glycol were recorded using a UV–VIS spectrophotometer (Kasuaki,
UV–VIS 1200).

Table 1
Nomenclature, average crystallite size, lattice parameters and unit cell volume of ZnO nanoparticles.

Nomenclature T (°C) Particle size-MET (nm) Crystallite size – XRD (nm) Lattice constants (nm) Unit cell volume (nm3)
a=b c
ZnO -1 400 20.5 18.3 3.2511 (8) 5.2110 (8) 47.702
ZnO -2 600 36.1 33.7 3.2497 (9) 5,2102 (7) 47.654
ZnO -3 800 72.0 75.1 3.2531 (4) 5.2108 (9) 47.758
ZnO -4 1000 120.1 88.6 3.2500 (7) 5.2101 (8) 47.661
 V.A. Soares et al. / Materials Letters 259 (2020) 126853
3. Results and discussion
Fig. 1(a) shows the XRD patterns of the ZnO nanoparticles cal-
cined at different temperatures. All samples that were only present
in the diffraction peaks corresponded to the crystallographic
planes (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0),
(1 1 2), and (201 l), characteristic of the hexagonal phase, wurtzite
type space group P63mc (ICSD: 26170) [2,3,11]. Fig. 1(b) shows a
typical Rietveld refinement fit for the XRD pattern of the ZnO sam-
ple calcined at 800 °C, achieved by considering the structural
parameters mentioned above. The fitted patterns agree with the
respective experimental data and indicate the accuracy of the
obtained results from v2 values for all refinements found between
1.88 and 2.54 variation. Table 1 presents the average crystallite
sizes and lattice parameters for the ZnO samples. The average crys-
tallite size decreased linearly at a rate of 0.2 nm/°C and micro
strain increased by approximately 0.3% with the increase in calci-
nation temperature. The average crystallite size of the ZnO
nanoparticles increased from 18.1 ± 0.3 nm to 88.6 ± 0.3 nm with
the increase of calcination temperature from 400 °C to 1000 °C.
The crystallization rate of solid phases increased due to the higher
mobility of atoms at high temperatures. This high mobility allows a
rapid arrangement of the crystalline structure, which should result
in higher aggregation of the crystallites to minimize the interfacial
surface energy [7].
Fig. 2(a) shows the Raman spectra of the ZnO nanoparticles cal-
cined at different temperatures. Raman modes at 379.5, 408.9,
438.5, 537.3, and 581.9 cm 1 are assigned to A1 (TO), E1(TO),
E2(H), A1(LO) and E1(LO) fundamental phonon modes of hexagonal
wurtzite crystal structure ZnO respectively. The other two Raman
prominent features at 331.7 and 979.3 cm 1 can be assigned to
the E2(H)-E2(L) and A1(LO) + E2(H) multiphoton scattering modes
respectively. The A1(TO), A1(LO), E1(TO) and E1(LO) modes result
Fig. 3. TEM images of ZnO-1. (a–b): Images of ZnO nanoparticles (c): electron diffraction pattern; (d): HRTEM.
3
from the displacement of the Zn sublattice with respect to the oxy-
gen sublattice that created a net oscillating polarization resulting
in an induced long-range electrostatic field splitting the polar
modes (A1 and E1). The A1(LO) and E1(LO) modes are associated
with the presence of oxygen vacancies or interstitial zinc [16,17].
Moreover, it worth highlighting the strong and dominant E2(H)
mode, indicating that oxygen vibrations occurred in highly crys-
talline ZnO nanoparticles. Furthermore, E2H phonon has an asym-
metric line shape and it tails toward low frequencies when
crystallite size decreases.
The UV–visible absorption spectra of the ZnO nanoparticles
(Fig. 2(b)) reveals a characteristic absorption peak of ZnO at a
wavelength range of 315–340 nm, which can be associated with
the intrinsic band gap absorption of ZnO related to electron transi-
tions from the valence band to the conduction band (O2p ? Zn3d)
[18]. Furthermore, it is quite clear that absorption peaks intensity
increases the redshift in the absorption edge as ZnO nanoparticles’
calcination temperature increases from 400 to 1000 °C. The
changes in the morphologies and particle size are (as indicated
by XRD and TEM) comparable to excitonic Bohr diameter is
6.48 nm for ZnO [19,20].
The average particle size determined from the TEM images for
the ZnO nanoparticles varied depending on the calcination temper-
ature between 20 and 120 nm which was in good agreement with
the crystallite sizes calculated from the Scherrer formula [20].
Fig. 3 illustrates representatives TEM images of the ZnO Nanopar-
ticles calcined at 400 °C. From Fig. 3(a), it can be seen that the
nanoparticles are spherical in shape and highly agglomerated.
Fig. 3(b) shows the high-resolution TEM image highlighting the
spherical shape size of approximately 17.2 ± 0.1 nm and the lattice
plane of an individual particle. In addition, the spacing between the
lattice fringes was found to be 0.30 ± 0.02 nm (Fig. 3(d)), which is
consistent with the interplanar spacing between the (1 0 0) lattice
4 V.A. Soares et al. / Materials Letters 259 (2020) 126853
planes of the ZnO phase. Moreover, selected area electron diffrac-
tion (SAED) ring patterns displayed a structure composed of six
concentric sharp rings (Fig. 3(c)), which correspond to the (1 0 0),
(0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), and (1 1 2) planes of the
ZnO in hexagonal structure [19,20]. Based on these results
obtained, it is possible to state that ZnO nanoparticles have a high
degree of crystallinity and free of spurious phases using whey as an
environmental friendly chelating agent. Additionally, this approach
can be readily scaled up toward the preparation of a variety of
other nanostructured transparent conducting oxides such as
SnO2, CdO and transition metal nanoparticles.
4. Conclusion
ZnO nanoparticles were successfully synthesized by a whey-
assisted sol-gel method. The XRD, TEM, and Raman spectroscopy
structural analysis confirms that all ZnO nanoparticles calcined in
the range of 400 °C to 1000 °C exhibited wurtzite crystalline struc-
ture and size between ~18 and 89 nm. TEM analysis revealed e a
spherical morphology for the ZnO nanoparticles. SAED patterns
consisting of bright uniform rings confirm a preferential orienta-
tion for nanocrystals instead of random orientation. UV–visible
spectroscopy showed that band gap of ZnO nanoparticles was
decreased by an increase in calcination temperature, as can be
observed in the absorption maximum shifted to higher wave-
lengths. The results herein reported and discussed, demonstrate
that whey is an efficient and ecologically friendly chelating agent
that allows the production of highly crystalline ZnO nanoparticles
with controlled shape and size.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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