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Research Article
of bromocrescol green
Jejenija Osuntokun1, Damian C. Onwudiwe1 , Eno E. Ebenso2
1Faculty of Natural and Agricultural Science, Material Science Innovation and Modelling (MaSIM) Research Focus Area, North-West University
Abstract: CaO nanoparticles have been prepared using CaCl2 and aqueous extract of broccoli as a precursor and reducing
agent, respectively. Different volumes of the aqueous broccoli extract were utilised to obtain Ca(OH)2 and subsequent
calcination gave CaO nanoparticles. The synthesised CaO was confirmed by powder X-ray diffraction (XRD). The morphology
was studied using transmittance electron microscopy (TEM), and the surface composition of Ca(OH)2 was explored using
Fourier transform infrared spectroscopy. The major functional groups present in the capping material responsible for the
reduction of the metal salt and the surface passivation of Ca(OH)2 were identified. The XRD pattern revealed cubic phase for all
the CaO nanoparticles, and the crystallite size was estimated using Scherrer's equation showed a variation which is dependent
on the volume of the extract used. TEM analysis showed different shapes, while the selected area electron diffraction (SAED)
results confirmed the crystallinity of the nanoparticles. Thermogravimetric analysis of Ca(OH)2 showed the decomposition
product to be CaO. Sample C3, which has the smallest particle size, was used as a catalyst for the degradation of bromocresol
green via photo irradiation with ultraviolet light and the result revealed a degradation efficiency of 60.1%.
1 Introduction Although CaO nanoparticles have been synthesised via all the
aforementioned chemical routes, there are only a few reports
One of the goals of nanotechnology is the synthesis of varieties of involving the green chemistry approach. Green synthesis of
nanoparticles in different morphologies and chemical nanoparticles using aqueous plant extract is an environmentally
compositions, with narrow size distribution, monodispersed and benign and cheap route to nanoparticles synthesis. Several cases of
their prospective applications to the benefit of mankind [1]. The plant mediated synthesis of metal and metal oxide nanoparticles
immense interest in the study of nanoparticles arose by virtue of have been reported such as Au, ZnO, SnO2 and CaO nanoparticles
their rare physiochemical characteristics viz. mechanical, optical,
[20–24].
electronic, magnetic, antimicrobial, and catalytic properties.
Broccoli belongs to Brassicaceae family whose origin is the
Calcium oxide (CaO) is an alkaline earth metal oxide and the
Mediterranean part of the world. This vegetable is rich in folic
heaviest among the group of light alkaline earth oxide. Bulk CaO
acid, vitamin C, fibre, carotene, phytochemicals such as
has a wide band gap of 7.1 eV [2] and a high dielectric constant of
polyphenols and glucosinolates. Phytochemicals in broccoli viz.
11.8. CaO nanoparticles are non-toxic, low cost, readily available
glucosinolates and flavonoids have been of interest for their
raw material for heterogeneous catalysis for diverse reaction
potential ability to maintain good health, and in green chemistry for
procedures [3–5]. There are many other applications of CaO
their use as reducing and capping agent in nanoparticle synthesis
nanoparticles such as additive in refractory [6], adsorbent
[25].
especially in catalysis [7], bactericides [8], in biomedical field [9],
The heavy use of dyes in industries is majorly responsible for
and as well as a precursor in bioceramics [10]. CaO nanoparticles
the unprecedented rate of water pollution in our environment. This
have been reported as a good adsorbent in the removal of Cr(VI)
scourge ultimately has a direct or immediate repercussion on the
from solutions [11], in the transesterification of sunflower [12] and
ecosystem [26]. For instance, organic dyes form the bulk of
palm oil [13], and also in the removal of other toxic metal ions
industrial effluent and the urgency of the need to eliminate these
[14].
types of contaminants cannot be overemphasised. These
CaO nanoparticles are rarely studied, and only a few reports
contaminants are not biodegradable and despite the development of
exist in the literature. Nevertheless, a range of methods has been
various ways of elimination, water pollution problems seem to
used for their preparation such as thermal decomposition [15],
remain unabated. Some techniques have been employed to carry
microwave [16] and sol–gel processes [17]. Of all these methods,
out environmental remediation and among such are ion exchange
thermal decomposition and sol–gel processes are the most
and precipitation [27], floatation [28], and adsorption processes
commonly used method of synthesising CaO nanoparticles. Low-
[29]. In spite of the application of these methods of waste water
dimensional nanoparticles can be obtained from the sol–gel
remediation, the issue of toxic by-products generated has been a
method; although, the route has the following demerits: (i) high
source of constant concern; hence the application of photocatalytic
cost, (ii) long reaction time, and it is complicated. On the other
degradation whose by-products are environmentally benign.
hand, thermal decomposition processes are better due to the
Photocatalysis is a process of degrading organic contaminants in
following: (i) high purity, (ii) simplicity, and (iii) low cost. CaO
water by the use of photo-irradiation source. Oxidation of organic
nanoparticles can be obtained from high temperature calcination of
contaminants in solution or suspension is accomplished by the
Ca(OH)2 and CaCO3 [18, 19].
generation of reactive hydroxyl or superoxide radicals, which are
Fig. 1 Overlapped p-XRD pattern of C1, C2, and C3 of CaO % degradation = Ao − At / Ao × 100,
nanoparticles formed from calcination of Ca(OH)2 at 650°C
where Ao and At are corresponding initial absorbance of dye before
involved in the degradation process. Photocatalytic degradation degradation and the final absorbance of dye at degradation time ‘t’.
under ultraviolet (UV) irradiation is an alternative method for the
degradation of organic materials using semiconductor materials. 2.5 Characterisation of biosynthesised CaO nanoparticles
In this work, we have prepared CaO nanoparticles through
reduction of the metal chloride to the metal hydroxide and high The X-ray diffraction (XRD) measurement was recorded over a 2θ
temperature calcination of the precursor, Ca(OH)2 (intermediate range of 20–85° on a Bruker D8 Advanced, equipped with a
product). After calcination, residues from the aqueous extract of proportional counter using Cu Kα radiation (k = 1.5405 A, nickel
broccoli were removed and it subsequently improved the crystal filter). Transmittance electron microscopy (TEM) measurements
phase given a homogenous product [30]. To the best of our were performed on a TECNAI G2 (ACI) instrument operated at an
knowledge, this is the first report on the use of aqueous broccoli accelerating voltage of 200 kV. Surface morphologies were
extract as a stabilising agent for the synthesis of CaO nanoparticles. measured by using a scanning electron microscope with the aid of a
JOEL JSM-6390 LVSEM operated at a voltage of 15–20 kV.
Absorption measurement was performed with a Cary 300 UV–vis
2 Experimental
spectrophotometer from Agilent technologies. Fourier transform
2.1 Materials infrared (FTIR) spectra of the aqueous broccoli extract and
synthesised CaO nanoparticles were measured in the range of
Fresh broccoli vegetables were purchased from Woolworth stores
in South Africa and properly identified; calcium chloride, sodium 4000–400 cm−1 on a Cary 670 FTIR spectrometer from Agilent
hydroxide and bromocresol green (BG) were purchased from Technologies. Thermogravimetric analysis (TGA) spectra were
Sigma Aldrich, South Africa. obtained from SDTQ 600 thermal instrument. Samples were heated
in an alumina crucible at the rate of 10 min−1 in the temperature
2.2 Preparation of fresh broccoli extract range of 25–800°C under a nitrogen atmosphere. Photocatalytic
studies were performed with a photo reactor fabricated by North-
Aqueous extract of broccoli was prepared by a slight modification West University science workshop.
of a reported method [31]. About 12 g of broccoli leaves were
carefully washed with double distilled water, air dried and 3 Result and discussion
pulverised. The leaves were then collected and boiled at 60°C in
250 ml flask containing double distilled water for 15 min. 3.1 Power XRD (p-XRD) studies
Thereafter, the aqueous extract was cooled, filtered using The p-XRD measurement of the samples was carried out to
Whatmann No. 1 filter paper (pore size 25 µm), and stored in a identify the composition and phase of the samples. Fig. 1 shows the
refrigerator for further use. overlapped p-XRD patterns of CaO nanoparticles C1, C2, and C3
prepared using 10, 20, and 30 ml of the extract, respectively. All
2.3 Preparation of CaO nanoparticles the three samples exhibit reflection peaks that can be indexed to a
An appropriate amount of aqueous extract of broccoli (10, 20 and cubic face-centred crystal structure and are consistent with the
30 ml) was separately added to a 50 ml CaCl2 (0.1 M) and stirred standard JCPDS No. 77-2376 [32]. The XRD pattern showed that
the calcination process was accompanied by the formation of a
continuously for 40 min. To this solution, aqueous (2 M) NaOH trace amount of CaCO3. This is due to rapid carbonation of
was added dropwise to adjust the pH to 12 and stirred for 2 h until
a white milky precipitate of Ca(OH)2 was observed. The product Ca(OH)2 and CaO by atmospheric carbon(IV) oxide [33].
was isolated by centrifugation at 4000 rpm for 15 min and washed Carbonation reaction for Ca(OH)2 and CaO has been reported to
several times with distilled water to remove any unreacted starting progress very fast, and the rate is directly proportional to the
material. Thereafter, the white Ca(OH)2 samples were dried in the increase in the surface area [34, 35]. This is a confirmation of the
oven for 8 h at 90°C. Three samples were produced based on the potential of the CaO in getting rid of CO2, a greenhouse gas from
different volumes of aqueous plant extract used for the synthesis, the air [36].
and the samples were labelled as C1, C2, and C3, respectively. The mean crystallite size was estimated to be in the range of
About 1 g of each of the sample was placed in a muffle furnace 32–45 nm using Scherrer's equation, (D = Kλ/β cos θ) [37], where
using ceramic crucible and calcined at 650°C for 2 h. β = full-width at half-maximum of diffraction peak, θ is the
position of the maximum of the diffraction peak, λ = 1.54 Å is the
wavelength of X-rays while K is the so-called shape factor, which
2.4 Photocatalytic studies
usually takes a value of about 0.9. Characteristic peaks were
A uniquely fabricated photocatalytic reactor fitted with a water observed to have high intensity and narrow spectra width, and this
jacket to ensure a continuous flow of water was employed for is indicative of the good crystallinity of the CaO nanoparticles.
photocatalytic degradation of BG dye. The function of the water Based on standard XRD data of cubic CaO nanoparticles, the
reflected peaks with a corresponding 2θ value of ∼37.30° is the The UV-absorbance spectra of the nanoparticles are depicted in
most prominent and authentic peak of CaO nanoparticle [38]. Figs. 6a–c. The absorbance spectra were recorded over a
wavelength range of 310–810 nm. The spectra showed absorption
edges at 298, 297 and 295 nm for C1, C2, and C3, respectively.
3.2 TEM studies
The bandgap energy of the nanoparticles was estimated using Tauc
TEM analysis was performed to study the morphology of the plot [39].
nanoparticles. The TEM images of C1, C2, and C3 are presented in The Tauc equation is represented as follows:
Figs. 2A, 3A, and 4A, respectively. The micrographs showed cube-
like shaped nanoparticles with average particle sizes of 38, 32, and αhv = D hv − Eg ,
n
(1)
29 nm for C1, C2, and C3, respectively. High-resolution
transmission electron microscopy (HRTEM) of the images where hv is the energy of the incident photon, α is the linear
presented in Figs. 2B, 3B, and 4B show the presence of lattice absorption coefficient of the material, Eg is the optical bandgap
fringes in the CaO nanoparticles which revealed the crystallinity of energy, D is the constant, n = 2 as exponential for indirect bandgap
the nanoparticles. The appearance of dispersive single crystals of semiconductors.
the SAED in insets, Figs. 2a, 3c, and 4b, confirm the crystallinity A Tauc plot of αhv versus hv for C1, C2, and C3 nanoparticles
of all the nanoparticles while the SAED spots with bright circular are depicted as insets in Figs. 6a–c. The Tauc plots revealed the
rings match the different crystallographic planes of the cubic face optical band gap of the nanoparticles as 4.16, 4.17, and 4.20 eV for
CaO. The concentration of aqueous extract seemed not to have any C1, C2, and C3, respectively. These band gap energies were
appreciable effect on the morphology of the nanoparticles except in calculated from the extrapolation of the linear portion of the
the size. respective plots to the x-axis (hv) or to absorption equal to zero.
The band gap energies for C1, C2, and C3 confirm that the
3.3 Scanning electron microscopy (SEM) and energy absorption of CaO nanoparticles lies in the UV region as seen from
dispersive spectroscopy (EDS) the spectra in insets. The calculated band gap is comparable to the
Representative SEM micrographs of the nanoparticles are similar band gap of 4.17 and 4.94 eV that have been reported [9,
presented in Figs. 5A–C. There is a noticeable variation in the 40, 41]. There is a noticeable correlation between the volume of the
morphology of the nanoparticles. The SEM micrograph of C1 aqueous broccoli extract and the crystallite size of CaO. As the
presented in Fig. 5A showed dense, nearly uniform spherical volume of broccoli extract increases, the crystallite size slightly
shapes with traces of agglomerations, while C2 (in Fig. 5B) reduces. This is similar to earlier report whereby a decrease in the
showed tightly packed and spheroid porous nanoparticles that ratio of the plant extract to the nanoparticles precursor resulted in
appeared like dense platelets with intercalated hexagonal shapes. an increase in the size of the nanoparticles [42]. However, an
Fig. 5C appeared to be similar to the first two SEM micrographs increase in the crystallite size of Au nanoparticles has been
with cluster-shaped nanoparticles that are around 0.25 µm in size. reported with an increase in the concentration of the plant extract
EDS analysis was performed to investigate the elemental [43].
composition of C1, C2, and C3. The results unequivocally
confirmed the presence of Ca and O elements as the major 3.5 Thermal study
composition of the biosynthesised samples. The percentage The decomposition process of the biosynthesised Ca(OH)2 was
elemental compositions of the nanoparticles are: O (47.86%), Ca
(50.02%), C (2.12%); O (47.17%), Ca (50.63%), C (2.20%); O investigated with TGA and the result is shown in Fig. 7. The
(47.01%), Ca (50.19%), C (2.80%) for C1, C2, and C3, samples were heated from 35 to 800°C at the rate of 10°C/min.
respectively. Two major weight loss stages were identified; C1: 388–440°C,
376–443°C; C2: 366–440°C, 440–632°C; and C3: 443–670°C,
440–628°C. The first set of weight loss corresponded to the
Fig. 8 Overlapped FTIR of C1, C2, C3, and aqueous extract of broccoli