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Nickel Oxide Nanoparticles Biosynthesized Characterization and Photocatalytic Application in Degradation of Methylene Blue Dye

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Nickel Oxide Nanoparticles Biosynthesized Characterization and Photocatalytic Application in Degradation of Methylene Blue Dye

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Inorganic and Nano-Metal Chemistry

ISSN: (Print) (Online) Journal homepage: www.tandfonline.com/journals/lsrt21

Nickel oxide nanoparticles: biosynthesized,


characterization and photocatalytic application in
degradation of methylene blue dye

Abdolhossein Miri, Fatemah Mahabbati, Ahmad Najafidoust, Mohammad


Javad Miri & Mina Sarani

To cite this article: Abdolhossein Miri, Fatemah Mahabbati, Ahmad Najafidoust, Mohammad
Javad Miri & Mina Sarani (2022) Nickel oxide nanoparticles: biosynthesized, characterization
and photocatalytic application in degradation of methylene blue dye, Inorganic and Nano-
Metal Chemistry, 52:1, 122-131, DOI: 10.1080/24701556.2020.1862226

To link to this article: https://doi.org/10.1080/24701556.2020.1862226

Published online: 14 Dec 2020.

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https://www.tandfonline.com/action/journalInformation?journalCode=lsrt21
INORGANIC AND NANO-METAL CHEMISTRY
2022, VOL. 52, NO. 1, 122–131
https://doi.org/10.1080/24701556.2020.1862226

Nickel oxide nanoparticles: biosynthesized, characterization and photocatalytic


application in degradation of methylene blue dye
Abdolhossein Miria, Fatemah Mahabbatia, Ahmad Najafidoustb,c, Mohammad Javad Mirid, and Mina Saranie
a
Department of Pharmacognosy, Faculty of Pharmacy, Zabol University of Medical Sciences, Zabol, Iran; bDepartment of Chemical
Engineering, Sahand University of Technology, Tabriz, Iran; cWater and Wastewater Company of Tabriz, Tabriz, Iran; dPediatric
Gastroenterology and Hepatology Research Center, Zabol University of Medical Sciences, Zabol, Iran; eZabol Medicinal Plants Research
Center, Zabol University of Medical Sciences, Zabol, Iran

ABSTRACT ARTICLE HISTORY


In the present study, nickel oxide nanoparticles were prepared using the aqueous extract of Received 22 August 2020
Zizyphus jujuba. The temperature and time calcination was studied on size and morphology of Accepted 1 December 2020
synthesized nanoparticles. In addition, the obtained nanoparticles were identified through PXRD,
KEYWORDS
UV-Vis, Raman, FESEM, and EDX methods. The results of PXRD, which were surveyed through
NiO NPs; Zizyphus jujuba;
Debye-Scherrer and Rietveld refinement, confirmed the face centered cubic (FCC) structure of syn- photocatalytic; methy-
thesized nanoparticles. The formation of synthesized NiO NPs was indicated by peak that was lene blue
revealed at 295 nm through UV-Vis spectrum. According to the FESEM results, the obtained nano-
particles (at 350 to 600 ˚C temperatures) were uniformed in shape and contained a size range of
about 5–30 nm. Subsequent to investigating their photocatalytic activity against methylene blue
(MB) dye in the role of a cationic dye, we estimated the degradation coefficient of methylene blue
to be 65.5% throughout 180 min of treatment time.

Introduction catalysts, antiferromagnetic layers, and magnetic separation


of proteins. Furthermore, nickel oxide nanoparticles are also
Today, the importance of nanotechnology in improving and
utilized in UV photodetectors and solar cells due to their
advancing different products, tools, and devices is well
high durability and stability.[14,15] The increasing population
known.[1] In recent years, the magnetic nanoparticles of
of earth and human needs have led to the construction of
iron, cobalt, and nickel have been widely exerted due to
industries and factories and thereby, the amount of pro-
their super-magnetic properties, which include the fields of
duced waste and water consumption has been intensi-
medicine, pharmacy, memory storage, sensors, MRI, and
cancer cell therapy.[2,3] Being the twenty-eighth element of fied.[16,17] Meanwhile, dyes stand as one the most
periodic table, nickel has proved to be metal-resistant and climacteric types of pollutants that are continuously released
malleable, while appearing in shiny silver and white colors from wastewater and industrial processes. Most of the exist-
and containing crystalline and cubic structures. Its magnetic ing dyes are toxic, resistant to biodegradation, and environ-
features and chemical activity are similar to those of iron mentally sustainable.[18] Therefore, the removal and
and cobalt.[4] Nickel oxide is a green or black crystalline degradation of organic dyes has become a major issue in
powder that has varying states including nickel trioxide or recent years. As it is known, Photooxidation is a cost-effect-
sesquioxide, nickel dioxide, nickelosic oxide, and nickel per- ive way for the removal of pollutants,[19–30] while Nickel
oxide.[5] Among the reported magnetic behaviors of nickel oxide stands as one of the metal semiconductors that can
oxide nanoparticles, one can mention their super paramag- provide the degradation of water pollutants under UV radi-
netic, super antiferromagnetic, and ferromagnetic properties, ation.[31,32] However, the mentioned synthetic methods for
which can be influenced by particle size, shape, and synthe- NiO NPs have been observed to be costly, time-consuming,
sizing method. Up to this day, Nickel oxide nanoparticles and complicated. According to many previous studies, a bio-
have been synthesized by different techniques such as chem- synthetic method that involves the usage of plants and
ical precipitation,[6] sol-gel,[7] thermal decomposition,[8] microorganisms can be considered as a cost-effective, inex-
microemulsion,[9] co-precipitation,[10] microwave irradi- pensive, and easy way for synthesizing nanoparticles.[3,33–44]
ation,[11] laser abrasion[12] and green synthesis[13]. The In this regard, the synthesis of NiO nanoparticles through
obtained nanoparticles have been widely applied in many the utilization of different plants such as Agathosma betu-
fields including semiconductor materials, smart window fab- lina,[45] Moringa oleifera,[46] Aegle marmelos,[47] Hydrangea
rication, electrochromic films, biosensors, gas sensors, paniculata,[48] Okra,[49] Rheum Turkestanicum[50] has been

CONTACT Mina Sarani [email protected]; [email protected] Zabol Medicinal Plants Research Center, Zabol University of Medical Sciences, P.O.
Box, 3333-669699 Zabol, Iran.
ß 2020 Taylor & Francis Group, LLC
INORGANIC AND NANO-METAL CHEMISTRY 123

Figure 1. Suggested mechanism for the synthesis of NiO NPs using aqueous extract of Z. jujuba fruit.

researched. Zizyphus jujuba is a drought-resistant tree with light and sample at 10 cm. In order to balance the nanopar-
an edible fruit that contains medicinal properties.[51] This ticles, the suspension was shaken for 30 minutes in the dark
plant grows in tropical and subtropical regions of Asia (east and exposed to UV light. Thereafter, the sample was taken
and south) and America, as well as in Mediterranean at specific time periods and centrifuged at 4000 rpm for
areas.[52] The bioactive compounds of Z. jujube fruit are 5 min; the obtained solution was scanned through the usage
capable of reducing metal ions, which include triterpenoid of a UV-Vis spectrophotometer. The control sample con-
acids, flavonoids, cerebrosides, phenolic acid, alpha-tocoph- tained a solution of Methylene blue without nanoparticles.
erol, beta-carotene, polysaccharide, and triterpenoid acid.[52] In addition, the degradation coefficient of methylene blue
Considering how the physicochemical properties of NPs can was calculated by the application of Beer-Lambert’s law. In
be influenced by their synthesizing method, this study has following, commercial NiO NPs sample (NiO nanopowder,
produced nickel oxide nanoparticles by utilizing the aqueous Sigma-Aldrich, >50 nm,) was tested in same condition for
extract of Z. jujuba fruit for the very first time, and also compared to synthesized sample.
investigated their photocatalytic activity.
Results and discussion
Experimental Plant metabolites, which include sugars, terpenoids, poly-
Synthesis of NiO NPs phenols, alkaloids, phenolic acids, and proteins, can take the
crucial role of reducing agents for converting metal ions
To prepare the aqueous extract of Z. jujube, its fruit (1:10 into nanoparticles. These metabolites are also capable of act-
ratio) was initially crushed and shaken overnight at 150 rpm ing as reducing and stabilizer agents toward nickel ions.[53]
with distilled water as the solvent. Then, the mixture was fil- In this regard, the extract compound of Z. jujuba fruit was
tered to store the resulting extract for performing further used to induce an oxidation transfer in nickel ions. To com-
experiments. As the next step, we diluted 5 mL of the extract plete the process, the composed Ni(OH)2 was converted into
into 50 mL and added (5 mM) of nickel nitrate solution. The NiO nuclei through the dehydration and growth of nanopar-
obtained solution was stirred at 80 ˚C for 4 h and dried ticles. Furtheremore, the phenolic and sugary compounds
afterwards at 90 ˚C. The dried powder was sintered at the that exist in the extract facilitated the stabilization of these
temperatures of 350, 400, 450, 500, 550, and 600 ˚C for nanoparticles (Figure 1).
120 min at separate sessions and achieved the black powder
of nickel oxide nanoparticles as the resultant.
UV-Vis spectroscopy

Photocatalytic assay UV-Vis spectroscopy stands as an effective method for


determining the formation and stability of metal and metal
To perform this assay, 10 mg of synthesized nickel oxide oxide nanoparticles in aqueous solutions. Figure 2 reveals
nanoparticles was added to 20 mL of aqueous solution of the UV-Vis spectrum of NiO NPs that were synthesized at
MB. The test was carried out in a Pyrex photoreactor that 450 ˚C. The observed peak at 301 nm was indicative of NiO
was equipped with a thermometer for controlling the tem- NPs formation, which this absorbance was differed with
perature. We used Methylene Blue in a concentration of extract of Z. jujuba fruit. It shows a blue shift relative to the
10 ppm with a pH ¼ 7 while adjusting the distance between bulk state. This peak was attributed to the electron transfer
124 A. MIRI ET AL.

Figure 2. UV-Vis spectra of synthesized NiO NPs (450 ˚C/120 min) and extract
of Z. jujuba fruit.

that occurred from the capacity band of 2p oxygen toward


the conduction band of 3d nickel.[54] Furthermore, the
results of previous studies have reported the detection of a
peak at 319, 320, and 299 nm regions.[54,55]

XRD analysis
XRD is one of the most practical diagnostic techniques that
can demonstrate the structural properties of nanoparticles
and provide sufficient information on their status. Figure 3. XRD graph of synthesized NiO NPs using extract of Z. jujuba fruit in
(A) different temperatures and (B) different calcination times.
Difference in peak width could be caused by varying particle
sizes. The XRD spectra of NiO NPs at six temperatures are
displayed in Figure 3A, while different calcination time
intervals (at 450 ˚C) are demonstrated in Figure 3B. One 13.98, 12.39, and 16.79 nm were estimated for the time
intervals of 60, 120, and 180 min at 450 ˚C, respectively.
can perceive 5 types of peaks throughout the XRD diagram
According to the outcomes, the size of synthesized nanopar-
of synthesized NiO NPs at the points of 37.2, 43.2, 62.95,
ticles increases as the temperature is heightened. In addition,
75.1, and 79.2 that were corresponding to the levels of
the lattice constant (a ¼ b ¼ c) can be increased by intensify-
(111), (200), (220), (311), and (222), respectively; these
ing the crystallite size of nanoparticles (Table 2).
results are related to the face centered cubic (FCC) structure Specific surface area (SSA) is considered as a basic unit
with the JCPDS code of 47-1049.[56] for the particle properties of nanoparticles. Sauter formula
The crystallite size of nanoparticles was estimated by the (d ¼ 6/qSx; where d represents the diameter of particles, q is
application of Debye-Scherrer equation (D ¼ 0.9k/bcosh, the density of particles, Sx stands for specific surface area)
where D stands for the size of crystals, h denotes the diffrac- was applied to calculate the SSA of synthesized nanoparticles
tion angle of highest peak, b represents the width of tallest (Table 1) and according to the gathered data, specific sur-
peak at half height, and k is the x-ray wavelength that corre- face area faces a decrease as the particle size is increased.
sponds to 1.5406 angstroms).[57] According to Debye- The method of Rietveld refines the differences between
Scherrer equation, the size of synthesized NiO NPs at the experimental and calculated patterns. The values of lattice
temperatures of 350, 400, 450, 500, 550, and 600 ˚C was cal- parameters and goodness of fit (v2) in regards to the synthe-
culated and observed to be 5.52, 10.54, 12.39, 18.45, 23.63, sized NiO NPs are presented in Table 2. The results of
and 26.27 nm, respectively. On the other hand, the sizes of Rietveld analysis, in comparison to the XRD experimental
INORGANIC AND NANO-METAL CHEMISTRY 125

and calculated patterns of the synthesized NiO NPs at 450 FT-IR analysis
˚C, are exhibited in Figure 4. In conformity to v2 values, an
The secondary metabolites of Zizyphus jujuba fruit, which
acceptable fit was observed between the XRD experimentally
and Rietveld calculated patterns. include flavonoids, triterpenoic acids, polysaccharides, and
phenolic acid,[58] are capable of acting as stabilizing and
covering agents. In brief, when salt dissolves in water, the
metal ion of nickel is created and the active agents such as
Table 1. The specific surface area (SSA) and grain size of synthesized NiO NPs.
ketone and hydroxyl groups attempt to form a binding and
Parameters
force the ions to be reduced, which results in their convert-
Specific Surface Area (m2/gr) Particle Size (nm) ing into nanoparticles. A complex (Ni2þ-polyphenol) is
NiO NPs (temp (˚C) /120 min) formed once a metal ion is bound to ligands and this pro-
350 522.5 5.52
400 273.8 10.54 cess can be captured through the employment of FT-IR.[59]
450 232.8 12.39 In regards to the captured spectrum, the peak of
500 256.3 18.45 3415 cm1 belonged to the OH group of phenolic or hydro-
550 122.0 23.63
600 109.8 26.27 gen bonds of alcohols. In addition, the observed peak at
NiO NPs (time (min) /450 ˚C) 2925 cm1 was related to the vibration of C-H bonds, while
60 206.3 13.98 the vibrations at 1127 and 1626 cm1 region indicated the
120 232.8 12.39
180 171.8 16.79 presence of aromatic and carbonyl groups, respectively. The
detected peak at 1626 cm1 can be assigned to carbonyl and
flavonoids groups, as well as the existing ester bonds in
Table 2. lattice constant (a ¼ b ¼ c), unit cell volume (V) and goodness of fit polyphenolic compounds.[57] According to Figure 5, the
(v2) of NiO NPs after Rietveld refinement. recorded peaks throughout the region of 618 and 474 cm1
Parameters represent the appearance of Ni-O bonds.[60]
a ¼ b ¼ c (Å) V (Å3) v2
NiO NPs (temp (˚C) /120 min)
350 4.1774(1) 72.897 1.18 Raman analysis
400 4.1779(5) 72.926 1.49
450 4.1782(7) 72.934 1.60 Raman spectroscopy is a molecular spectroscopy technique
500 4.1786(5) 72.959 1.67 that is based on the interaction between light and matter. In
550 4.1789(5) 72.985 1.74 this method, each material contains its own peak that is
600 4.1794(4) 73.003 1.74
NiO NPs (time (min) /450 ˚C) called the fingerprint of that certain material. In regards to
60 4.181(1) 72.914 1.73 the excited states of pure NiO, Raman scattering has exhib-
120 4.1782(7) 72.934 1.60
180 4.1777(9) 73.082 1.76
ited one phonon (TO and LO) and two phonons (2TO,
TO þ LO and 2LO), as well as one, two, and four excited

Figure 4. Rietveld fits of synthesized NiO NPs using extract of Z. jujuba fruit at 450 ˚C and 120 min.
126 A. MIRI ET AL.

Figure 5. FT-IR spectrum of synthesized NiO NPs using extract of Z. jujuba fruit in 450 ˚C and 120 min.

comparison between bulk nickel oxide and NiO NPs, the


occurrence of a reduction in the size of nanoparticles can
affect their magnetic behaviors and alter their peak location.

FESEM and EDX analysis


The practicality of FESEM technique in examining the mor-
phological characteristics of nanomaterials and dispersion in
a bulk or matrix state has been well proved. The spherical
and uniformed particles of NiO NPs can be observed in
Figure 7A. It can be indicated from the histogram of Figure
7C that the particles size distribution has been 10–20 nm.
Next to reflecting the energy difference of two layers, the
energy of X-rays (EDX) can display the atomic structure of
elements that are being emitted and measuring the compos-
Figure 6. Raman spectrum of synthesized NiO NPs using extract of Z. jujuba
fruit in 450 ˚C and 120 min.
ition of sample elements.[14] Figure 7B displays the results of
EDX images that had been taken from the synthesized nano-
particles at 450 ˚C. The atomic percentage of nickel and
oxygen was observed to be 24.51 and 75.49%, respectively.
states of magnon (Figure 6). The Raman spectra of single- The presence of oxygen and nickel has been recorded
crystal NiO has displayed several bands above the point of throughout the EDX spectra, of the lack of impurity in the
400 cm1. It should be noted that the origin of first four synthesized nanoparticles. The peaks that are recorded
bands was the vibrational origin including TO and LO within 1–5 keV were related to gold since it had been used
modes of one-phonon (1 P) (within the range of 561 cm1), to prepare the sample of EDX analysis.
2TO modes of two-phonon (2 P) (in range of 710 cm1),
and TO þ LO (855 cm1) and 2LO (1009 cm1) modes.
Photocatalytic activity
Meanwhile, the last strong band observed at 1392 cm1 has
been apparently caused by two-magnon (2 M) scattering. The photocatalytic activity of synthesized and commercial
This mode can be clearly perceived at room temperature NiO NPs was measured through the application of methy-
due to the available high Nile temperatures. However, the lene blue dye under ultraviolet irradiation, which was based
1 P band has been more evident owing to the defect or sur- on irradiation time as a parameter. The absorbance peak for
face effect of powders, while the three bands of 2 P had methylene blue dye was recorded to be within the 665 nm
appeared to be more extended and the 855 cm1 band has range. The adsorption rate of synthesized and commercial
virtually disappeared.[61] According to the peak location nanoparticles was compared in Figure 8A. The results show
INORGANIC AND NANO-METAL CHEMISTRY 127

Figure 7. Analysis images of (A) FESEM, (B) EDX and (C) Histogram of particles size distribution of synthesized NiO NPs using Z. jujuba extract at 450  C for 120 min.

that the adsorption rate of synthesized sample was 34.2%, to oxidize dye macromolecules and break them down into
but it was 21.9% for commercial sample. It means that the small mineral molecules. In addition, the electrons (e-) that
surface area of synthesized sample in more than commercial are produced on conduction band have been observed to
sample. Degradation rate of above samples were illustrated contain good reducibility and can be reduced by binding to
in Figure 8B, that show synthesized sample is approximately an electron acceptor such as O2 for producing HO2, O2-, or
2 fold more than commercial sample. In the case, degrad- H2O2 with strong oxidizing properties (Figure 8B).
ation rate of synthesized and commercial NiO NPs were Therefore, the significant functionality of these active sub-
65.5% and 32%, respectively. stances throughout the degradation of colored macromole-
The possible mechanism for the expression of photocata- cules cannot be denied.
lytic activity of nanoparticles is related to an electron donor In order to investigate the efficiency of the synthesized
and acceptor process, where the surface of nanoparticles acts nanoparticles regarding to degradation of methylene blue
as a substrate for electron transfer reaction.[62–64] solution, TOC (Total Organic Carbon) analysis was per-
Previous studies have stated that the exposure of NiO formed in three steps by TOC-V CSH device. In order to
NPs to ultraviolet light can cause the electrons of valence measure TOC of solution, the repeatability of device set to
band of nickel oxide to be excited toward the conduction 3–5 and calibration diagram has R2¼ 0.9945. A 10 mg/L
band and create holes (hþ) on the valence band. hþ has a solution of methylene blue was prepared and TOC of men-
strong oxidizing agent that can adsorb the existing H2O or tioned was reported 8.09 mg/L. In the next step, in order to
OH on the surface of NiO, while the OH radicals are able create an adsorption–desorption equilibrium, the reactor
128 A. MIRI ET AL.

Figure 8. (A) Adsorption speacta and (B) Degradation of synthesized and commerical NiO NPs nanoparticles in MB dye under visible light at different
time intervals.

expose to visible light. It is worthy to say the photoreactor


was placed in ice water bath during the test to keep the
solution temperature constant at room temperature. Samples
were taken after 180 minute and after centrifuging the pho-
tocatalysts were separated and amount of total organic car-
bon (TOC) removal was 36.71%, it is necessary to mention
the number of TOC which device gave to us was 5.12 mg/L.

Conclusion
Nickel oxide nanoparticles were successfully synthesized by
the usage of aqueous extract of Zizyphus jujuba fruit, which
involved the application of a facile, fast, safe, and low-cost
Figure 9. Suggested mechanism of dye degradation by synthesized NiO NPs.
method for the first time. The analysis results indicated that
the synthesized nanoparticles contained a spherical shape
was located in the dark place for 60 minute on stirrer, and with a crystal face centered cubic (FCC) structure and the
then sampled again, and the reported number was 7.42 mg/ size range of 5–30 nm. According to the photocatalytic activ-
L. After turned on the lamp and placed the solution to ity assessment, these nanoparticles were capable of
INORGANIC AND NANO-METAL CHEMISTRY 129

degrading the MB dye by 65.5%, which can nominate them 15. Hammadi, O. A.; Khalaf, M. K.; Kadhim, F. J. Farbication of UV
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