Hindawi Publishing Corporation

International Journal of Analytical Chemistry

Volume 2016, Article ID 3512145, 14 pages
http://dx.doi.org/10.1155/2016/3512145

Review Article
Recent Advances in the Synthesis and Stabilization of Nickel and
Nickel Oxide Nanoparticles: A Green Adeptness

Muhammad Imran Din and Aneela Rani

Institute of Chemistry, University of the Punjab, New Campus, Lahore 54590, Pakistan

Correspondence should be addressed to Muhammad Imran Din; [email protected]

Received 21 December 2015; Revised 16 May 2016; Accepted 24 May 2016

Academic Editor: Frantisek Foret

Copyright © 2016 M. Imran Din and A. Rani. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

Green protocols for the synthesis of nanoparticles have been attracting a lot of attention because they are eco-friendly, rapid,
and cost-effective. Nickel and nickel oxide nanoparticles have been synthesized by green routes and characterized for impact of
green chemistry on the properties and biological effects of nanoparticles in the last five years. Green synthesis, properties, and
applications of nickel and nickel oxide nanoparticles have been reported in the literature. This review summarizes the synthesis
of nickel and nickel oxide nanoparticles using different biological systems. This review also provides comparative overview of
influence of chemical synthesis and green synthesis on structural properties of nickel and nickel oxide nanoparticles and their
biological behavior. It concludes that green methods for synthesis of nickel and nickel oxide nanoparticles are better than chemical
synthetic methods.

1. Introduction well defined pure NPs but they have low productivity, high
cytotoxicity, low antioxidant potential, and low antimicrobial
Nanoparticles (NPs) are cluster of atoms having at least one activity and are not environmental friendly [12].
dimension in the size range of 1–100 nm. Owing to their There is a great concern to search for environmentally
unique optical, magnetic, catalytic, and electrical properties, benign methods which results in the development of bionan-
they have potential applications in various fields [1]. The otechnology. Bionanotechnology synthesizes NPs by using
physicochemical properties of NPs are different as compared biological systems including bacteria, fungi, yeast, plants,
to those of their bulk counterparts owing to the fact that and naturally occurring small molecules such as vitamins,
surface area to volume ratio increases and quantum effects proteins, peptides, and reducing sugars [13–16].
become dominant as the size decreases. The increase in The combination of biological principles (i.e., oxida-
surface area to volume ratio alters the mechanical, catalytic, tion/reduction) by microbial enzymes or plant phytochem-
and thermal properties of material [2]. icals with physical and chemical approaches results in the
In recent years there is an emerging interest to synthesize synthesis of NPs with desired functions [17, 18]. Biolog-
magnetic NPs of Fe, Co, and Ni due to their superior mag- ical synthesis provides an environmental friendly, simple,
netic properties and potential uses in many fields including inexpensive approach for synthesizing NPs with an added
catalysis, memory storage devices, and sensors. In the field advantage of stabilizing the formed NPs as plant secondary
of medicine they are used for magnetically controlled drug metabolites besides acting as synthetic agents also act as
delivery, magnetic resonance imaging, and hyperthermia capping agent. Moreover, NPs synthesized by using green
treatment of cancer cells [3–5]. chemistry have no or low cytotoxicity as compared to chem-
Many physical and chemical methods including copre- ically synthesized NPs which makes them efficient carrier of
cipitation [6], sol-gel [7], microemulsion [8], hydrothermal drugs for in vivo drug delivery applications [19].
reaction [9], electrospray synthesis [10], and laser ablation Herein, we review the work done in the field of green
[11] are used to synthesize NPs. These methods may produce synthesis of Ni and NiO NPs and discuss the role of reaction
2 International Journal of Analytical Chemistry

parameters on the structural properties of formed Ni NPs. They also find environmental applications in the field
We also present a comparative overview of influence of of adsorption of hazardous dye and inorganic pollutants
chemical synthesis and green synthesis on the Ni and NiO and thus play a vital role in the cleanliness of environment
NPs structural properties and biological properties. [31]. Due to their good antibacterial and anti-inflammatory
activities they are used in the field of biomedicine [19, 32].
2. Properties of Nanoparticles They also show cytotoxicity against cancerous cells as is
evident from the distortion of morphology of these cells after
The physical and chemical properties of NPs are function of their treatment with Ni NPs [23, 33]. The biocompatibility
their size and shape and are therefore different as compared of Ni NPs capped with biomolecules such as glucose is
to size independent constant physical properties of bulk highly increased and these are used as biosensors and heat
material. This difference in properties at nanoscale is due to nonmediator for cancer hyperthermia [34].
their large surface area which makes them highly reactive and
quantum size effects which become dominant at nanoscale.
Some of the size dependent properties of NPs are briefly
4. Strategies for Nanoparticles Synthesis
described here: Principally there are 2 approaches used to synthesize NPs
(i) Band Gap. The band gap between the valence band including top-down approach and bottom-up approach.
and conduction band increases as the size of NPs
decreases. 4.1. Top-Down Approach for NPs Synthesis. This method
(ii) Melting Point. The melting point or phase transition comprises a set of synthetic technologies which synthesize
temperature of NPs is low and this decrease becomes NPs by removing certain parts from a bulk material substrate.
more pronounced when the particle size gets below The different methods for removal of parts from bulk mate-
5 nm. rials may include chemical, electrochemical, and mechanical
methods. The choice of a particular method is based on the
(iii) Mechanical Properties. The probability of defects is material of bulk substrate and desired sizes of NPs. This
low at nanoscale, due to which their mechanical technique however does not provide a full control on particle
strength is high and they are characterized as highly size. Top-down method is extended to obtain nanosized
tough and hard materials. domains and coupled the mechanical removing techniques
(iv) Electrical Properties. The electrical conductivity is with electrochemical and chemical techniques [35].
influenced in 2 ways at nanoscale. It decreases because
of large surface scattering while it may increase
because of better ordering. 4.2. Bottom-Up Approach for NPs Synthesis. This approach
consists of set of synthetic technologies which synthesize
(v) Optical Properties. Color or optical properties of NPs larger and more complex systems by stacking materials on
are highly dependent on the size of particle. This the top of a base substrate and maintaining good control
change in color can be explained on the basis of shift over molecular structure. One of the basic requirements
of 𝜆 SPR to higher wavelengths as the particle size for this fabrication approach is that there must be strong
increases in case of plasmonic NPs. adhesion forces between the surface layer and base substrate
(vi) Magnetic Properties. Due to large surface energy of and for this purpose surfactants are added which increase the
materials at nanoscale, ferromagnetism vanishes and adhesion between surface layer and base substrate [35].
shifts to supermagnetism.
(vii) Catalytic Properties. The catalytic efficiency of NPs is 5. Mechanism for Biosynthesis of Metal and
very high as compared to bulk material due to their Metal Oxide Nanoparticles
large surface area [20].
The secondary metabolites of plants and microbial/fungal
3. Significance of Nickel Nanoparticles enzymes are responsible for the reduction of metal ions
into metal atoms. The metal salts like nitrates, chlorides,
Nickel NPs find potential applications in various fields oxides, and sulphates have high reduction potential due to
including electronics, magnetism [21], energy technology attachment of metal with the chloride, oxide, and sulphide
[22], and biomedicines [23]. Due to their high reactiv- parts and their tendency to donate electrons. As a result of
ity, operational simplicity, and eco-friendly properties they both these factors electronic density on the conjugative salts
are used to catalyze various organic reactions including of metal increases. So metals in their ionic form can easily
chemoselective oxidative coupling of thiols [24], reduction get detached from their anionic part and get reduced into
of aldehydes and ketones [25], hydrogenation of olefins stable form by using plant/microbial/fungal extract. The sec-
[26], synthesis of stilbenes from alcohol through Wittig-type ondary metabolites of plant including alkaloids, flavonoids,
olefination [27], and 𝛼-alkylation of methyl ketone [28]. They polyphenols, and terpenoids act as chelator to metal ions
also catalyze certain inorganic reactions like decomposition and reduce them into zero-valent states. Mostly the –OH
of ammonia [29]. One of their recent applications is their role group of polyphenols and flavonoids develop coordination
in the fabrication of carbon nanotubes (CNTs) [30]. with metal ions, while in case of microbial mediated synthesis
International Journal of Analytical Chemistry 3

O biomolecules/enzymes which act as capping agent and sta-

M+ M+ Plant reducing agents
M O M bilize the formed NPs [36]. Mallikarjuna and coworkers
+
M OH
M O reported that the hydroxyl and carbonyl groups of amino
acid residues or proteins can strongly adhere to metal NPs
as capping agent and prevent them from aggregation [38].
Reduction and nucleation The crystal shape of metal and metal oxide NPs is
Phytochemical a function of rate of growth in different crystallographic
Growth
stabilizes NPs directions. The surface energy of crystal faces varies because
the capping agents interact differently with different faces.
Drying/calcination
in air This results in anisotropic growth of metal crystals, while
M-O M in case of isotropic growth, rate of reaction is high and
spherical shaped crystals are obtained. In case of higher rate
of reaction, process of nucleation dominates over growth and
Metal oxide NPs capped Metal NPs capped vice versa. The size of NPs also increases when their growth
with phytochemicals with phytochemicals
is anisotropic. However, the dimensions of anisotropically
Figure 1: Mechanism of plant mediated synthesis of metal and metal growing nanomaterials (e.g., nanoprisms) can be controlled
oxide nanoparticles. by adjusting the experimental conditions like pH, ratio
of metal ion and reducing agent, irradiation time and its
strength (in case of microwave heating), and reaction time.
Figure 3 shows the different shapes of NPs crystal that result
from their isotropic and anisotropic growth [39].
the reductase enzyme of bacterial or fungal cell wall donates
electron for reduction of metal ions.
We can describe mechanism of plant mediated synthesis 6. Biosynthesis of Nickel Nanoparticles
of metal and metal oxide NPs by considering the following
Very few literature is available on the biological synthesis
three phases: (1) activation phase involves the reduction of
of Ni and NiO NPs as compared to chemical synthesis. The
metal ions and reduced metal atoms undergo nucleation;
physical and chemical methods of NPs fabrication are accom-
(2) growth phase involves the spontaneous coalescence of
panied by some disadvantages like high cost, complexity
small adjacent NPs into larger size NPs, that is, Ostwald
(involving multiple steps), use of harmful organic chemicals,
ripening (a process in which NPs are directly formed through
and environmental pollution. So there is a great need to
heterogeneous nucleation and growth and further reduction
develop alternative eco-friendly and low cost fabrication
of metal ion); this process enhances the thermodynamic
methods for NPs. Nature has devised numerous processes for
stability of NPs; (3) termination phase decides the final shape
the fabrication of micro- and nanoscaled inorganic materials
of NPs. In case of metal oxide NPs the end product is air-
using naturally occurring biomolecules or microorganisms
dried or calcined in air to get final metal oxide NPs [36]. The
and plant extract as reducing agent. Green synthesis of NPs
schematic diagram for mechanism of NPs synthesis by plants
is a type of bottom-up technique where main reaction taking
is shown in Figure 1.
place is reduction/oxidation. There are 3 basic requirements
The mechanism of microbial mediated synthesis of metal
for biosynthesis of NPs including (i) choice of proper solvent,
and metal oxide NPs is also described by the following three
(ii) choice of an eco-friendly reducing agent, and (iii) choice
phases: (1) the metal cation is trapped by bacterial or fungal
of nontoxic stabilizing agent for NPs. Thus by choosing
cell wall due to electrostatic interactions between negatively
proper solvent, surfactant and reductant biosynthesis pro-
charged cell wall and positively charged metal cation; (2) the
duces NPs with controlled morphology without producing
cell wall then releases reductase enzyme which reduced the
any toxic environmental pollutant [35].
metal cations into metal atom; (3) these atoms then aggregate
In plant mediated synthesis of Ni NPs commonly extract
and form metal NPs. The formed NPs might be capped by
of different parts of plants is used as a reducing agent, while
the biomolecules of bacterium or fungi which prevent further
in some other cases rather than using the extract either whole
aggregation of metal NPs and finally the formed NPs diffused
plant is grown on a metal substrate or an entire part of plant
out from cell wall [37].
is soaked in metal solution. Here, in situ reduction of metal
In case of metal oxide NPs the end product is air-dried
ions occurs and their morphology can also be controlled as
or calcined in air to get final metal oxide NPs. The schematic
porous parts of plants also act as biotemplate [40]. Some
diagram for mechanism of NPs synthesis by plants is shown
naturally occurring biomolecules such as glucose, sucrose,
in Figure 2.
or plant secretions may also work as good reducing agent
As the growth phase duration increases, aggregation of
and stabilizing agents and thus are used to fabricate Ni NPs
NPs occurs and nanohexahedrons, nanotubes, nanoprisms,
[16, 34, 41].
and different kinds of irregularly shaped NPs are formed.
The aggregation occurred because of stronger binding energy
between 2 metal atoms as compared to atom-solvent binding 6.1. Biosynthesis of Ni Nanoparticles Using Plants. In recent
energy. The aggregation of NPs is prevented somewhat by years the fabrication of NPs using plants has fascinated the
the secondary metabolites of plants and fungal/microbial researchers because of its simple, cost effective, fast, and
4 International Journal of Analytical Chemistry

−
−
− n NADH X−
−
− n NAD +
M+ n e−
− M+ −

(2) Bioreduction
M+ M +
(1) Trapping
n M+ X−
− −
M-O
M M
− M-O
− M-O
M
M M-O
−
(3) Growth

(5) Calcination or
drying in air
−
−
M M
M
− M − M M
M M
− (4) Diffusion
−
−
−

Figure 2: Mechanism of microbes mediated synthesis of metal and metal oxide nanoparticles.

Decahedron

Anisotropic growth
Tetrapod

Triangular
Nuclei
bipyramid

Isotropic
Rod
growth

Sphere
Cube

Figure 3: Growth of nanoparticles by different ways and their resulting geometrical shapes.
International Journal of Analytical Chemistry 5

Table 1: Optimal reaction parameter conditions for maximum It was observed that adsorption of dye and inorganic
percentage removal of dyes and inorganic pollutants. pollutants increased by using large initial concentration of
both Ni NPs and pollutants and increasing contact time of
Contact Initial conc. of dyes and
Adsorbate pH adsorbent and adsorbate.
time (min) pollutants (mg/L)
CV 8 40 40
EY 3 20 20 6.1.2. Fabrication of Nickel Nanoparticles Using Plants as
Biotemplate. The leaves and petals of plants are porous and
OR 3 30 30
they serve as biotemplate for fabrication of Ni NPs. This
NO3 − 7 10 10 method of Ni NPs synthesis is advantageous since it has
SO4 2− 7 10 10 good control on size of particle and Ni NPs formed are not
prone to agglomeration. Kar and Ray [40] developed a green
method for fabrication of metallic Ni NPs using petals of
environmental friendly protocol [42]. Biosynthesis is a single Hibiscus rosa-sinensis as biotemplate and reducing agent. The
step technique for synthesis of NPs which provides stable NPs petals of hibiscus flowers are porous and beneath these pores
of different morphologies. The rate of production is rapid tunnels are present which supply nutrients and moisture
compared to microorganisms based biosynthesis of NPs. to whole parts of petal. These pores adsorbed NiCl2 ⋅6H2 O
Infra-red spectroscopy showed that secondary metabolites which then subsequently reduced into Ni NPs by C2 H4 which
including terpenoids, flavones, pyrones, aldehydes, amides, is one of the products obtained during pyrolysis of petals.
and carboxylic acids derived from plant extracts are responsi- The formation of Ni NPs was confirmed by the attraction
ble for reduction of metal salts into their respective NPs [43]. of end product of reaction towards the magnet. The size of
Only few research articles are reported so far on the synthesis obtained Ni NPs was in the range of 10 nm–200 nm and was
of Ni NPs using plants. Different parts of plants such as leaves coated with the mesoporous carbon which prevents them
and roots are used for synthesizing Ni NPs. from agglomeration. The formed Ni NPs were stable even
after 20 days.
6.1.1. Fabrication of Ni NPs Using Leaf Extract of Plants. Chen
et al. [44] reported the synthesis of face-centered cubic Ni 6.2. Fabrication of Bioconjugated Nickel Nanoparticles Using
NPs by reducing aqueous solution of Ni(NO3 )2 with aqueous Naturally Occurring Biomolecules. The magnetic nanoparti-
extract of Medicago sativa (alfalfa). The typical synthetic cles of nickel are prone to oxidation and therefore most of
method of Ni NPs involved the vigorous stirring of precursor synthesis protocols utilize toxic and expensive organic media
solution with alfalfa solution at 60∘ C for 4 hours. The reaction and hydrophobic capping agents to prevent agglomeration
was carried out at 60∘ C because at room temperature it is and surface oxidation of magnetic nanoparticles [45]. The sta-
difficult to completely reduce Ni(II) into Ni(0). Then NPs bility of nickel nanoparticles in aqueous media is a challenge.
solution was freeze-dried for 24 h in order to obtain Ni NPs The naturally occurring biomolecules such as vitamins,
powder. reducing sugars, and plant secretions containing polyphenols
Pandian and coworkers [31] synthesized Ni nanoparticles are good antioxidants and they can potentially be applied
by using aqueous solution of Ni(NO3 )2 ⋅6H2 O as precursor to produce stable dispersions of nanoparticles in aqueous
and leaf extract of Ocimum sanctum as reducing agent as well media where they act both as reductant and as capping
as stabilizing agent. The Ni(II) ions were reduced into Ni(0) agents. Moreover, the biocompatibility of formed NPs is also
by hydrated electrons of O. sanctum aqueous leaf extract and increased which thus increases their applications in the field
Ni(0) nuclei were formed. These Ni(0) atoms then aggregate of drug delivery.
and Ni NPs were formed. A UV/Vis spectrum of the sample Raj and Viswanathan [16] reported the synthesis of Ni
was recorded and peak centered at 395 nm corresponding to NPs in ethanolic media by using sucrose as reducing agent
Ni NPs confirmed the formation of Ni NPs. The XRD pattern and vegetable oil as capping agent. In order to establish
was recorded for Ni NPs confirming that Ni NPs have face suitable precursor and reducing agent several precursors
centered cubic structure and average particle size was 30 nm (nickel nitrate, nickel acetate, and nickel chloride) and reduc-
as calculated by Debye-Scherrer equation. This particle size ing agents (hydrazine, sodium borohydride, and sucrose)
showed good agreement with that calculated by SEM (particle were investigated. The calculated heat of reaction showed
size was 15 and 36 nm) and by TEM (particle size was 12 and that nickel nitrate was best precursor and sucrose was best
36 nm). reducing agent.
These Ni NPs were then used to adsorb organic dyes Bioconjugated NPs have wide range of applications in the
including crystal violet (CV), 2-naphthol orange or Orange II biomedical field as NPs become more biocompatible for in
(OR), eosin Y (EY), and anionic contaminants sulfate (SO4 2− ) vivo applications and often used as luminescence tagging,
and nitrate (NO3 − ) from aqueous solution. Their adsorption labeling, imaging, and drug delivery [46–48]. Some work
capacity was studied as a function of change in pH, Ni NPs has been done in the direction to synthesize bioconjugated
dosage, contact time, and initial concentration of pollutants Ni NPs in aqueous media using environmentally benign
and dyes. The optimal conditions of pH, contact time, initial reducing and capping agent.
concentration of dyes, and inorganic pollutants for maximum Vaseem et al. [34] synthesized highly water-stable bio-
adsorption capacity of Ni NPs are summarized in Table 1. conjugated glucose-capped nickel nanoparticles (G-Ni NPs)
6 International Journal of Analytical Chemistry

through aqueous solution process by using glucose both as reaction mixture and by UV/Vis spectroscopy. The color
a reducing agent and as a capping agent in the presence of reaction mixture changes from light blue to dark brown
of liq. NH3 . Due to their enhanced biocompatibility these indicating the formation of Ni NPs. Their formation was
were used as biosensors and heat nonmediator for cancer further confirmed by taking their UV/Vis spectrum in which
hyperthermia. The mechanism involved in the synthesis of G- absorbance maximum at 285 nm was assigned to SPR peak for
Ni NPs was proposed as follows: firstly by the addition of liq. Ni NPs. The plasmonic band had symmetrical shape which
NH3 into Ni(NO3 )⋅6H2 O and glucose solution, green color suggested that formed NPs were uniform and well-dispersed
ppt. of Ni(OH)2 were formed. By the further addition of liq. [50].
NH3 these ppt. dissolved and transparent green color solution FTIR spectroscopy is used to investigate the biomolecules
is formed which was due to formation of [Ni(NH3 )4 ]2+ responsible for reduction of metal salt into metal NPs and
complex. This complex was refluxed in ambient atmosphere their subsequent growth inactivation through the capping
at 80∘ C for 2 h. In the presence of liq. NH3 the aldehyde effect of these biomolecules. For this purpose, the FTIR
group of glucose oxidized into carboxylate ion and resulting spectrum of plant extract and metal NPs is recorded. The
free electrons reduced [Ni(NH3 )4 ]2+ complex into Ni metal. absorption band corresponding to biomolecules which are
Usually, glucose remains in open chain format; however in responsible for bioreduction should appear only in extract
aqueous solution it transforms its structure into cyclic chair spectrum and should disappear in NPs spectrum. This helps
form. So, in addition to being acting as a reducing agent, here, not only in the identification of biomolecules responsi-
it also acts as capping agent by developing complexation with ble for bioreduction but in proposing the mechanism of
Ni NPs through its five –OH groups. It is considered that reaction.
at high pH condition surface of Ni NPs oxidizes to develop Mamuru and Jaji synthesized Ni NPs using NiCl2 ⋅6H2 O
a negative charge (Ni-O− ). Usually, in aqueous media metal as a salt precursor and leaf extract of Moringa oleifera as a
NPs have negative surface charges; that is why it is considered reducing agent. The change in color of solution from light
that hydrogen bonding interactions develop between Ni NPs blue to dark reddish brown indicated the formation of Ni NPs
surface and glucose which facilitates capping of Ni NPs. which was further confirmed by observing their SPR peak at
297 nm. They tried to explore the biomolecules responsible
for bioreduction of Ni(II) ions into Ni(0) by recording the
6.3. Characterization of Ni Nanoparticles. UV-Visible spec-
FTIR spectrum of both leaf extracts of M. oleifera and Ni
troscopy (UV-Vis) [31], Fourier transformation infrared
spectroscopy (FTIR) [44], X-ray diffraction (XRD) [23, NPs. It was observed that IR band at 1636 cm−1 was the
40], scanning electron microscopy (SEM) [31], transmission only one band that was present in M. oleifera spectrum and
electron microscopy (TEM) [44], zeta potential measure- was absent in IR spectrum of Ni NPs. All other bands of
ment [19], thermogravimetric analysis (TGA) [41], X-ray M. oleifera were present in Ni NPs spectrum. This band
photoelectron spectrometry (XPS) [44], photoluminescence was of amino aryl ketones, that is, anthraquinones, so it is
(PL) [41], energy-dispersive X-ray spectroscopy (EDS) [34], possible that this is the biomolecule which was responsible
and atomic force microscope (AFM) [41] are literature for reduction. The presence of anthraquinone was confirmed
reported fundamental characterization techniques for Ni NPs by the appearance of cherish red color after the addition of
[31]. 25% NH3 solution into leaf extract which is a confirmatory
Ni NPs are plasmonic; that is, they show surface plas- test for anthraquinones [49].
mon resonance (SPR) and absorption band in the range of Another way to identify the biomolecules responsi-
300 nm–400 nm is due to SPR of Ni. The phenomenon of ble for bioreduction is to record the FTIR spectrum of
SPR occurred because the metallic NPs physically absorbed plant/microbial extract before and after bioreduction. The
light and as a result of this absorption conduction electrons bands of those biomolecules which are responsible for biore-
of metal undergo coherent oscillation. This happened when duction change their position in the spectrum recorded after
the frequency of incident photon becomes equal to natural bioreduction. In this regard, Chen and coworkers tried to
frequency of surface electrons; at this frequency amplitude of explore the biomolecules of alfalfa grass which were respon-
oscillation becomes maximum and this frequency is called sible for the bioreduction of Ni(II) ions and stabilization of
SPR. The absorbance of light is measured with the help of Ni(0) NPs by recording IR spectrum of extract before and
UV/Vis spectrophotometer. after bioreduction. The bioreduction of Ni(II) was caused by
The shape of SPR band, its width, and its spectral position flavonoids and reducing sugars of extract as indicated by the
depend on the size of NPs and their size distribution. The SPR change in band position of C–O group of flavonoids and
peak shows a red shift in position as the size of NPs increases, reducing sugar. The band was observed at longer wavelength
and blue shift is observed when particle size decreases. When after bioreduction as compared to the band recorded before
the NPs are monodisperse in size distribution then shape of bioreduction. The IR result suggesting flavonoids and reduc-
SPR peak is symmetrical and it became broad and split into ing sugar as reductant was further supported by low amount
two bands when size distribution became nonuniform [49]. of these biomolecules in extract measured after bioreduction
Mamuru et al. synthesized Ni NPs using aqueous leaf as compared to their amount measured before bioreduction
extract of Annona squamosa as reducing agent and aqueous [44].
NiO solution as precursor salt at neutral pH. They mon- XRD is used for the identification, purity, and quantitative
itored the formation of Ni NPs by visual color change of analysis of NPs. The phase of NPs is determined by recording
International Journal of Analytical Chemistry 7

the peaks at 2𝜃 value; these peaks give the value of crystal concentration of leaf extract, concentration of precursor salt,
planes for particular type of NPs. By comparing the position temperature, pH of medium, and reaction time. Chen et al.
and intensity of these diffraction peaks with Joint Committee studied the effect of concentration of alfalfa extract on the
on Powder Diffraction Standard (JCPDS) card number (each size of Ni NPs. It was observed that not only particle size
type of metal has specific JCPDS card number) one can increased but also widening of size distribution occurred
identify the NPs and their phase (spherical, wurtzite, etc.). at high concentration of extract. This was due to the fact
The intensity of XRD spectrum peaks is function of particle that by increasing the concentration of extract concentration
crystallinity. When the NPs have good crystallinity then of reducing agents increased for the same concentration of
intense and sharp peaks are observed and vice versa. The precursor salt and thus size of Ni(0) particles grew with more
NPs size can also be calculated using Scherrer equation; when and more Ni(0) produced by bioreduction [44].
particle size is large then XRD patterns become broad [51]:

0.98𝜆 6.5. Impact of Green Synthesis on the Biological Behavior of Ni

𝐷= , (1)
𝛽 cos 𝜃 NPs. NPs synthesized by green routes are more biocompati-
ble and nontoxic because in this route the reducing agent and
where 𝐷 is particle size, 𝜆 is wavelength (Cu K𝛼), 𝛽 is FWHM, stabilizing agents for NPs are plants or microbial reducing
and 𝜃 is diffraction angle. sugars and flavonoids which do not have cytotoxic effects. In
Pandian et al. recorded the XRD spectrum for Ni NPs this regard Sudhasree et al. [19] carried out comparative study
synthesized by reducing Ni(II) ions with leaf extract of between conventional chemical method using hydrazine as
Ocimum sanctum. They observed 5 distinct diffraction peaks a reducing agent and biological method using Desmodium
in XRD spectrum at 2𝜃 values 37.32∘ , 44.82∘ , 47.92∘ , 63.11∘ , gangeticum (DG) root extract for Ni NPs synthesis. DG
and 72.97∘ and the peak at 2𝜃 value 44.82∘ showed maxi- possesses antioxidant and antiapoptotic properties. They
mum intensity. Their resulting miller indices (111) and (200) compared the antioxidant potential and cytotoxicity and
affirmed that the NPs were face centered cubic (fcc) Ni. The antimicrobial activity of Ni NPs synthesized by both routes.
average particle size calculated by Debye-Scherrer formula The antioxidant potential of Ni NPs was assayed by study-
was found to be 30 nm [31]. ing the scavenging assay of 2,2-diphenyl-1-picrylhydrazyl
SEM is used to study the surface morphology and (DPHH) and superoxide radical. DPHH violet color in the
composition of NPs by scanning the surface with high energy presence of radical changes to yellow color on hydrogenation.
electron beam, produced by heated filament. Angajala et al. The higher percentage scavenging was observed in case of
[52] synthesized Ni NPs by using the aqueous leaf extract Ni NPs synthesized by green route (NiGs) as compared to
of Aegle marmelos Correa (AmC) as a reducing agent and Ni NPs synthesized by chemical methods (NiCs). This was
aqueous solution of NiCl2 ⋅6H2 O as a precursor salt. The attributed to the presence of an additional moiety in NiGs
formation of Ni NPs was indicated by color change of solution which was phenolic compounds and the presence of phenolic
from dark green to light green. The surface morphology of compounds was confirmed by high superoxide scavenging
formed Ni NPs was investigated by employing SEM. The activity of NGs (phenolic compounds possess O2 − scavenging
results indicated that NPs were polycrystalline in nature with activity) [19].
average particle size of 80–100 nm having triangular shape. NPs have ability to cross physiological barriers and
Their SEM images exhibited that NPs were capped by organic thus can enter and damage cells of living organisms. The
biomolecule layer which is derived from leaf extract of AmC cytotoxicity of both types of NPs was checked by both in
having surface functional –OH groups that take part in vitro and in vivo methods. In both these methods the activity
bioreduction of Ni(II) ions into Ni(0) NPs, besides acting as of lactate dehydrogenase (LDH) which was released from
stabilizing and capping agent. Within the agglomerates the plasma membrane because of discharge from damaged cell
NPs were not in direct contact and aggregation was seen only as a result of NPs presence was monitored to check the
between the outer surfaces of organic material surrounding cytotoxicity of Ni NPs. The in vitro assay was carried out
the Ni NPs. on epithelial cell line and in vivo assay was carried out on
TEM is used for the identification of details of internal LLC PK1 kidney cell lines of male rate. The results showed
composition of NPs including their shape, size, size distribu- that NiGs are nontoxic as compared to NiCs as confirmed
tion, and defects. Mariam et al. synthesized Ni NPs by using by the low activity of LDH (formation of formazon by LDH
leaf extract of Azadirachta indica and NiO NPs using Psidium catalyzed reduction of tetrazolium salt) in case of NiGs
guajava leaf extract. Their morphology was determined by nanoparticles [19].
taking their TEM images. It was exhibited by their TEM The antibacterial activity of NPs is a function of chemical
images that both Ni and NiO NPs were spherical in shape composition, shape, concentration, photoactivation, and size
and their size was <100 nm. Their size distribution was also of NPs. The antibacterial activity of NiGs and NiCs NPs, pre-
narrow and NPs showed aggregation in order to reduce the cursor salt, and reducing agent was assayed on Gram negative
total surface energy of system [23]. and Gram positive bacteria using agar gel diffusion method.
Two control experiments, one positive control and one
6.4. Effect of Reaction Parameters on Structural Properties of negative control, were also conducted to check antimicrobial
Ni NPs. The structural properties of Ni NPs such as their activity. The large value for zone of inhibition in case of
size and shape are function of reaction parameters including NiGs (Figure 4) confirmed that NiGs have high antibacterial
8 International Journal of Analytical Chemistry

25 16
14

Zone of inhibition (mm)

12
20 10
8
Zone of inhibition (mm)

6
15 4
2
0
Staphylococcus Escherichia coli Bacillus cereus Klebsiella
10 aureus pneumoniae
Bacterial strains

Figure 5: Comparison of effectiveness of Ni nanoparticles against

5 different bacterial strains.

0 NPs surface. The intracellular inhibitory effect of Ni NPs

associated 𝛽-sitosterol upon entering into inflammatory sites
(negative control)
NiCs

NiGs

NiCl2

DG

(positive control)

Distilled water
Ciprofloxacin

results because they develop association with receptor site by

generating therapeutic effects and together assist the growth
of peripheral blood lymphocytes. It was observed that the
therapeutic efficacy of Ni NPs associated 𝛽-sitosterol was
higher as compared to 𝛽-sitosterol of aqueous leaf extract.
Staphylococcus aureus Vibrio cholerae This was due to high surface area of Ni NPs as compared to
Klebsiella pneumoniae Proteus vulgaris
aqueous leaf extract of AMC, which cause the 𝛽-sitosterol to
Pseudomonas aeruginosa
remain on the surface of Ni NPs rather than in the interior of
Figure 4: Comparison of antibacterial activities of NiGs, NiCs, particle and therefore enhance its exposure to receptor sites
NiCl2 , DG, positive control, and negative control. in order to produce therapeutic effect.
Mariam et al. [23] synthesized Ni NPs using leaf extract of
Azadirachta indica and NiO NPs using Psidium guajava leaf
extract. The synthesized nanoparticles showed cytotoxicity
activity as compared to that of NiCs, precursor salt, and DG against HT29 cell line (human colon adenocarcinoma).
extract [19]. Thus NiGs were nontoxic and possess higher Two types of experiment were conducted on human colon
stability and higher antioxidant and antimicrobial potential adenocarcinoma cells; one of them was control experiment
than chemically synthesized Ni NPs [19]. (untreated cells) and the other was test experiment in which
Helen and Rani [53] synthesized Ni NPs using aqueous cells were treated with Ni and NiO NPs. The cytotoxicity
solution of nickel sulphate and root tuber extract of Dioscorea of Ni NPs and in turn the percentage viability of cancer
(Elephant Yam) as reducing and capping agent. The color cells were assayed by conducting a colorimetric assay, MMT
change of solution from blue to yellow indicated the forma- assay (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium
tion of Ni NPs. The UV/Vis peak of Ni NPs was centered at bromide). MMT is a yellow tetrazol which can be reduced
207 nm. The antibacterial activity of these Ni NPs was assayed to insoluble crystals of purple formazan by the action of
by disc diffusion method against 4 bacterial strains including oxidoreductase enzymes of living cells. The insoluble crystals
Staphylococcus aureus and Bacillus cereus (Gram positive) and of formazan can be solubilized by adding dimethyl sul-
Klebsiella pneumonia and Escherichia coli (Gram negative). foxide and absorbance of purple solution is quantified by
The Ni NPs were most effective against Staphylococcus aureus recording spectra at certain wavelength (540 nm) using a
and were least effective against Klebsiella pneumonia as indi- spectrophotometer. The absorbance is directly proportional
cated by their zone of inhibition. The result of effectiveness of to number of living cells. The results of Mariam et al.
Ni NPs against different microbes is shown in Figure 5. [23] study showed that absorbance was decreased in cell
Angajala and Radhakrishnan [32] synthesized Ni NPs culture treated with Ni NPs (concentration > 6.25 𝜇g/mL)
by using aqueous leaf extract of Aegle marmelos Correa as compared to that of untreated cells. These results were
(AMC) and also checked their synergistic efficacy with 𝛽- further supported by the morphological analysis of treated
sitosterol to induce anti-inflammation and compared their and controlled cells. The control cells showed smooth and
anti-inflammatory activity with the different leaf extracts regular surface with normal morphology, whereas Ni and
of AMC by employing 2 tests, albumin denaturation assay NiO treated cells showed changes in cell morphology due to
and membrane stabilization test. 𝛽-Sitosterol is a plant sterol cell swelling and breaking as a result of apoptosis.
identified from the AMC aqueous leaf extract and it possesses Nanoparticles are efficient drug carriers for both in
anti-inflammatory properties. The –OH group of 𝛽-sitosterol vitro and in vivo applications. Chen and coworkers [33]
develops bonding with AMC leaf extracts’ synthesized Ni checked the synergistic impact of Ni NPs with antitumor drug
International Journal of Analytical Chemistry 9

Verbascoside (VB) both in vitro and in vivo on the induction 90

of apoptosis of K562 cancer cells. They conducted four types 80
of experiments; one of them was control experiment in which 70

Bacterial reduction (%)

cells were not treated and the other 3 experiments involved
60
the treatment of cells with VB-Ni NPs, Ni NPs alone, and
VB alone for 72 h, 48 h, and 24 h, respectively. The rate 50
of apoptosis for in vitro drug and NPs treated cells was 40
checked by identifying the characteristics feature of apoptotic 30
nuclei like fragmented DNA and condensed chromosomes
20
using fluorescence microscope. The result showed that rate of
apoptosis was higher in VB-Ni NPs treated cells as compared 10
to that of alone Ni and VB treated cells. The in vivo studies 0
on the cancerous cells of female mice were conducted on the 1 2 5 10 15 20 25
same line as was done for in vitro study, but here a magnet Number of washing cycles
was also placed under mice skin near cancer cells. In this
S. aureus
study, again rate of apoptosis was higher in VB-Ni NPs treated
E. coli
cells. These results suggested that Ni was transferred from
VB-Ni into cancer cells through the action of magnetic field Figure 6: Effect of washing cycles on the antibacterial activity of
generated by the magnet placed near the cancer cells where it NiO nanoparticles coated cotton fabric.
suppresses the growth of tumor cells and kills the tumor cells
together with drug.
and complex apparatus. Therefore, recently environmental
benign green chemistry approach is used to synthesize NiO
7. Nickel Oxide (NiO) Nanoparticles NPs.
Metal elements are capable of forming large diversity of
compounds with oxygen (metal oxides). These metal oxides 7.1. Fabrication of NiO Nanoparticles by Using Plant Extract.
can be insulators, semiconductors, or conductors depending Yuvakkumar and coworkers [61] synthesized NiO nanocrys-
on their structural geometries which give rise to particular tals by utilizing nickel nitrate as precursor and rambutan peel
electronic structure. Metal oxides are widely used in the waste as reducing and stabilizing agent and then checked
manufacturing of fuel cells, microelectronic circuits, piezo- their antibacterial activity by coating them on cotton fabric
electric devices, sensors, and corrosion resistant coatings and surface.
as catalysts. The metal oxide NPs possess distinct physical The probable mechanism for synthesis of NiO nanocrys-
and chemical characteristics because of their smaller size and tals from rambutan peel extract is the formation of nickel-
highly dense edge or corner surface sites. In any material, ellagate complex through ligation of phenolic hydroxyl group
particle size affects the 3 most crucial groups of fundamental and ester oxygen atom of polyphenols with nickel at pH
properties; first group is of structural properties, namely, 5–7. The complex after calcination at 450∘ C decomposes
cell parameters and lattice symmetry; second group is of and NiO nanocrystals are formed. The active components
electronic properties and the above mentioned two properties of rambutan are vitamins, polyphenols, flavonoids, and
then induce changes in physical and chemical properties of alkaloids which serve as antioxidants, antiviral, and radical
materials. Among the metal oxide NPs, magnetic metal oxide scavengers. Among these active components the polyphenols
NPs are gaining much interest because their properties can be such as ellagic acid, geranin, and corilagin are present in large
modified according to their shape and size [54]. amounts and serve as antioxidants.
Recently, NiO NPs are studied widely because of their These NiO nanocrystals were then adsorbed on cotton
electrocatalysis, high chemical stability, superconductance fabric by pad-dry-cure and citric acid acts as crosslinker
characteristics, and electron transfer capability [55]. NiO is a in this adsorption. The fabric untreated and treated with
p-type semiconductor metal oxide having a band gap ranging NiO nanocrystals was tested for antibacterial activity
from 3.6 to 4.0 eV depending upon the nature of defects and against Staphylococcus aureus (Gram positive bacteria) and
their density. It is an antiferromagnetic material having Neel Escherichia coli (Gram negative bacteria) by employing
temperature 𝑇N of ∼523 K and besides a high isoelectric point a disc diffusion method. The mechanism of antibacterial
of ∼10.7, it also shows high ionization. The potential appli- activity is described as follows: by the action of UV and
cations of NiO are in various areas like in water treatment, visible light activation of NiO occurs which leads to
gas sensing, electrochemical performance, and antimicrobial formation of electron-hole pairs. By the hydrolysis and redox
activities. Numerous methods to fabricate NiO NPs have reactions hydrogen peroxide is produced which can enter
been reported in the literature which includes solvothermal cell membrane and kill bacteria. The antibacterial activity of
[56], precipitation-calcination [57], chemical precipitation fabric treated with NiO NPs was significant after 10 washes
[58], microwave-assisted hydrothermal [59], and thermal but after that the percentage of bacterial reduction was very
decomposition [56, 60] methods. These methods involve low and after 20 washes this activity completely diminishes
ample reactants and starting materials, draggy procedures, as shown in Figure 6.
10 International Journal of Analytical Chemistry

Thema and coworkers synthesized single phase Bunsen- 7.2.1. Preparation of Microbial Extract. The general method
ite NiO NPs using Agathosma betulina leaves extract. The reported in the literature for the preparation of microbial
formed NPs were characterized for their surface/interface extract involved the culturing of microbes on an appropri-
and volume room temperature characteristics by various ate broth medium followed by their incubation at suitable
analytical techniques. The photodiode behavior in the NIR temperature and rpm on a rotary shaker for set number of
spectral range for standard blade made film of pressed p-type days specific for microbes. Then culture is centrifuged at
NiO NPs onto n-type Si substrate was studied. The average suitable rpm for specific time and supernatant is utilized
size of NiO NPs was 26.7 ± 0.4 nm as calculated by their for fabrication of Ni NPs. Incubation of fungi is carried out
TEM and the crystalline aspects of these NPs were confirmed at 150 rpm and temperature of 25∘ C for 5 days [62], while
by observing many diffraction rings with strong diffraction bacteria are incubated at 200 rpm and temperature of 30∘ C
spots using selective area electron diffraction (SAED). The for 120 hours [63]. The dead fungal biomass can be prepared
elemental composition of formed NPs was confirmed by by autoclaving the live biomass and then drying it at 50∘ C
recording EDS spectrum which revealed the presence of till it becomes crispy. The uniform size biomass particles are
Ni and O in the nanopowder. The presence of C and Cu obtained after grinding the biomass [62].
elements was assigned copper grid and its carbon coating.
The crystallographic analysis of formed NPs was carried
out by recording their XRD profile. The obtained crystal 7.2.2. Fabrication of NiO NPs Using Fungi. Both living and
planes were corresponding to cubic NiO phase which is also dead fungal biomass can be used for fabrication of NPs. Use
called Bunsenite phase. The average diameter of NiO NPs of dead fungal biomass is advantageous as it can be stored
using Debye-Scherrer formula was within the range of 15.23– for longer period of time and does not require nutrients and
23.15 nm which was with close approximation with that size growth media and also it has limited toxicity. One of the
calculated by TEM. advantages of fungus mediated green synthesis of NPs is that
NiO is a p-type semiconductor material having a weak large surface area can be recovered by optimum growth of
absorption band in the visible region and an electrical resis- mycelia. Moreover, the fungal biomass can tolerate metal tox-
tivity on the basis of Ni cation vacancies concentration. There icity by adsorbing the metal species on their cell wall which
are no such Ni vacancies in the stoichiometric NiO; however is composed of chitosan, chitin, amino group phosphates,
at nanoscale there is probably a nonstoichiometric state of glucan, lipids, sulphates, phospholipids and hydroxides, and
Ni depletion. The presence of these defects at nanoscale is so forth. These functional groups serve as binding sites for
attributed to the breakage of 3D symmetry at the NPs surface. biosorption of metals [62].
Thus, any n-Si/p-type NiO NPs film heterojunction could One of the major dilemmas of this century is the increased
show a photodiode behavior in the UV/Vis/NIR spectral contamination of natural aquatic bodies and sediments with
range. The photodiode behavior of p-type NiO NPs deposited toxic metals. During the last decade the introduction of Ni in
on n-type Si in the NIR spectral range was studied by the environment has been enhanced due to increased smelt-
applying Choi et al. photodiode experiment with these NPs. ing and mining activities. The interaction between microbes
The normal incidence irradiation of photodiode was carried and metals has been well established and the capability of
out employing a Hg lamp having a monochromator which microbes to accumulate and/extract metals is already used in
covered the spectral range of 290–1100 nm. The p-NiO/n- bioremediation by the biosorption of toxic metals. However
Si reverse biased diode generated photocurrent at numerous the mechanism behind this phenomenon has not been well
wavelengths which covers the UV/Vis/NIR spectral range. By established. Fungi are attractive candidates for biosorption
observing photo I-V profiles (photocurrent-voltage profiles) of metals as they are capable of growing under extreme
it is revealed that red illumination (748 and 650 nm) gener- conditions of temperature, pH, and nutrient availability and
ated highest photoresponse followed by blue (430 nm) and at high concentration of metal [64].
zero current in dark. This can be explained in terms of the fact Salvadori and coworkers [62] synthesized NiO NPs by
that the penetration depth of blue light in Si is smaller than using nickel chloride as precursor and dead, dried, and
red light so a smaller number of photocarriers are generated living biomass of filamentous fungus Aspergillus aculeatus
by blue light compared to that of red light which resulted (MIC = 2000 mg L−1 ) as reducing agent. Among the three
in lower photocurrent in case of blue light illumination types of fungal biomass used in this experiment maximum
[55]. adsorption capacity and hence maximum resistance to metal
toxicity were exhibited by dead biomass. The required doses
of biomass and precursor solution were shaken under suit-
7.2. Fabrication of NiO Nanoparticles by Using Microbes. able reaction conditions and then the Ni(II) solution was
Microbes such as bacteria, yeast, and fungi are potential separated from biomass by vacuum filtration using Millipore
candidates that act as reductant and stabilizing agents for membrane. The obtained NiO NPs were analyzed through
fabrication of nanoparticles. Although the rate of produc- various techniques. The energy-dispersive X-ray spectro-
tion of microbial synthesized nanoparticles is slower as scopic analysis revealed the presence of proteins which may
compared to that of nanoparticles synthesized by using serve as capping agent on the NiO NPs surface in the form of
plant extracts they offer certain advantages like economic film.
viability, simple scaling up, easy processing, and biomass The same group of researchers synthesized NiO NPs by
handling. the biosorption of Ni(II) ions on the Hypocrea lixii fungus
International Journal of Analytical Chemistry 11

(MIC = 1473 mg L−1 ) living, dried, and dead biomass. The Microbacterium sp. MRS-1 which was isolated from effluent of
Ni(II) retention capacity of Ni for dead biomass was highest nickel electroplating industry (effluent diluted with sodium
for dead biomass which indicated that dried and live biomass chloride was plated on nutrient agar and incubated for
were susceptible to toxicity generated by high concentration bacterium growth at 30∘ C). The bioremediation of Ni(II) ions
of metal. The TEM and HRTEM micrographs of fraction was achieved by incubating the bacterium with industrial
of dead biomass loaded with NiO NPs revealed that NPs effluent having Ni(II) of 2172 mg/L concentration at 30∘ C
were present on the fungal cell wall both extracellularly for 120 h at 200 rpm, followed by centrifugation of bacterial
and intracellularly through biosorption. The micrographs culture in order to remove cells of bacteria. The pale green
revealed that because of autoclaving process ultrastructural precipitates were obtained at the bottom of flask which
changes like shrinkage of cytoplasm were present both in were then collected, washed, dried, and then characterized.
NiO loaded dead biomass and in control sample. The average The formation of metal oxide NPs is explained by efflux
diameter of extra- and intracellular NiO fabricated NPs was mechanism, which involves the extracellular fabrication of
3.8 and 1.25 nm while their shape was spherical in both nanomaterials and by considering the role of metabolism
cases. dependent and biologically controlled processes which play
The mechanism for both above mentioned synthetic major role in the nucleation and deposition of inorganic
methods of NiO NPs by fungi is not fully elucidated. particles. The characterized precipitates were of NiO NPs
However, a 2-step mechanism was proposed; in first step having size in the range of 100 nm–50 nm with a flower like
adsorption of Ni(II) occurred with fungal cell wall through structure. Thus, this method provides a green route for the
its amide group and then their reduction into metallic Ni by remediation of soluble toxic Ni(II) ions with an efficiency of
the enzymes of fungal cell wall. In the second step Ni was 95% nickel removal.
oxidized into NiO by the H2 O and O2 present in the medium.
The proteins/peptides of fungal cell wall acted as capping
agent for formed NPs. This was confirmed by the EDX pattern
7.3. Characterization of NiO Nanoparticles. UV-Visible spec-
of NiO NPs in which additional peaks for C, N, and O
troscopy (UV-Vis) [23], atomic force microscope (AFM), X-
were present and further by their FTIR analysis in which
ray diffraction (XRD) [65], X-ray photoelectron spectrom-
band for N-H of amide II linkages of proteins/polypeptides
etry (XPS) [62], transmission electron microscopy (TEM)
at 1535 cm−1 was shifted to 1542 cm−1 ; this indicated the [61], scanning electron microscopy (SEM) [65], and energy-
deformation of N-H group as it capped the NiO NPs dispersive X-ray spectroscopy (EDS) [62] are fundamental
[64]. techniques reported in literature for the characterization of
Ullah and coworkers [65] synthesized NiO NPs by using NiO nanoparticles.
nickel nitrate hex hydrate as precursor and Rhizopus nigricans
fungus as reducing and stabilizing agent. The fungus was The NiO NPs synthesized extracellularly from Microbac-
obtained from bread and its fine pieces were added into terium sp. MRS-1 showed broad UV/Vis absorption band
precursor solution. The pH of solution was adjusted by using around 370–450 nm. The NiO NPs and functional groups
1 M NaOH solution. The solution after stirring for 5 hours of bacterial cell wall were studied by FTIR spectroscopy.
was kept overnight and then filtered by using Whatman The intense IR band at 580 cm−1 was assigned to Ni-
filter paper. This filtrate was then calcined at 500∘ C for 5 O vibrations and present in both NIPE (NiO fabricated
hours and the obtained sample was ground tiny particles. by the reaction of electroplating industrial effluent with
The characterization of NiO NPs revealed that the NPs are MRS-1) and NiO (fabricated by the reaction of NiSO4
polydisperse with an average diameter of ∼40 nm. Since these with MRS-1) and was absent in control (MRS-1 present
NPs are polydisperse, monodisperse NPs can be obtained by in a solution without Ni(II) ions). The strong absorption
varying the experimental conditions like pH, temperature, peaks at 1024.34 cm−1 and 1064.74 cm−1 were assigned to
and concentration of reductant and precursor. amine group and these peaks suggested the role of amine
group of bacterial cell wall in the adsorption of metal ions
7.2.3. Fabrication of NiO NPs Using Bacteria. Nickel is widely through hydrogen bonding and electrostatic interactions
used in steel, batteries, and electroplating industries and [63].
the Ni(II) ions discharged from these industries are car- Salvadori et al. [62] fabricated film of NiO NPs coated on
cinogenic so there is a need to reduce or remove their the surface of dead biomass of fungus and recorded the SEM
concentration in industrial effluents. The conventional efflu- images of dead biomass before and after coating of NiO NPs.
ent treatment methods are not efficient since they mostly It was observed that after binding of NiO NPs the surface
introduce secondary pollutants in environment besides being of biomass becomes modified. The EDS spectra of biomass
costly. So there is a great concern to develop cost-effective were also recorded before and after NiO formation and the
and environmentally benign treatment methods which can spectra recorded after formation of NiO NPs gave a signal
either completely remove soluble Ni(II) ions from industrial not only for Ni but also for C, N, and O which suggested
discharge or convert them into insoluble separable form such the presence of proteins on the surface of NiO NPs. The
as NiO which is insoluble in water. proteins act as capping agents which stabilize the NiO NPs
Sathyavathi and coworkers [63] converted the soluble and are also responsible for the organization of NiO NPs
NiSO4 present in discharged effluents of electroplating indus- on the surface of dead biomass of fungus in the form of
try into insoluble NiO by using cells of nickel resistant film.
12 International Journal of Analytical Chemistry

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