GREEN SYNTHESIS OF NANOPARTICLES & ITS

CHARACTERIZATION
 Ni-Mn Nps Synthesis & Characterization

nn

Research Paper
Submitted to Ma’am Shazia
Submitted by Nayab, Asba, Ayesha, Tayyaba

Roll no 95, 117, 59, 89

Semester 8Th (Physical)
Course Code Chem-456
Course Title Physical Chemistry Advance Lab II

GC Women University Sialkot

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Contents:
Subtopics Page no.

Abstract 03

Experiment; Green Synthesis of Mn & Ni 04-09

Bimetallic Nanoparticles.
 Introduction

 Phytochemical profile of Radish leaves 10

 Review of literature 11-16

 Material & Method 17-18

 Application: Degradation of dye 18-23

 Result and Discussion 23

 Characterization 23-27

 References 28-35

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Green Synthesis of Manganese Nickle (Mn-Ni) Bimetallic
Nanoparticles and their application as Dye removal
Abstract:
The development of efficient green chemistry methods, in recent years, for metal nanoparticle’s
synthesis has become a focusing point for researcher. In order to find eco-friendly method for
nanoparticle synthesis many investigation has been done in this regard. The method which used
organisms for nanoparticle’s production are considered more preferable than any other method.
The plant among these organisms are considered as the best and suitable for nanoparticle’s
biosynthesis. Nanoparticle’s synthesis rate is enhanced by using plant and produced nanoparticles
are more stable. By using plant the various types of shape as well as size of nanoparticle were
obtained. Nickel and manganese bimetallic nanoparticle synthesized by reduction of their salt
solution with help of reducing agent present in leaves plant i.e. Radish leaves. Nickel chloride
hexa-hydrate and manganese chloride salt solution are prepared in separate measuring flask.
Bimetallic alloy nanoparticle of Mn-Ni are prepared by addition of manganese and nickel salt
solution simultaneously in prepared and filtered leaf extract and maintain the temperature about
50-60oC with continuous stirring for about 1:30 hours. The formation of nanoparticle are
monitored by observed color change in solution. The benefits of this method are that all resources
are easily available and inexpensive. This taken not so much time and can be carried out easily.
Also this method not produced any toxic agent which may cause contamination in environment or
toxic for human health. All salt solution are prepared easily and not so much complex calculation
are required in this regard. Nanoparticles are used as an application for dye degradation. Many
factors like pH, Sunlight, Concentration of dye, Concentration of nanoparticles affect the
degradation process. Though UV-Vis, technique used for confirmation nanoparticle synthesis. All
these factors are also further monitored by UV visible spectrophotometer for spectral studies to
determine either the degradation is increased or decreased at different stages. SEM, TEM, XRD,
FTIR, EDX are used in order to characterize nanoparticles.

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1. Introduction:
The word Nano is used to describe one billionth of something, the concept of nanotechnology was
introduced by Nobel Laureate Richard P Feynman. It is field of applied science which is used to
control matter size at molecular level smaller than 1 micrometer and normally 1-100 nanometer
either by scaling up from single group of atom or by refining or reducing bulk material. [1]
Nanotechnology finds its application in drug development water decontamination information and
communication technology and production of stronger and lighter material. [2]

Nanoparticle are agglomeration of atoms and molecule in range of 1-100 nm. They are made of
one or more species of atoms and can have a wide range of size dependent properties. NPs bridge
the gap between small molecules and bulk materials on basis of energy states. Because of variation
in synthesis NPs are classified on the basis of dimension, morphology, composition, uniformity,
and agglomeration. [3]
Many methods are used for the synthesis of metallic NPs such as physical, chemical & biological
methods. Physically NPs are prepared by evaporation-condensation and laser ablation etc.
Chemically NPs are prepared by Sol Gel method, hydrothermal method etc. But Green Synthesis
preferred over them because of their disadvantages. The greatest disadvantage of chemical and
physical method is that they are costly, and use of toxic and hazardous chemicals involve. [4]

Green synthesis is set of principles that decrease or eliminate the generation of toxic substances in
application of chemical products. It is done by minimizing the waste at source, use of catalysts in
place of reagents, by using the renewable resources to improve efficiency. The purpose of green
is to implement sustainable processes. This method is simple cost effective, reproduce able and
often results in more stable material.

Microorganisms are not preferred for synthesis because rate of synthesis is slow and only a limited
number of sizes and shapes are produced. Plants are preferred because they produced more stable
NPs due to its advantages, it is used in all important fields of science focusing on greener
environment. It is safe, eco-friendly and biocompatible method which give more preference over
the chemical method that is of high cost using toxic chemicals and harsh conditions. [5]

The single metallic nanoparticle is known as monometallic nanoparticle such as Ni, Mn and Cu
NPs. The term bimetallic NPs refer to combination of two metallic nanoparticles. The application
of nickel monometallic nanoparticle are anode of solid oxide fuel cells or conductive electrolytic
layer proton exchange membrane fuel cells, automotive catalytic converters, coatings, plastics,
nanowires, nanofibers and textiles, magnetic fluid and catalyst.[6]

The major application of manganese nanoparticle are Magnetic data storage, Magnetic resonance
imaging, Biosensors, Textiles, Coatings, nanowires, plastics, and nanofibers. The improvement in
catalytic properties is the biggest advantage of bimetallic over monometallic. It is used to create
new properties in addition to original single-metal catalyst property. One of the metal in bimetallic

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NPs controls the activity in various reactions, allows selectivity and stability of the catalysts.it is
also used to avoid poising of catalyst. [7]

The plant used for preparation of Ni-Mn bimetallic NPs is Radish plant. Its scientific name is
Raphanus sativus L and common name is Muli.

Figure: Radish Leaves

1.1. Phytochemical profile of Raphanus Sativus L: [8]

Phytochemical Result
Alkaloids +ve

Tannins +ve

Flavonoids +ve

Saponins +ve

Terpenoids +ve

Steroids +ve

Phenolic compound +ve

Carbohydrates -ve

Reducing sugars -ve

Proteins -ve

Amino acid -ve

Glycoside +ve

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1.2. Reason to use Radish leaves:
Radish leaves are used because a bit research was performed in past. This plant is chose as a source
of reducing agent for preparation of nanoparticles. Also this plant contains a lot of phytochemicals.
Phytochemicals serve as reducing ,capping agent and stabilize the nanoparticles during NP
synthesis to convert metal ion to metal nanoparticles, so large amount of phytochemicals convert
large amount of metal ions into metal nanoparticles.

Phytochemical investigation of Raphanus sativus L. shows the presence of Alkaloids, Flavonoids,

Glycosides, Cardiac glycosides, Tannins, Saponin, Protein, Amino acid, Terpenoids and steroids
etc. Flavonoids show anti-allergic, anti-inflammatory, anti-microbial and anti-cancer activity.
Glycosides play an important role in lowering the blood pressure. They are also used in treatment
of congestive heart failure and cardiac arrhythmia. The extract contains phytochemicals like
phenols and flavonoids that cause inhibition, this property of plant may be important in preventing
oxidative stress related diseases. [9]

1.3. Degradation of dye:

Degradation of dye is a process in which large molecule of dye are chemically broken down into
the smaller molecules. The products which are formed as a result of degradation are water, carbon
dioxide and mineral products due to which original color of dye appear. All molecules of dye are
not used during the process of dying.
Degradation of dye can be catalytically, photo catalytically. Photo catalytically degradation of dye
is an intensive process for the last half of 20th century. Synthetic dye process are used now a days
in products like clothes, furniture and plastic products. During the process of dying 12 percent is
excluded as waste and 20percent out of this waste excluded to environment. During this process
from a semiconductor surface (mostly sulphides and oxides) electro transfer from a valance band
to conduction band, when it illuminate by wavelength of light.
As a result the excitation which are generated react with water or oxygen produce hydroxide
radicals and superoxide anions. Catalytic degradation of dye is a slurry-phase reaction which have
catalyst in solid phase and reactant in liquid phase. The surface catalyzed reaction done by reaction
between reactant absorbed at the surface of catalyst.[10]
1.3.1. Mechanism of degradation of dye:
There are two mechanisms for the degradation of dye.
1. Direct Mechanism

2. In-direct Mechanism

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Direct mechanism for dye degradation:
The direct mechanism of photo catalytic degradation of dye occurs under visible light. In this
mechanism excitation of dye occur in visible light (wavelength 400nm) from ground state to
excited state. The excited state of dye (dye*) species next convert to semi-oxidized radial cationic
(dye+) by the injection of electron into conduction band. These trapped electron then react with
dissolved oxygen in the system radicals of superoxide anions are formed(O2-) which in turn form
hydroxide radicals(OH-).These (OH-) radicals is responsible for oxidation of organic compounds.
.

Figure 2: Direct method for dye degradation

Indirect mechanism of dye degradation:

The indirect mechanism of dye degradation can be explained as follows.
Photo excitation:
The reaction is initiated when electron is promoted from filled valance band to empty conduction
band as a result of light. During the excitation process a hole is left behind. As a result hole and
electron pair is generated.

Ionization of water:
The hole generated react with water to generate OH- radicals.
H2O (ads)+ h+(VB) OH-(ads) +H+(ads)
The OH- radicals are powerful oxidizing agent.it attack on adsorb molecule and mineralize them
according to structure.

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Oxygen ionosorption:
The hole which is generated react with surface which is bound to water. Oxygen takes the electron
in the conduction band and generate anionic superoxide radicals (O2-).This superoxide prevents
electron-hole combination.

Protonation of superoxide:
Hydroperoxyl radicals are formed by protonation of superoxide, and then H2O2 which dissociate
to highly reactive hydroxyl radicals. [12]

O2-(ads) +H+ ⇋ HOO*(ads

2 HOO*(ads) H2 O2 (Ads) + O2
H2 O2 (Ads) 2OH*(ads)
Dye + OH* CO2 + H2 O (dye intermediate)
Dye +h* Oxidation product
Dye +e- reductions products

Figure 3: The complete process of indirect degradation

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1.4. Orange G:
Orange G is called a synthetic azo dye which is used in histology in many staining formulation.
Orange G is also called Acid Orange 10, or orange gelb. The appearance of orange G is like
orange crystal or powder. Orange G is more soluble in water and is slightly soluble in 95%
ethanol. Dye content is quantatively controlled in modified formula of OG. In its modified
formula, in 95% ethanol the orange G is reduce to a level of its solubility. The solution strains
intensely and rapidly when glacial acetic acid is added to its formula. Orange G is used to strain
keratin. When it combined with other yellow dye it is used to stain erythrocytes in trichrome
methods.

1.4.1. Structure:

Figure 4: Structural representation of Orange G

1.4.2. PH indicator:
It has two ionizable group,in aquous solution it shows two colour brilliant orange in neutral and
acedic pH,and in pH greater than 9 it shows red colour.[13

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1.5. Degradation of Orange G:

Figure 5: Degradation mechanism of Orange G dye

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2. Review of literature:
Manganese monometallic and bimetallic NPs are prepared by many methods. Green synthesis by
using plant extract, microorganisms etc. has the benefits i.e. medical applicability, scalability and
biocompatibility. This method is only based on the metal reduction by the different compounds
present in the plant extract i.e. polysaccharides, terpenoids etc. [14]

Jayandran et al., (2015) reported the manganese NPs synthesis by using lemon methanolic extract
as a reducing agent and turmeric curcumin as a capping agent. The reagents used is manganese
acetate and NPs produced having the size of about 50nm at 50-60 C temperature, 3-4 pH. [15]

Moon et al., (2015) reported the production of manganese dioxide NPs by using Potassium
permanganate and extract of Kalopanax pictus as reducing agent. NPs produced at room
temperature having size about 19.2nm. [16]

Kumar et al., (2017) synthesized MnO NPs by using Clove (Syzygium aromaticum) extract at 25
to 85 C temperature. The TEM and XRD analysis showed that MnO NPs were 2.5 and 1.8nm in
the size. [17]

Prasad and Patra et al., (2017) reported the synthesis of manganese nano rods by using Phyllanthus
amarus extract at room temperature, at pH 6.8. [18]

Prasad et al., (2014) reported the synthesis of Mn3O4 by using Malbur Nut [19] and in another
method by using Ananas comosus extract at room temperature. [20]

Souri et al., (2018) reported the synthesis of MnO NPs by using Dittrichia graveolens extract at
room temperature. [21]

Hoseinpour et al., (2018) explained the process by using Yucca gloriosa extract at room
temperature and pH 8 and produced MnO2 NPs. [22]

Najafpour et al., (2012) reported the synthesis by using microorganisms i.e. yeast, bacteria, fungus
have been used to produce Mn NPs. MnO2 produced by using Bacillus sp. cells without disturbing
the experimental conditions. [23]

Camacho L.M et al., (2011) reported the synthesis of Manganese sulfate bimetallic NPs by using
Streptomycin sp. [24]

Mamaev, Kishore et al., (2006) reported the synthesis of Manganese iron ferrate NPs by using
Thermoanaerobacter sp. by incubating the reaction mixture for 3 weeks at pH maintained at 6.5.
[25]

Nagwa M et al., (2017) reported the synthesis of Mg and Mn inter metallic nanoparticles by using
Pseudomonas stutzeri B4 Mg/W and Fusarium nygamai, F4 Mn/S. The Supplemented Metal
Nutrient having different metal concentration is used. Its UV-visible range fall at 415nm. [26]

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Vidhisha Jassal et al., (2016) reported the syhthesis of MnO NPs by using Sapindus mukorossi
(raw reetha) extract in the presence of reagents such as manganese chloride and potassium
permanganate. UV range for manganese oxide nanoparticles varies from 200 to 900nm. [27]

Waghmare et al., (2005) reported the synthesis of Zn and Mn bimetallic NPs by using aqueous
solutions of metals and actinomycetes which were grown in sterile malt extract and glucose yeast
extract peptone. Their UV visible range lie in the region of 380 and 350nm respectively. [28]

Parithviraj Challamuthu et al., (2019) reported the synthesis of Manganese dioxide NPs by using
Brassica oleracea extract and Potassium permanganate. Spectrophotometrically analyzed peak is
at 340 nm. SEM proved their structure in the range of 10-20 micrometer. [29]

Arun S. Parsad et al., (2015) reported the formation of MnO NPs by using Justicia adhatoda or
Adhatoda vassica nees extract and manganese sulphate used as the source of metal and sodium
hydroxide catalyst used to speed up the reaction. Their UV range lies in between 200-1000nm. [30]

Keerthana Sivanesan et al., (2017) reported the synthesis of Manganese monometallic NPs are by
using Aegle marmelos fruit extract and potassium permanganate as substrate and gives peak in
the range of 300-500nm. [31]

Urooj Kamran et al., (2018) reported the synthesis of Manganese NPs by using Cinnamomum
verum bark extract and manganese acetate tetrahydrade solution as Mn precursor at pH 7. [32]

Saneha Bhatnagar et al., (2014) reported the synthesis of MnO NPs are by using Lawsonia innerms
extract (henna Solution), manganese sulfate solution (10%). [33]

J Johan Peter Paul et al., (2017) reported the synthesis of Manganese NPs by using aqueous extract
of Ctenolepis garcini and Potassium permanganate as manganese source. Pellets of NPs are
collected by acetone etc. UV range were between 415-417nm. [34]

Solabomi Olaitan Ogunyemi et al., (2019) reported the synthesis of MnO2 and MnO NPs by using
Matricaria chamomilla extract and metal solution used. SEM and TEM shows the size of NPs is
about 16.5nm. [35]

Harish Kumar et al., (2013) reported the synthesis of MnO2 by the Co-precipitation technique by
using the manganese sulfate and oxalate. NaOH solution is added until the pH becomes 12. The
sharp peak observed at 339.6nm. [36]

Samikannu kanagesan et al., (2016) reported the synthesis of Manganese Ferrite NPs by Sol gel
self-combustion technique followed by calcination at 150C. Manganese nitrate, ferric nitrate, citric
acid and nitrates used as source of metals. UV range for manganese ferrite nanoparticles fall at
665nm. [37]

James F. Bhondi et al., (2009) reported the chemical synthesis of Mn NPs by using Diphenyl
ether and n-butyl lithium (n-BuLi, 1.6 M in hexane) as solvents. Argon is used for air stabilization.

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MnCl2 (anhydrous), oleic acid, oleyl amine and trioctylphosphine (TOP) are used as source of
metal. UV visible range of manganese fall around 425nm. [38]

Like Manganese, Nickle nanoparticles are also prepared by many methods. Green synthesis are
preferred over other because of non-toxicity of the method.

Ismat Bibi et al., (2017) reported the green synthesis of nickel nanoparticles by using Camellia
sinensis which act as reducing and capping agent. Common name of this plant is tea plant.
NiCl2.6H2O solution is used as the source of Ni NPs. The peak on the spectra is visible in the range
of 250-370nm. [39]

Imran Din et al., (2018) reported the synthesis of Nickle and nickel oxide nanoparticles by using
Calotropis gigantea extract which is act as reducing agent due to presence of phenolic agents and
anti-oxidants. (NiNO3)2.6H2O salt is used for the source of nickel. The peak of UV visible is at
400nm for Ni and 415nm for NiO. [40]

Onder Metin et al., (2010) reported the synthesis of NiO nanoparticles by using aqueous extract of
Tamarix serotine as reducing agent in nickel nitrate hexahydrate as a precursor. The UV range of
nanoparticle is 350-450nm. [41]

Samah Eldebaiky et al., (2017) reported the process of Nickle oxide nanoparticle by using
Fusarium verticilioid fungus which reduced the nickel ion in solution of nickel nitrate hexahydrate.
The observed UV range in this case is 200-400nm. [42]

Abhijit Kar et al., (2014) reported Nickle nanoparticles synthesis by using Hibiscus flower petals
(Hibiscus Rosa sinensis petals). Its UV range vary from 10-200nm. [43]

M Nasrollahzadeh et al., (2019) reported Nickel copper bimetallic nanoparticle by using Crataegus
azarolus (Mediterranean medlar) leaf extract as reducing and stabilizing agent. The
phytochemicals in this leaf used to reduce nickel and copper ions. Its UV range is 238-256 nm. [44]

Xiulan Weng et al., (2016) reported bimetallic iron-nickel nanoparticles by using Eucalyptus leaf
extract act as reducing agent, Nickel sulphate hexahydrate and ferrous sulphate heptahydrate salts
are used. [45]

Yuanzhi Chen et al., (2008) reported Iron Nickel bimetallic nanoparticles by Chemical reduction
method. (Fe (NO3)3) and Ni (NO3)2 used as salt source. It is a chemical reduction method. [46]
S T fardood et al., (2017) reported Nickel oxide nanoparticles by using Acacia senega (Arabic
gum) used as reducing agent, nickel chloride is used as salt. Its FTIR range is 400 per cm – 3900
per cm. [47]

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MM van Schooneveld et al. (2012) reported Tunable cobalt and nickel nanoparticles below 10nm
by chemical method to reduce cobalt and nickel from solution of nickel acetylacetonate and cobalt
acetylacetonate using reducing agent, trioctylphosphine oxide, dioctyl ether, 1,2- dichlorobenzene
(anhydrous,99%), 2-propanol and cyclohexane (anhydrous,99.5%). Nickel (II) acetylacetone,
Cobalt (III) acetylacetone used as salt. . Its UV visible range vary between 350-750nm. [48]

V. helan et al., (2016) reported NiO nanoparticles by using Neem leaves as using agent, we can
determine its magnetic properties, coercively and antibacterial analysis by this method, Nickel
chloride used as salt source. It give a UV peak at 412nm. [49]

Muhammad Imran et al., (2003) reported nickle and nickel oxide nanoparticles are prepared by
using Calotropis gigantea extract which is act as reducing agent due to presence of phenolic agents
and anti-oxidants. (NiNO3)2.6H2O salt is used for the source of nickel. The peak of UV visible is
at 400nm for Ni and 415nm for NiO. [50]

MA Nasseri et al., (2016) reported NiO nanoparticles by using aqueous extract of Tamarix serotine
as reducing agent in nickel nitrate hexahydrate as a precursor. The UV range of nanoparticle is
350-450nm. [51]

S.A El-Debaiky et al., (2015) reported that nickle oxide nanoparticle by using Fusarium
varicelloid fungus which reduced the nickel ion in solution of nickel nitrate hexahydrate. The
observed UV range in this case is 200-400nm. [52]

Mahmood Nasrollazadeh et al., (2019) reported that Nickel copper bimetallic nanoparticle by
using Crataegus azarolus (Mediterranean medlar) leaf extract as reducing and stabilizing agent.
The phytochemicals in this leaf used to reduce nickel and copper ions. Its UV range is 238-256
nm. [53]

Xiulan Weng et al., (2017) reported that bimetallic iron-nickel nanoparticles by using Eucalyptus
leaf extract act as reducing agent, Nickel sulphate hexahydrate and ferrous sulphate heptahydrate
salts are used. [54]

Gunay G. Valiyava et al., (2019) reported that Iron Nickel bimetallic nanoparticles can be
synthesized by Chemical reduction method. (Fe (NO3)3) and Ni (NO3)2 used as salt source. It is a
chemical reduction method. [55]

Ali Ramazani et al., (2017) reported that nickel oxide nanoparticles can be synthesized by using
Acacia senega (Arabic gum) used as reducing agent, nickel chloride is used as salt. Its FTIR range
is 400 per cm – 3900 per cm. [56]

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C. Vedhi et al., (2018) reported that Nickel oxide nanoparticles can be synthesized by using
Mangroves leaves (Rhizophora mangla) as reducing agent, also we used nickel nitrate solution, in
which nickel nitrate is reduced and form nanoparticles. Its UV range is observed at 319nm. [57]

Ravindra D.Kale et al., (2001) reported that Nickel nanoparticles can be synthesized from Betel
leaves (Piper betle) as reducing agent, Nickel sulphate hexahydrate is used as source of salt for the
synthesis of nanoparticles. Acetic acid is used to adjust pH. Its UV range is vary from 250-370nm.
[58]

P.S,Schabes-Retchkiman et al., (2006) reported in that Titanium nickel bimetallic nanoparticles

are synthesized by using Alfalfa plant (Medicago Sativa). Complex nitrate salts of both metals
used as precursor. UV visible range for nickel is 250-370nm and for titanium is 440-450nm. [59]

Anuoluwa Abimbola Akinsiku et al., (2017) reported silver and silver nickel bimetallic
nanoparticles are synthesized by using Canna Indica leaf extract (khizran, Indica shot) and silver
nitrate, nickel nitrate hexahydrate is used as source of metals. Their UV visible range is 200-
800nm. [60]

Angajala et al., (2014) reported Nickle nanoparticles by using Hibiscus flower petals i.e. Aegle
marmelos (Bael, Golden apple). Nickle chloride hexahydrate is used as the source of metal. UV
range for Ni is 300-370nm and for NiO is 300-400nm. [61]

B.T. Sone et al., (2016) reported that NiO nanoparticles are synthesized by using Callistemon
viminalis and metal solution used. P-type Bunsednite NiO powders with an average crystalline
size particles are produced. The optical band gab calculated for NiO is 3.35eV. [62]

S.R.Kuchekar et al., (2018) reported Nickle NPs synthesis by using Ocimum sanctum (Tulsi
extract), Nickle sulphate is used for metal solution. UV visible spectra obtained at 656nm. [63]

A.Ayesha Mariam et al., (2014) reported NiO and Ni NPs by using Azadirachta indica and
Psidium guajava leaves extract. Nickle chloride salt solution used for precursor. The band gap
values produced at 327nm. [64]

Vasudeo K et al., (2016) reported that Nickle NPs can be synthesized by using leaf extract of
Coriander (Coriandrum sativum L.). Nickle chloride salt solution used whose reduction take place.
Nickle NPs give peaks in the range of 400-700nm. [65]

Javed Iqbal et al., (2019) reported that the medicinal plant Rhamnnus virgate used for the synthesis
of nickel oxide NPs. Nickle nitrate solution used for the synthesis of desired NPs. Sharp peak
obtained at wavelength of 415nm. [66]

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R. Yuvakkumar et al., (2014) reported that nickle oxide NPs are produced by using leaf extract of
Rambutan peel waste which act as reducing and capping agent. Metal solution of any compound
used. By this method a sharp peak visualized at 415nm. [67]

Marica et al., (2005) reported synthesis of NiO NPs by using Aspergillus aculeatus extract. By
using nickel chloride as precursor. The method is basically the reduction of metal solution. [68]

Salvadori MR et al., (2009) reported the synthesis of NiO NPs by using Hypocrea lixii fungus.
Metal solution of any compound can be used. SEM, TEM characterization proved the synthesis of
NiO NPs. [69]

Youraj et al., (2006) reported Nickle monometallic NPs synthesis by using Conocarpus erectus
leaf extract. NPs produced having size in the range of 30-90nm. It gives a sharp peak at 365nm by
spectrophotometer. [70]

Teyeb ould-Ely et al., (2005) reported Nickle Bismuth bimetallic nanoparticles by using wet
chemical method. Bis (Cyclooctadiene), Tetraphenyldibismuthine are used chemical agents. This
process is carried out in the absence of stabilizing agent and involved decomposition of precursor
organometallic compound that are the solution of the metals. Addition of stabilizer leads to the
formation of NiBi nano wires. [71]

Y P Vinichenko et al., (2015) reported that Nickle hydroxide nanoparticles are synthesized by
using precipitation chemical deposition method. Nickle nitrate and sodium hydroxide used as
reagent. Beta nickel hydroxide hexagonal lattice nanoparticles are produced. Their UV range is
350-400nm. [72]

Yu. G. Morzov et al., (2010) reported that Nickle nanoparticles synthesis by using Crucibles
levitation jet method. For this purpose metallic nickel is suspended in quartz tube. For NPs
production oxygen gas added. [73]

Suleh Chandra et al., (2011) reported that Nickle monometallic nanoparticles are synthesized by
using ethanolic solution of benzyl diethylene triamine and nickel nitrate hexahydrate. The range
for Ni NPs is 250-370nm. This is actually a chemical method. [74]

H. Ipser et al., (2019) reported that Pure Ni and Ni-Sn nanoparticles synthesized by using chemical
reduction method. Diethyl glycol and Poly vinylpyrrolidone used as reducing and surfactant agents
respectively. UV peak for nickel is at 325nm and for nickel tin intermetallic nanoparticles at
385nm. [75]

Jyoti Chaudary et al., (2019) reported Cu-Ni bimetallic nanoparticles synthesis by using ethylene
glycol and diethylene glycol which act as reducing agents and solvents. These are prepared by

16
using suspensions of nickel carbonate, copper carbonate and solutions of nickel nitrate and copper
nitrate. These bimetallic NP give peak at 565nm. [76]

3. Materials and Method:

Chemicals:
Manganese (II) Chloride, nickel (II) Chloride from star company, Radish plant leaves from the
local market.

Apparatus:
Hot plate, beakers, measuring flask with stopper, funnel, filter paper, magnetic stirrer, and
thermometer and weigh balance.

4. Procedure:
Leaf extract:
Take leaf from plant, washed with distilled water and dried the leaves. Dried leaves were ground
in an electric grinder to obtain fine powder. About 4 g of the powder is put into 100ml distilled
water. Put this beaker on hot plate with magnetic stirrer and thermometer and maintain the
temperature at about 60oC. After 30 minute the beaker is taken off from hot plate and filter it with
help of funnel and stand. The extract of leaf is prepared.

Figure 6: Preparation of leaf extract

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Solution Preparation:
Take about 3.15g of NiCl2 in 50ml flask and 5.95g of MnCl2 in separate 50ml flask. Now add
distilled water in it up to mark to make the 0.5M solution of both salt.

Synthesis of bimetallic nanoparticle:

Take about 30ml of each salt solution in a beaker of 100 ml and add about 40 ml of leaf extract.
Add magnetic stirrer to stir the solution thoroughly and thermometer to maintain the temperature.
Put this solution at hot plate with temperature about 60oC for about 1 and half hour until color
change from green to dark green is observed. Phytochemicals in leaf extract are used as reducing
agent which reduce the Mn and Ni metal ion into metal nanoparticle indicated by color change.
After taking off solution from hot plate, it must be settled for almost 24hours in order to synthesize
NPs. After 24hours NPs solution is centrifuged for 10 minutes at 5000 rpm. NPs are prepared in
wet form. Then dry it in oven or in open air to get NPs in powder form. Repeat the same procedure
for bulk synthesis of NPs. [77]

5. Degradation of dye by using NPs:

Nanoparticles play important role in every field of life on large scale due to its unique material
characteristics and submicroscopic size. One of its important application is degradation of dye to
check its reliability for industrial applications.

Preparation of dye Solution:

Take about 50mg of Orange G dye in 100ml flask and add distilled water up to the mark to make
solution of 500ppm. Take 20 ml of stock solution and add to a 100 ml flask and fill it up to the
mark to make 100ppm dilute solution.

6. Effective factors:
Factors which mostly affects the degradation process are following:

6.1. Effect of pH:

pH is an effective factor for photo-degradation. It is difficult to maintain different pH. In order to
determine the effect of pH, take 5 test tubes and add 10ml of dye solution and 10mg of Nps into
each test tube. Then maintain different pH (4, 6, 8, 10, 12) by using pH meter. Orange G has an
optimum pH at 6. By adding 2 drops of HCl pH drops to 4. When 1 drop of NaOH is added then
pH at 6 is maintained. When 4 drops of NaOH is added then pH increased to 10. When 6 drops of
Mao is added then measured pH is 12. Now by maintaining all the required pH stand all the
solution in test tube in the test tube rack for 40-50 minutes. After standing the solutions take their
spectra by using spectrophotometer at 𝜆𝑚𝑎𝑥 which is 475nm for Orange G. Their Spectra gives
percentage absorption verses pH which means that how degradation varies with pH.

18
 pH % Degradation
4
6
8
10
12

Figure 7: The graph show that degradation of dye is maximum at pH 6, by increasing the
pH the degradation rate decrease

Chemistry behind pH Factor:

At pH 6 there is maximum photo degradation. When pH reaches to 10 degradation decreases. It
is because Orange G dye is negatively charged in acidic solution whereas NPs are positively
charged at low pH. So when pH changes then it changes the charge on our NPs i.e. towards
negative charge by the absorption of hydroxide ions that leads to the formation of hydroxyl radical.
So that repulsion between nanoparticles and dye increases gradually and degradation decreases.
[78]
As at higher pH electron-hole pair recombination increases and dye degradation decreases.
Also the hydroxide ions form layer on the NPs and make them inactive for the degradation. So at
lower pH negatively charged dye attracts the positively charged NPs and the process of oxidation
is maximum which further leads to the formation of hydrogen gas by absorption of hydrogen ions
from water. So at the end reduction is performed so that the end product aniline is formed which
is used for various lab reactions. [79]

19
 Mn–Ni + H+ → Mn+– Ni + Ho

Mn+–Ni + H+ → Mn++ –Ni + Ho

Mn++–Ni → Mn – Ni ++

Ho + Ho → H2

6.2. Effect of Sunlight / Time:

In order to determine the effect of sunlight or time either the time is varied or sunlight. First of all
time is varied i.e. place the test tubes containing reaction mixture of dye and NPs in sunlight for
various time that is for 1 hour, 4 hours, 8 hours, 12 hours, 1 day etc. Then their degradation
percentage is determined by using spectrophotometer. In another process time remains constant
and intensity of sunlight changes and their spectra is recorded. It is observed that when equilibrium
is established then degradation becomes constant. Actually sunlight acts as an inducer for
degradation. It enhances the degradation process. Spectrophotometric analysis will give [80]

Time Adsorbed Dose

1 hour
4 hours
8 hours
12 hours
1 Day

Figure 8: degradation rate increase with increase in intensity of sunlight / time.

20
6.3. Effect of Dye Concentration:
The photocatalytic rate of certain dye depends upon its concentration, nature and presence of other
existing compound present in the solution to be determined. Prepare five aqueous solution of dye
orange G at different concentrations i.e., 100,150,200,250,300 mg/l. The concentration of
bimetallic nanoparticles of Ni-Mn was fixed. After analysis of all the solution it is indicated that
with the increase in the concentration of the dye, the rate of the degradation is decreases. Nappoline
studied the same effect for different dyes i.e. Reactive Yellow 17, Reactive Red 2 , Reactive Blue
4 at different concentrations. He observed that with increases concentration of dye the rate of
degradation decreases gradually.

Dye Concentration(mg/l) Degradation Rate (min-1)

100 0.095
150 0.090
200 0.085
250 0.080
300 0.075

Figure 9: Increase in concentration of dye lead to reduce the rate of degradation

Chemistry behind decrease:
As the reduction of the Orange G dye is heterogeneous reaction which take place by the adsorption
of the dye on to the surface of the nanoparticles. At initial the rate of degradation increases as the
active sites are available for the adsorption of the dye on to the surface of the Ni-Mn nanoparticles.

21
As the Ni-Mn nanoparticles have finite adsorption efficiency thus at a certain limit adsorption take
place after that as no more active site is available. Thus the rate of degradation is decreases because
no more active site available hence no more adsorption occur.Also there are great chances for
formation of OH radicles on the surface of the Ni-Mn nanoparticles and interaction of OH radicles
with the dye molecules.

These factors also influence the rate of the degradation. Initially at high dye concentration, more
molecules of dye are available for the excitation and energy transfer. High dye concentration is
favorable for the formation of monolayer at the active site of the Ni-Mn nanoparticles and cover
the whole surface. Hence significant amount of UV is adsorbed by the monolayer which is formed
at the surface of nanoparticles than the Ni-Mn nanoparticles.

Thus the rate of light penetration to the surface of the nanoparticles decreases. As the concentration
of the Ni-Mn nanoparticles is constant thus formation of the free radicle is also constant, the
number of free radicles which interact with dye and degrade it also low in this way rate of
degradation also decrease with increases in concentration of dye. [81]

6.4. Effect of Ni-Mn Nps Dosage:

The dosage of nanoparticle also play important role in determining the rate of degradation of dye.
As the adsorption of dye take place at the surface of the nanoparticle thus the active site is
important factor. An increase in active site increase the rate of degradation as large amount of
active site available for dye degradation. Wei and Wan reported that same result is obtained with
Ni-Mn Nps when it is used to degrade Gentian Violet. The degradation rate of Chromotrope 2B
and Amido black dye also increases with increases in dosage of nanoparticles.
But some studies show that the amount of nanoparticles show both negative and positive impact
on the rate of degradation of dye. Zhang studied the rate of degradation of methylene blue with
Ni-Mn nanoparticles, initially the rate increase with increase in concentration of the bimetallic Ni-
Mn nanoparticles but at a certain limit after that the rate becomes constant with further increase.
Reactive Yellow 17, Reactive Red 2 and Reactive Blue 4 also degrade with Ni-Mn nanoparticles
but after increasing the concentration of the nanoparticles Reactive Red 2 and Reactive Blue 4
slightly decrease and then constant but rate of degradation for Reactive Yellow 17 remain constant.

Ni-Mn Np Concentration(mg/l) Degradation Rate (min-1)

0.1 50
0.3 60
0.5 70
0.7 80
0.9 90

22
Figure 10: Rate of degradation of dye increase with increase in concentration of Ni-Mn
Nps, but after certain limit it tends to decreases with increase in Ni-Mn Nps
Chemistry behind Decrease:
An increase in the concentration of the nanoparticles increases the amount of photons adsorb and
hence the rate of degradation of dye. However increase in concentration of nanoparticle from a
certain limit lead to increase in opacity of solution and thus reduce the photon flux to reach the
mixture and thus reduce the rate of degradation. Also the increase in the concentration of the
nanoparticles cause agglomeration of the nanoparticles thus cause a loss in the surface area of the
reactive site on nanoparticles, thus reduce the rate of the degradation of dye. Due of increase
concentration of the nanoparticles, particles may be suspended and thus cause the scattering of
light and influence the rate of reaction. [82]

7. Result and Discussion:

Synthesized NPs are known in solution by the color changing from green to dark green due to
metal ion reduction. The phytochemicals in leaves extract reduce the metal ions to zero valent
metal nanoparticles and stabilizes by being adsorbed. The color change can be easily identified by
the naked eye. It was clearly indicates the formation of well reduced and stabilized nanoparticles.
The nanoparticles are used in many fields due to its unique properties. Ni-Mn nanoparticles are
used to degrade the dye Orange G in aqueous solution. The degradation of dye was observed with
the help of spectrophotometer. The spectral studies showed that pH, time, concentration of Orange
G and dosage of Ni-Mn nanoparticles are main factors that affect the rate of degradation of dye.
At pH 6, rate of degradation id high. By increasing the concentration of dye rate of degradation is
decreased and with increase the dose of Ni-Mn nanoparticles the rate of degradation increases but
at certain limit.

23
8. Characterization:
8.1. UV-Vis Spectra Studies:
One of the most convenient techniques for characterization of nanoparticles is UV-Vis
spectroscopy. The synthesized extract of radish plant was confirmed by the strong broad
absorption peak at around 320 nm. UV-Vis spectroscopy of Mn-Ni bimetallic NPs showed
maximum absorption at 225 nm. In this spectrum the peak of extract is absent which indicates that
nanoparticles are synthesized and leave extract is used only for reduction and stabilization of metal
ion into metal nanoparticles.

Figure 11: UV-Vis spectra of Radish leaves show peak at 320nm.

Figure 11: Uv-Vis spectra of Mn-Ni bimetallic NPs give peak at 225nm.

24
8.2. Scanning Electron Microscope (SEM):
The image obtained by SEM shows the shape and size of the biosynthesized Ni-Mn bimetallic
nanoparticles that are prepared from Radish leaves (Raphanus sativus L.). The size of the
nanoparticles was observed by adjusting different magnification at SEM. From the image obtained
from SEM, it is noted that nanoparticles contain spherical and rod like shape with high
agglomeration.

Figure 13: Rod and Spherical shaped Ni-Mn Nps

It is also observed that due to aggregation of small sized nanoparticles, large sized nanoparticles
may form. Polydispersed nanoparticles were dispersed and the surface of nanoparticles was seems
to be rough in SEM image. Basically the agglomeration of nanoparticles was firstly reported by
Ramgopaletal by using extract of soap nuts. The reason behind the agglomeration of nanoparticles
is deficiency of capping agent in the leaf extract during the synthesis of nanoparticles. Capping
agent act as stabilizing agent and provide colloidal stability also prevent agglomeration and
uncontrolled growth of nanoparticles.

8.3. X-Ray Diffraction (XRD):

XRD determine the crystalline structure and size of the nanoparticles. After obtaining results from
the SEM, further demonstration and confirmation of bimetallic Ni-Mn nanoparticles was needed.
It took place by characteristic peaks obtained by XRD image. From XRD images it is demonstrated
that four diffraction peaks are obtain which indicates that Ni-Mn nanoparticles are fcc and
crystalline in nature. Broadening of Bragg’s peak indicate the formation of nanoparticles.

Figure 14: Spectrum obtained from XRD, confirms the fcc and crystalline structure of Ni-
Mn Nps

25
8.4. Energy Dispersive X-Ray Analysis (EDX):
EDX perform elemental analysis of nanoparticles. The spectra obtained from EDX reveal strong
signals in the region of Bimetallic Ni-Mn nanoparticles which confirm the formation and elemental
nature of bimetallic Ni-Mn nanoparticles. These signal are basically due to Plasmon response of
bimetallic Ni-Mn nanoparticles. Also some weak signals of Ni oxides of or Mn oxide may be
obtained due to impurities present in the extract of leaf during the preparation of nanoparticles.

Figure 15: EDX; Sharp peaks confirm the formation of bimetallic Ni-Mn Nps
8.5. Fourier-Transform Infrared Spectroscopy (FTIR):
To identify potential functional groups of biomolecules in the leaf, that are responsible for the
reduction of Ni-Mn ions into nanoparticles FTIR is performed. Spectrum shows a strong peak for
the carboxylic group which is modified into bimetallic Ni-Mn nanoparticles. A broad adsorption
band also observed due to O-H stretching of alcohol and H bonded phenol groups. A weak band
also obtained due to N-H bending due to primary amines. This band modifies into a broader band
indicate the presence of C=O stretching vibrations of carbonyl group.
New narrow bands are formed due to synthesized bimetallic nanoparticles of Ni-Mn indicating the
-NO2 aliphatic nitro group and C-N stretching of carboxylic groups. A small peak also obtained
due to presence of alkyl halides. In addition, FTIR spectrum confirm the presence of functional
biomolecules such as hydroxyl, carboxyl, phenol and amine groups in the Raddish leaves. [83]

26
Figure 16: FTIR;Sharp peaks indicate the presence of Carboxylic, Amido, Alcohol and
Phenols along Ni-Mn Nps.

8.6. Transmission Electron Microscopy (TEM):

Transmission electron microscopy is usually uses an electron beam to produce an image of
nanoparticles sample along higher resolution than the light based imagining techniques. It is used
to directly measured nanoparticle size, grain size, size distribution and morphology. In this
technique, electron diffraction pattern were collected from HR-TEM to identify the phase and size
of the nanoparticles. The images obtained from TEM shows that the nanoparticles are spherical
and eclipsed morphology. The nanoparticles are in dispersed form and crystalline structure. [84]

Figure 17: TEM: Eclipsed morphology of Ni-mn Nps

27
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