UNIVERSITY OF ENGINEERING AND TECHNOLOGY

UNIVERSITY OF ENGINEERING AND TECHNOLOGY, LAHORE
Title of Research
Synthesis of Nickel and Copper nanoparticles and their possible applications

Name of student: Maria Aziz
Registration No.: 2017-M.Phil-App-Chem-40
Date of Registration: 23-01-2017
Part Time/full Time: Full Time
Supervisor: Dr. Zahoor Ahmad
Dept. of Chemistry, UET Lahore

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University of Engineering and Technology, Lahore.

Year
2017-2019
1.Problem Statement
Recently, synthesis of nanoparticles has became area of interest for many scientists for various applications like drugs and medications, manufacturing and materials, electronics, energy harvesting, and mechanical industries. Nanoparticles are very small sized particles ranging from 1-100 nm. Inorganic nanoparticles have several applications in physics, medical sciences and chemical engineering for their optical, therapeutical and catalytic applications. In particular, the production of composite materials has been boosted by nanotechnology owing to their worthwhile applications to sensors and membrane separation processes. Recently, nanotechnologies for hydrogen manufacturing led to amazing results in photocatalytic conversion of pollutants as hydrogen sulphide. Other than biotechnological manufacturing methods, it has been observed that physical and chemical methods for nanoparticle synthesis are essentially based on top–down and bottom–up techniques , according to a well-known classification currently accepted in the scientific community. Top–down techniques in wet-chemical synthesis of nanoparticles, in spite of an intrinsic simplicity in their processing steps, did not find extensive application due to some problems in controlling shape and size distribution function of the nanostructured phase. In fact, size polydispersity shows a crucial drawback in many fields, as in optics and electronics, in which usually both mean and standard deviation of   diameters have to be minimized. Recently there is an emerging interest to synthesize magnetic NPs of Fe, Co, and Ni due to their superior magnetic properties and potential uses in many fields as in catalysis, memory storage devices, and sensors. In the medicine field they are used for magnetically controlled drug delivery, magnetic resonance imaging, and hyperthermia treatment of cancer cell. Copper  nanoparticles are essential in modern world because of their potential dielectric, magnetic, electrical, optical, imaging, catalytic, biomedical and bioscience properties.

Copper nanoparticles act as an anti-biotic, anti-microbial, and anti-fungal agents.

They have to be added to plastics, coatings, and textiles
Copper nanoparticles diet supplements have efficient delivery characteristics
They are high strength  metals and alloys
EMI shielding
Use as heat sinks and highly thermal conductive materials
They are efficient catalyst for chemical reactions and for the synthesis of methanol and glycol
Use as sintering additives and capacitor materials
Applied in conductive inks and pastes containing Cu nanoparticles can be used as a substitute for very expensive noble metals used in printed electronics, displays, and transmissive conductive thin film applications
Use in superficial conductive coating processing of metal and non-ferrous metal
Manufacturing of MLCC internal electrode and other electronic components in electronic slurry for the miniaturization of microelectronic devices;
Applied in nanometal lubricant additives.

The key applications of Nickel nanoparticles are:
As anode of solid oxide fuel cells
As conductive electrolytic layer of proton exchange membrane fuel cells
In automotive catalytic converters
In coatings, plastics, nanowires, nanofibers and textiles
As magnetic fluid and catalyst
As propellant and sintering additive.

2.Aims and Objectives
Production of Nickel and Copper nanoparticles nanoparticle with strict control of homogeneity, particle size and shape.

Investigation of structural properties of the respective nanoparticle using different advanced techniques.

Nanocomposite produced might be of high efficiency.

Nanoparticles will be assessed for their possible applications.

3.Literature Survey
Rajesh et al.1 synthesized copper nanoparticles from Syzygium aromaticum bud extract. The copper nanoparticles (CuNPs) were prepared using Syzygium aromaticum (clove) bud extract through simple and eco-friendly green route. The synthesized nanoparticles were subjected further for structural, morphological, optical and antimicrobial studies. The high crystalline nature of Cu-NPs with a face centered cubic phase is revealed by the X-ray diffraction (XRD) pattern. Morphological studies were performed to study the shape and size of the synthesized nanoparticles. Energy dispersive spectroscopy (EDS) attested the high intense metallic peak of copper (Cu) and low intense peaks of carbon (C), oxygen (O), chlorine (Cl) and phosphorus (P) elements owing to the capping action of biomolecules of bud extract in CuNPs formation. The zeta (?) potential of the CuNPs testified the stability of the nanoparticles. Ultraviolet-visible (UV–vis) absorption spectrum showed the characteristic absorption peak of CuNPs. Fourier transform infrared spectroscopy (FTIR) analysis confirmed the presence of different functional groups at various positions. The antimicrobial activity was testified against the selected pathogens using bio-CuNPs. The positive test results of zone of inhibitions of 8 mm and 6 mm were obtained against Bacillus spp. and Penicillium spp., respectively.

Asghar et al.2 used black and green tea leaves for copper nanoparticles. They developed an eco-friendly synthesis of iron (Fe), copper (Cu) and silver (Ag) nanoparticles (NPs) using green tea and black tea leaves extracts. Synthesized NPs were characterized using techniques SEM, FTIR, EDX and UV/Vis spectroscopy . Antibacterial activity of NPs was tested against methicillin- and vancomycin-resistance Staphylococcus aureus strains. Antifungal activity was investigated against Aspergillus flavus and A. parasiticus which is fungal species. Adsorbent ability with aflatoxin B1 (AFB1) was also investigated in solution. Ag-NPs showed increased antibacterial/antifungal activities and less the aflatoxins production in comparison to Fe-NPs and Cu-NPs. Adsorption capacity of all NPs with AFB1 contamination has been founded in the order of Fe-NPs > Cu-NPs > Ag-NPs. The equilibrium data investigated the favorability of Langmuir isotherm with the adsorption capacity (131–139 ng/mg), Cu-NPs (114–118 ng/mg) and Ag-NPs (110–115 ng/mg). Thermodynamic parameters and kinetic studies showed that adsorption process is spontaneous, endothermic and followed the pseudo-second order. These results suggested that the synthesized NPs could have been effectively utilized as an alternative antibacterial/antifungal agent against diseases caused by multiple drug resistant pathogens. Further, these metal NPs may be utilize as a possible aflatoxins adsorbent in human food and animal feed such as rice, wheat, maize, red chillies and poultry feed.

E. et al. 3 synthesized Nickel nanoparticles using a simple hydrazine hydrate reduction method in the presence of tween 80 as a capping agent. Nanoparticles found applications in multiple fields as food and beverages, waste water management, electrical and electronics owing to their interesting properties. These properties can be fine-tuned using various synthesis methods ranging from solid state route to different wet chemical techniques as precipitation, sol-gel, hydrothermal and solvothermal methods. A simple wet chemical synthesis of nickel nanoparticles using Tween 80 as the capping agent is developed. Scanning electron microscopy (SEM) revealed a hierarchical nanowire- like morphology with thorn like sharp edges while the presence of nickel was confirmed by energy dispersive spectroscopy (EDS). X-ray diffraction studies revealed the crystalline nature of nickel nanowires and also the purity of the as-synthesized nanowires. Transmission electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED) analysis of the sample revealed the existence of a small quantity of nickel hydroxide. The magnetic property of the synthesized nickel samples investigated using vibrating sample magnetometer (VSM) which revealed a high saturation magnetization of ?43?emug?1. Antibacterial activity confirmed that nickel nanowire have an excellent bactericidal activity against both gram- positive and gram- negative bacteria which could be attributed to the morphology of the nickel nanowires.

Khani et al.4 used green synthesis method by fruit extract of Ziziphus spina-christi (L.) Willd. One of the main subjects in nanoscience is the implementation of green chemistry principles to nanotechnology. Recently the need to develop eco-friendly metal nanoparticle synthesis processes is observed. The ability of the fruit extracts of Ziziphus spina-christi (L.) Willd. was examined as novel reducing agents for the green synthesis of copper nanoparticles (Cu-NPs). Biosynthesized Cu-NPs were characterized by techniques UV–Vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). It has been found that the as-prepared Cu-NPs could be used as an efficient adsorptive nanomaterial to remove crystal violet (CV), from aqueous solution. The impacts of independent variables such as pH, initial dye concentration, adsorbent dosage and stirring time on CV removal were revealed using central composite design (CCD). Optimization of the variables for maximum adsorption of dye was performed using desirability function (DF) combined response surface methodology (RSM). The results revealed that 95% of CV with a high adsorption capacity (37.5 mg g?1) was removed with a small amount of adsorbent (80 mg) in a short time (7.5 min). In addition, antibacterial activity of the Cu-NPs were investigated on two different (g? and g+) bacteria; Escherichia coli and Staphylococcus aureus.

Logutenko et al.5 Synthesized Nickel Nanoparticles by the reduction of Its salts using the modified Polyol Method in the Presence of Sodium Polyacrylates, using various molecular weights by hydrazine hydrate in a polyol medium in the presence of sodium polyacrylates with molecular weights of 1200, 5100, and 8000. The nanoparticles has been characterized by X-ray diffraction, scanning and transmission electron microscopy, IR spectroscopy, and thermogravimetric analysis techniques. The effect of the manufacturing parameters, such as temperature, molecular weight of sodium polyacrylate, and polyol and precursor types, on the reduction products has been studied. The average particle sizes, their aggregation and polydispersity degrees increased as the polymer molecular weight increased.

Woodard et al.6 synthesized nickel nanoparticles from the dissociation of nickelocene (Ni(Cp)2) in an argon?hydrogen (Ar?H2) low pressure continuous?flow non?thermal plasma. The affect of process parameters on the synthesized Ni nanomaterial structure, size, size?dispersion, and carbon content has been characterized by EDS and TEM analysis techniques. The role of hydrogen dilution and plasma input power on material throughput is carefully handled. These studies, along with the prediction of the electron affinity and ionization potential of Ni(Cp)2 by DFT calculations, supports the hypothesis that the material loss?mechanism to the reactor walls is due to the inherent ambipolar diffusion present in this synthesis technique. This study suggested that precursors must be screened with care while attempting to produce nanoparticle via a l ow pressure, continuous flow plasma reactor.

Roberts et al.7 used High-Throughput Continuous Flow Synthesis of Nickel Nanoparticles . The high-throughput flow methods addressed scaling concerns associated with the implementation of colloidal nanoparticle (NP) catalysts for industrial processes. A favorable method for the synthesis of Ni-NPs was adapted to a continuous millifluidic (mF) flow method, achieving yields >60%. Also, NPs prepared in a batch (B) reaction under conditions analogous to the continuous flow conditions gave only a 45% yield. Both mF- and B-Ni-NP catalysts were supported on SiO2 and compared to a Ni/SiO2 catalyst synthesized by traditional incipient wetness (IW) impregnation for the hydrodeoxygenation (HDO) of guaiacol under ex situ catalytic fast pyrolysis conditions (350 °C, 0.5 MPa). Inn contast to the IW method, both colloidal NPs showed increased morphological control and narrowed size distributions. NPs prepared by both methods showed similar size, shape, and crystallinity. The Ni-NP catalyst prepared by the continuous flow method exhibited similar H-adsorption site densities, site-time yields, and selectivities toward deoxygenated products compared to the analogous batch-prepared catalyst, and it outperformed the IW catalyst with respect to higher selectivity to lower oxygen content products and a 31-fold decrease in deactivation rate. These results showed the utility of synthesizing colloidal Ni-NP catalysts using flow methods that can produce >27 g/day of Ni-NPs (equivalent to >0.5 kg of 5 wt % Ni/SiO2), while adjusting the catalytic properties displayed by the batch equivalent.

Issaabadi et al.8 used Green synthesis of the copper nanoparticles supported on bentonite. This was a cost effective and environment friendly method for the synthesis of the copper nanoparticles which were supported on bentonite (bentonite/Cu NPs) using Thymus vulgaris L. leaf extract as a mild, renewable and non-toxic reducing agent and efficient stabilizer without adding any surfactants. The catalytic performance of the catalyst was investigated for the degradation of methylene blue (MB) and Congo red (CR) in aqueous medium at 25 C using sodium borohydride (NaBH4) as the source of hydrogen. This indicated that the composite had an excellent catalytic activity, convenient reusability and long-term stability for the reduction of organic dyes.

Khan et al.9 prepared copper nanoparticles of high purity for the advancement of material science and also in technology. Starch-protected zero-valent copper (Cu) nanoparticles have been successfully synthesized via a novel facile route. The method used the chemical reduction in aqueous copper salt using ascorbic acid acting as reducing agent at low temperature (80 C). X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy techniques were used to revealed the size, structure and composition of synthesized Cu nanocrystals, respectively. Average crystallite size of Cu nanocrystals calculated by diffraction peaks using the Scherrer formula was about 28.73 nm. The outcomes of the study took us a step closer toward designing rational strategies for the synthesis of nascent Cu nanoparticles without inert gas protection.

Reverberi et al.10 synthesised Copper nanoparticles in ethylene glycol (EG) using copper sulphate as a precursor agent and vanadium sulfate as an a typical reductant which is being active at room temperature. It has been a technique for a relatively simple preparation of such a reagent, which was electrolytically produced without using standard procedures which require an inert atmosphere and a mercury cathode. Several stabilizing agents were attested and cationic capping agents were discarded owing to the formation of complex compounds with copper ions leading to insoluble phases contaminating the metallic nanoparticles. The elemental copper nanoparticles, were maintained with polyvinylpyrrolidone (PVP) and sodium dodecyl sulphate (SDS).They were characterized for composition by energy dispersive X-ray spectroscopy (EDS), and for size by dynamic light scattering (DLS), and transmission electron microscopy (TEM),and gave a size distribution in the range of 40–50 nm for both stabilizing agents. The process may represent an alternative to other wet-chemical techniques for metal nanoparticle synthesis in non-aqueous media based on old organic or inorganic reductants.

Khalid et al.11 synthesized Copper nanoparticles by using chemical reduction method in which de-ionized water was used as solvent. The surface morphology has been observed by Atomic Force Microscope (AFM). The formation of copper nanoparticles is confirmed by UV-Visible spectrophotometer (UV-Vis), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FTIR) techniques. Copper nanoparticles obtained by chemical reduction method have diameter in the range 14 nm to 55 nm. Structural analysis revealed the face centered cubic (fcc) crystal structure of copper nanoparticles.

Pandian et al.12 prepared Nickel nanoparticles by Green synthesis using Ocimum sanctum leaf extract. The physiochemical properties of green synthesized nickel nanoparticles (NiGs) were characterized by UV–Vis spectroscopy (UV–Vis), Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM). NiGs has been used as adsorbent for the removal of dyes such as crystal violet (CV), eosin Y (EY), orange II (OR) and anionic pollutant nitrate (NO3?), sulfate (SO42 ?) from aqueous solution. Adsorption capability of NiGs was examined in batch modes at different pH, contact time, NiG dosage, initial dye and pollutant concentration. The adsorption process was pH dependent and the adsorption capacity enhanced with increased in contact time and with that of NiG dosage, whereas the adsorption capacity decreased at higher concentrations of dyes and pollutants. Maximum percentage removal of dyes and pollutants were revealed at 40, 20, 30, 10 and 10 mg-L? 1 initial concentration of CV, EY, OR, NO3? and SO42 ? respectively. The maximum adsorption capabilities in Langmuir isotherm has been found to be 0.454, 0.615, 0.273, 0.795 and 0.645 mg·g? 1 at pH 8, 3, 3, 7 and 7 for CV, EY, OR, NO3? and SO42 ? respectively. The higher coefficients of correlation in Langmuir isotherm showed monolayer adsorption. The mean energies (E), 2.23, 3.53, 2.50, 5.00 and 3.16 kJ·mol? 1 for CV, EY, OR, NO3? and SO42 ? respectively, calculated from the Dubinin–Radushkevich isotherm revealed physical adsorption of adsorbate onto NiGs. Adsorption kinetics data was better suited to pseudo-second-order kinetics with R2 > 0.870 for all dyes and pollutants. NiGs were found to be an effective adsorbent for the elimination of dyes and pollutants from aqueous solution and can be applied to treat textile and tannery effluents.

Nasrollahzadeh et al.13 prepared copper nanoparticles using Ginkgo biloba L. leaf extract. Copper nanoparticles (Cu NPs) using Ginkgo biloba L. leaf extract as a reducing and stabilizing agent under surfactant-free conditions were prepared by green synthesis. The formation of Cu NPs is exmined by recording the UV–vis absorption spectra. The green synthesized Cu NPs are characterized by TEM, EDS, FT-IR and UV–visible spectroscopic techniques. According to UV–vis results, the synthesized Cu NPs by this procedure are quite stable even after one month showing the stability of Cu NPs. As environmental impact and economy, metallic Cu NPs offer several advantages over homogeneous and traditional heterogeneous catalysts. In addition,owing to the large metal surface area, Cu NPs shows very high catalytic activity for the Huisgen 3 + 2 cycloaddition of azides and alkyne at 25C. Also, the catalyst can be simply recovered and reused several times even almost no loss in activity.

Nasrollahzadeh et al.14 synthesised eco friendly Cu NPs/perlite composites without employing any toxic reductants or capping agents. Renewable natural Euphorbia esula L. not only acted as a reductant, but also served as a stabilizer for the formation of Cu NPs. Cu NPs synthesized using aqueous extract of the leaves of E. esula L. which was immobilized on perlite by a very simple and inexpensive method. The structural investigation was achieved using XRF, XRD, SEM, EDS, TEM, TG–DTA, BET and FT-IR. The Cu NPs/perlite showed favorable activity and separability on the catalytic reduction of 4-nitrophenol, and can be reused several times without a decrease in the catalytic activity. Their reaction rate constant was investigated according to the pseudo-first-order reaction equation.

Kruk et al.15 prepared monodisperse copper nanoparticles using the chemical reduction method. Metallic monodisperse copper nanoparticles at a relatively high concentration (300 ppm CuNPs) have been prepared by the reduction of copper salt with hydrazine in the aqueous SDS solution. The average particles size and the distribution size were investigated by Dynamic Light Scattering (DLS), Nanosight – Nanoparticle Tracking Analysis (NTA). The morphology and structure of nanoparticles were revealed using Scanning Electron Microscopy (SEM). The chemical composition of the copper nanoparticles was exmined by X-ray Photoelectron Spectroscopy (XPS). Monodisperse copper nanoparticles with average diameter 50 nm were obtained. UV/vis absorption spectra confirmed the formation of the nanoparticles with the characteristic peak 550 nm. The antimicrobial studies revealed that the copper nanoparticles has high activity against Gram-positive bacteria, standard and clinical strains, including methicillin-resistant Staphylococcus aureus, comparable to silver nanoparticles and some antibiotics. They also possessed antifungal activity against Candida species.

Mat Zain et al.16 prepared copper nanoparticles by microwave heating using ascorbic acid and chitosan. Copper nanoparticles were prepared by chemical reduction of their respective nitrates by ascorbic acid in the presence of chitosan using microwave heating. Particle size was increased by increasing the concentration of nitrate and reducing the chitosan concentration. Surface zeta potentials were positive for all nanoparticles synthesized and these varied from 27.8 to 33.8 mV. Antibacterial activities of Ag, Cu, mixtures of Ag and Cu, and Ag/Cu bimetallic nanoparticles were attested using Bacillus subtilis and Escherichia coli. The B. subtilis proved more susceptible under all conditions investigated. Silver nanoparticles showed higher activity than copper nanoparticles and mixtures of nanoparticles of the same mean particle size. On an equal concentration basis Cu nanoparticles proved more lethal to the bacteria due to a higher surface area. The highest antibacterial activity has been obtained with bimetallic Ag/Cu nanoparticles with minimum inhibitory concentrations (MIC) of 0.054 and 0.076 mg/L against B. subtilis and E. coli, respectively.

Shende et al.17 synthesized copper nanoparticles using Citrus medica Linn. (Idilimbu) juice. The synthesis of copper nanoparticles (CuNPs) by using Citron juice (Citrus medica Linn.), is nontoxic and cheap and it is eco-friendly method. The biogenic copper nanoparticles were eximined by UV–Vis spectrophotometer showing a typical resonance (SPR) at about 631 nm which is specific for CuNPs. Nanoparticles tracking analysis by NanoSight-LM20 revealed the particles in the range of 10–60 nm with the concentration of 2.18 × 108 particles per ml. X-ray diffraction showed the FCC nature of nanoparticles with an average size of 20 nm. The antimicrobial activity of CuNPs was obtained by Kirby-Bauer disk diffusion method against some selected species of bacteria and plant pathogenic fungi. The synthesized CuNPs showed a significant inhibitory activity against Escherichia coli followed by Klebsiella pneumoniae, Pseudomonas aeruginosa, Propionibacterium acnes and Salmonella typhi. The comparisons of plant pathogenic fungi tested, Fusarium culmorum was found to be most sensitive followed by F. oxysporum and F. graminearum. The achievement of this work is that for the first time citron juice was used for the synthesis of CuNPs.

Kathad et al.18 synthesised copper nanoparticle by green chemistry and biological synthesis. In both method copper source was same i.e. Copper Sulphate. Synthesis of the copper nanoparticles by green chemistry took normal time in synthesis using reducing agent ascorbic acid and size controlling by CTAB. The synthesis of copper nanoparticles by green method was done use of the plant (Artabotrys odoratissimus) which belongs to Annonaceae family which has local name “Nag champo”. Size comparision of particles prepared via both two different techniques were done by Particle Size Analyser (PSA). Which indicate that between both method synthesized by Green Chemistry method gave average size particles of 35nm. While in case of Biological, it was 135nm.

Neiva et al.19 obtained Size-controlled nickel nanoparticles by polyol method. Nickel nanoparticles stabilized by polyvinylpyrrolidone (PVP) were synthesized through modifications to the polyol procedure. Controlling the Ni/reducing agent (NaBH4) ratio led to different nanoparticles samples with average sizes of 3.4, 2.8 and 2.2 nm. The crystalline structure, the presence of PVP and the size of the nanoparticles were exmined by using X-ray diffraction (XRD), Fourier transformed–infrared spectroscopy (FT–IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) techniques. One sample was used to make carbon paste electrodes, which were electrochemically characterized and applied as a glycerol amperometric sensor in a NaOH medium. Several parameters were investigated, including the presence of PVP on the nanoparticles, the NaOH concentration, the Ni/Nujol/graphite ratio, the number of cycles applied and the type of support electrolyte. The application of the Ni nanoparticle-modified electrode as an amperometric sensor revealed a good sensitivity of 24.4 ?A M?1 and a low detection limit of 95.0 ?mol L?1.

4.Methodology
Nanoparticles will be prepared by chemical method and by green synthesis.
Preparation of Copper nanoparticles by chemical method.

Preparation of Copper nanoparticles by green synthesis .

Preparation of Nickel nanoparticles by chemical method.

Preparation of Nickel nanoparticles by green synthesis.

4.2Materials
Copper acetate hydrate
Tween 80
Distilled water
Copper sulphate solution
Coriander leaf extract from coriander leaves.

Nickel chloride solution
4.3Experimentation:
Chemical method for copper nanoparticles
Copper nanoparticles were synthesized using modified polyol method by the reduction of copper acetate hydrate in the presence of Tween 80 by refluxing between 190° and 200 °C. The X-ray diffraction pattern was used to analyze the formations of phase and crystal structure.

Green Synthesis of Copper nanoparticles from Eucalyptus sp. leaves
The Eucalyptus leaves should  thoroughly washed and dried in shade. To prepare the plant broth solution, 20 g dried leaves of Eucalyptus sp.leaves should cut into small pieces and wash with distilled water. This will be taken in a 250 ml beaker with 100 ml of distilled water and boiled for 20 minutes at 80C.The extract will be filtered through Whatman filter no.1 stored at 5C and will be used within a week. The colour of the extract will be brown. Ten ml of Eucalyptus sp. leaf extract will be added to 100 ml of 1 mM aqueous copper sulphate solution in a 250 ml Erlenmeyer flask.The colour of the solution changes from blue to pale yellowwhen the solution of Eucalyptus sp. Leaves extract and copper sulphate solution will be stirred for homogeneous mixing. The flask will be kept at room temperature overnight and the Cu nanoparticles separated out which settled at the bottom of this solution. The Cu nanoparticles thus obtained will be purified by repeated centrifugation method at 12,000 rmp for 15 minutes followed by re-dispersion of the pellet in deionized water. Later the Cu nanoparticles will be dried in oven.

Chemical method for Nickel nanoparticles
For the synthesis of Ni NPs ethylene glycol (EG), polyvinylpyrrolidone (PVP, average molecular weight 12,600 ± 2700), NiCl2 × 6H2O, and sodium borohydride will be used. A solution of NiCl2 × 6H2O in ethylene glycol with PVP will be used as an initial mixture. The ratio between Ni and the stabiliser will 1 : 5. The reduction will be performed by a stoichiometric amount of sodium borohydride under an efficient magnetic stirring at the temperature varied from 23°C to 170°C, with the system being maintained under magnetic stirring at required temperature for 1 h. Nickel NPs will be synthesised under air atmosphere.

Green synthesis for Nickel nanoparticles
Preparation of coriander leaf extract from coriander leaves.  
The coriander leaves will be thoroughly washed and dried in shade. For preparing the plant broth solution, 20 gm dried leaves of coriander have to cut into small pieces and washed with distilled water. Then it will be taken in a 250 ml beaker with 100 ml of distilled water and then boiled the mixture for 20 min at 80°C. The extract will filter through Whatman filter No. 1 and then will store at 5°C and can be used within a week.

Synthesis of Ni nanoparticles using coriander leaf extract. A volume of 10 ml of coriander leaf extract will be added to 100 ml of 1 mm aqueous nickel chloride solution in a 250 ml Erlenmeyer flask. The colour of the solution will be change from green to pale yellow after addition of coriander leaf extract and stirred the resulting solution for homogeneous mixing. The flask should kept at room temperature for overnight and Ni nanoparticles separate out and settle at the bottom of mixed solution of nickel chloride and coriander leaf extract. The Ni nanoparticles thus obtained will be purified by repeated centrifugation method at 5000 rpm for 15 min followed by re-dispersion of the pellet in deionized water. Then the Ni nanoparticles will be dried in oven at 80°C.

The pH of nickel chloride solution will be 4.0, when we added coriander leaf extract to this solution, pH changes from 4.0 to 4.24. The pH of coriander leaf extract will be 6.78. From this we confirmed that the capping between nickel and coriander leaf extract was taken place.

5.Expected Result:
As expected copper and nickel nanoparticles can be effectively synthesized. There will their beneficial applications. These nanoparticles are expected to possess high efficiency. The obtained data will be significant and will be of such quality that can be publish  in international journal of repute.

6.Research Time Table.

Sr.no Research Time Time duration
1. Literature Survey 2 month
2. Proposal presentation 2 months
3. sample preparation 2 months
4. Experimentatio and computation of results 3 months
5. Thesis write-up 2 months
6. Submission of Final Thesis Next month
7.References
K.M.Rajesh, B.Ajitha, Y. Ashok Kumar Reddy, Y.Suneetha, P. Sreedhara Reddy, Assisted green synthesis of copper nanoparticles using Syzygium aromaticum bud extract: Physical, optical and antimicrobial properties, Optik – International Journal for Light and Electron Optics, 2018, 154, 593-600.

Muhammad Asif Asghar, Erum Zahir, Syed Muhammad Shahid, Muhammad Naseem Khan, Muhammad Arif Asghar, Javed Iqbal, Gavin Walker, Iron, copper and silver nanoparticles: Green synthesis using green and black tea leaves extracts and evaluation of antibacterial, antifungal and aflatoxin B1 adsorption activity, LWT, 2018, 90, 98-107.

Deepa E., Helen Annal, Therese, Hierarchical Nickel nanowire synthesis using polysorbate 80 as capping agent, Applied Surface Science, 2018, 449, 48-54.

Rouhollah Khani, Batoul Roostaei, Ghodsieh Bagherzade, Maryam Moudi, Green synthesis of copper nanoparticles by fruit extract of Ziziphus spina-christi (L.) Willd.: Application for adsorption of triphenylmethane dye and antibacterial assay, Journal of Molecular Liquids, 2018, 255, 541-549.
O. A. Logutenko, A. I. Titkov, A. M. Vorob’ev, I. K. Shundrina, Yu. M. Yukhin, N. Z. Lyakhov, Synthesis of Nickel Nanoparticles by the Reduction of Its Salts Using the Modified Polyol Method in the Presence of Sodium Polyacrylates with Various Molecular Weights, Russian Journal of General Chemistry, 2018, 88, 388-294.

Austin Woodard, Lihua Xu, Alejandro A. Barragan, Giorgio Nava, Bryan M. Wong, Lorenzo Mangolini, On the non-thermal plasma synthesis of nickel nanoparticles, plasma processes and polymers, 2017, 15, 1-7.

Emily J. Roberts, Susan E. Habas, Lu Wang, Daniel A. Ruddy, Erick A. White, Frederick G. Baddour, Michael B. Griffin, Joshua A. Schaidle, Noah Malmstadt, Richard L. Brutchey, High-Throughput Continuous Flow Synthesis of Nickel Nanoparticles for the Catalytic Hydrodeoxygenation of Guaiacol, ACS Sustainable Chem. Eng. 2017, 5 (1), 632-639.

Zahra Issaabadi, Mahmoud Nasrollahzadeh, S. Mohammad Sajadi, Green synthesis of the copper nanoparticles supported on bentonite and investigation of its catalytic activity, Journal of Cleaner Production, 2017, 142 (4), 3584-3591.

Ayesha Khan , Audil Rashid, Rafia Younas, Ren Chong, A chemical reduction approach to the synthesis of copper nanoparticles, International Nano Letters, 2016, 6, 21-26.

Andrea Pietro Reverberi , Marco Salerno , Simone Lauciello , Bruno Fabiano, Synthesis of Copper Nanoparticles in Ethylene Glycol by Chemical Reduction with Vanadium (+2) Salts, Materials, 2016, 9 , 809.

Hina Khalid, S. Shamaila, N. Zafar, SYNTHESIS OF COPPER NANOPARTICLES BY CHEMICAL REDUCTONS METHOD , Sci.Int.(Lahore), 2015, 27, 30855-3088.

Chitra Jeyara Pandia, Rameshthangam Palanivel, Solairaj Dhananasekaran, Green synthesis of nickel nanoparticles using Ocimum sanctum and their application in dye and pollutant adsorption, Chinese Journal of Chemical Engineering, 2015, 23, 1307-1315.s
Mahmoud Nasrollahzadeh, S.Mohammad Sajadi, Green synthesis of copper nanoparticles using Ginkgo biloba L. leaf extract and their catalytic activity for the Huisgen 3 + 2 cycloaddition of azides and alkynes at room temperature, Journal of Colloid and Interface Science, 2015, 457, 141-147
Tomasz Kruk, Krzysztof Szczepanowicz, Joanna Stefa?ska, Robert P.Socha Piotr Warszy?ski, Synthesis and antimicrobial activity of monodisperse copper nanoparticles, Colloids and Surfaces B: Biointerfaces, 2015, 128, 17-22.

N. Mat Zain, A.G.F.Stapley, G.Shama, Green synthesis of silver and copper nanoparticles using ascorbic acid and chitosan for antimicrobial applications, Carbohydrate Polymer, 2014, 112, 195-202.

Sudhir Shende, Avinash P. Ingle, Aniket Gade , Mahendra Rai, Green synthesis of copper nanoparticles by Citrus medica Linn. (Idilimbu) juice and its antimicrobial activity, World Journal of Microbiology and Biotechnology, 2015, 31, 865-873.

Ratiram Gomaji Chaudhary, Jay A. Tanna, Nilesh V. Gandhare, Alok R. Rai, Harjeet D. Juneja, Synthesis of nickel nanoparticles: Microscopic investigation, an efficient catalyst and effective antibacterial activity, Advanced Materials Letters, 2015, 6 (11), 990-998.

Umesh Kathad, Harsukh Gajera, Synthesis of copper nanoparticles by two different methods and size comparision, International Journal of Pharma and Bio Sciences , 2014, 5 , 533-540.

Eduardo G.C. Neiva, Marcio F. Bergamini, Marcela M.Oliveira, Luiz H. Marcolino Jr., Aldo J. G. Zarbin, PVP-capped nickel nanoparticles: Synthesis, characterization and utilization as a glycerol electrosensor, Sensors and Actuators B: Chemical, 2014, 196, 574-581.

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