Synthesis, Characterization · PDF fileSynthesis, Characterization And Application Of Ni...
Transcript of Synthesis, Characterization · PDF fileSynthesis, Characterization And Application Of Ni...
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Synthesis, Characterization And
Application Of Ni Nanoparticles Using
Bimolecules As Capping Agent
By
Mr. Nazar Hussain Kalwar
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Introduction
Aims and objectives
Overview of the Literature
Experimental work
Part I- Fabrication of Ni Nanoparticles
Part II- Characterization of Ni Nanoparticles
Part III- Application of Ni Nanoparticles
Results and Discussion
Conclusion
Contents
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Nanotechnology is defined as the field of applied science and technology based on controlling the matter on the atomic and molecular scale, normally 1 - 100 nanometers in size,
1nm =10-9 m or (1 billionth part of a meter)
1nm = 10 angstrom unit (A0)
nm/ meter = marble / earth
1 A
1 nm
10 nm
102 nm
103 nm
104 nm
105 nm
bulk
nanoparticles
quantum dots molecules
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The nature construct its objects atoms by atoms or molecules by molecules.
Where as the current science and technology divides the things into nanoscale dimension
Nanotechnology is based on
Bottom-up ApproachTop-down Approach
Continue……..
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The nano scale materials and nanostructures are proved to be very attractive, because they hold many novel and unusual properties.
For this these have been paying much attention and have promoted a big deal of excitement since the period of last two decades.
Due to this it is thought to be a mysterious world, where atoms and molecules individually are responsible for the properties of a material.
Continue……..
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An important facet in making metal NPs is, the capability to maintain them physically away from one another, preventing their agglomeration and growth.
These are commonly stabilized by capping with different protective agents, which interact and bind with their surfaces, help in solubilizing them in different solvents and avoiding their aggregation.
The preparation of nanoscale materials with desired properties represents a significant challenge.
Continue……..
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The synthesis of metal NPs of few coinage metals such as
iron (Fe),
cobalt (Co) and
nickel (Ni)
are relatively more tedious because these are easily oxidized.
Along with the efforts to develop existing experimental procedures into mature techniques.
New methods are being explored that are more controllable with respect to particle properties.
A CHALLENGING JOB
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Technique Capping Agent Reducing agent Solvent/Medium Author/Year
Electro spinning technique. poly(vinyl alcohol) Electro spray Aqueous Nasser et. al
2009
chemical reductionpotassium
sodium tartrate(C4H4KNaO6·4H2O)
Hydrzine Aqueous Zhenguo et. al 2009
Microwave irradiation
method
Polyvinylpyrolidine Hydrzine Ethylene Glycol W. Zu et.al 2008
Reduction by Wet-chemical method
Without Protective agent
Hydrzine Ethylene GlycolSzu-Han et.al
2003
SolvothermalWithout Protective
agent Hydrzine Ethanol Liuyang Bai et.al 2007
Laser-Driven Aerosol No Hydrogen
Gaseous medium
(i.e. H2, He2)
Yuanqing et. al 2004
Solvothermal Oleic acid Sodium borohydride Aqueous Alexander et. al
2004
Some Reported Methods for Synthesis of Ni NPs
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Technique Capping Agent Reducing agent Solvent/Medium Author/Year
Hydrothermal Cysteine Same Aqueous Junhua et.al 2008
Hydrothermal Cysteine Same Aqueous Benxia et.al 2007
Wet chemical Cysteine Same Aqueous Partha et.al 2007
Wet chemical Cysteine Sodium borohydride Aqueous Martin et. Al 2006
Hydrothermal Cysteine Same Aqueous Bin Bang et.al 2006
Wet chemical Cysteine Sodium borohydride Aqueous Saikat et.al 2001
Reported Methods for Cyst-MNPs
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Use of environmental friendly and less expensive materials for reduction and encapsulation of Ni NPs.
Investigation of newer interactions between NPs and used stabilizing/capping materials.
Control of particle size at lower level to get enhanced catalytic properties for the formed NPs.
Characterization of particles to investigate new geometrical changes in the formed products.
Application of nanoparticles in the environmental processing.
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The newly developed method for synthesis of Ni NPs is recommended as new procedure in some relevant technologies such as
catalytic hydrogenation in some organic reactions
reduction/oxidation of some environmental toxic materials and others.
The electronic and photonic industry may also be benefited if these particles are finding new chemically effective procedural usage in this regard.
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UV-Vis spectra of Ni Nps containing solution were recorded with model Lambda 2 spectrometer of Perkin-Elmer. Analytical Scanning Electron Microscope (ASEM) model, JSM 6380Aof Jeol Company was used for SEM imaging of dried drop from Ni NPs containing solution on microscopic glass cover slip just after coating with gold layer for 5 minutes duration in a DC ion sputtrermodel, JFC-1500.
Crystalline patterns of Ni NPs samples were obtained by powder method using XRD of Bruker D-8 Advance model.DSC thermograms were recorded on Mettler Toledo DSC822.
FTIR spectra were recorded by using Nicolet 5700 FT-IR of Thermo.
INSTRUMENTATION
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0.6 ml Cysteine the sample was added and mixture was diluted to 6 ml with EG
Synthesis Procedure for Cysteine capped Ni NPs
Adding 0.1 ml NaOH
The sample was then removed from oven and cooled to room temperature in ice cold water
As prepared sample was then put into quartz cuvet to record UV-Viss spectra
1 ml of NiCl2 and 0.3ml Na2CO3 ml were placed in a 25 ml stoppered conical flask
This scheme was followed repeatedly for preparation of each sample during optimization of various parameters as well as sample preparation for different
characterization techniques.
The sample was heated in microwave oven for 1 mint
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Optimization Studies by UV –Visible Spectroscopy
Various parameters were optimized such as
Concentration of reducing and capping agent,
Heating time of the reaction,
pH of solution and
Stability of the as prepared NiNPs
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300.0 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600.00.000
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.000
nm
A
Reducing and capping agent
λ = 386 A = 0.54920λ = 388 A = 0.23424λ = 390 A = 0.20227
Little blue shift in λmax as well as increase in absorbance
0
0.1
0.2
0.3
0.4
0.5
0.6
385 386 387 388 389 390 391
λ max nm
A
Different ratios of L-cysteine to NiCl2.6H2O were observed
Colour change in the colloidal dispersion from brown to deep-black occurred.
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300.0 320 340 360 380 400 420 440 460 480 500 520 540 560.00.000
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.600
nm
A
0
0.1
0.2
0.3
0.4
0.5
0 20 40 60 80 100
There is no shift in λmax (386 nm) but increase in absorbance due to formation of more nanoparticles in the same solution
Heating time
time (sec)
A
a. A = 0.13196b. A = 0.14668c. A = 0.18249d. A = 0.17620e. A = 0.20520f. A = 0.33478g. A = 0.32654h. A = 0.33380
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320.0 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500.00.000
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.481
nm
A
pH of solution
Basic10-11
Neutral-Weakly basic7-9
Acidic3-5
Due to the interactions of Ni with different functional group
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300.0 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600.00.00
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.00
nm
A
Stability of the NiNPs
a. Ab = 0.50165b. Ab = 0.49680c. Ab = 0.50340
0
0.2
0.4
0.6
0.8
1
380 385 390 395 400
A
λmax
As prepared Ni NPs were stable for several days
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4048
417.4
440.5
458.5
475.8
485.0
611.0
979.4
1111
.611
68.4
1384
.5
1578
.21608
.8
3230
.732
85.0
3425
.5
447.6
538.6
637.5
822.7
866.8
941.4
1063
.7
1139
.811
95.4
1296
.513
47.1
1393
.914
23.7
1543
.415
85.4
2080
.4
2551
.72964
.3
3174
.1
Cystiene-ninps 12-2-09cysteine std
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Abs
orba
nce
500 1000 1500 2000 2500 3000 3500 Wavenumbers (cm-1)
FTIR spectra of Strd: Cysteine (Upper) Ni NPs (lower)
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Ni COOHNH
2
S
CO
OH
NH
2
S
COOH
NH2
S
COOH
NH2
SCOOH
NH2
S
CO
OH
NH 2
S
NiCOOH
NH2
S
CO
OH
NH
2
S
COOH
NH2
S
COOH
NH2
S
COOH
NH2
SC
OO
H
NH 2
S
Ni COOHNH
2
S
CO
OH
NH
2
SCOOH
NH2
S
COOH
NH2
SCOOH
NH2
S
CO
OH
NH 2
S
NiCOOH
NH2
S
CO
OH
NH
2
S
COOH
NH2
S
COOH
NH2
S
COOH
NH2
SC
OO
H
NH 2
S
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Proposed Mechanism
2HOCH2CH2OH + 2Na2CO3
+ NiCl2.6H2O +6 Cyst
2CH3COONa + 2NaCl + 8H2O + 4H2 ↑
2CO2 ↑ + Ni(Cyst)6
Heat
NaOH
Ni
CO
OH
NH
2
HS
COOH
NH2
HS
CO
OH
NH
2H
S
COOH
NH2
HS
COOH
NH2
HS
COOH
NH2
HS
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Differential Scanning Calorimetric (DSC) Analysis
Thermogram of standard Cysteine (Red) and our products (black).
C y s t - N iN P s , 2 9 . 0 1 . 2 0 0 9 06 : 4 8 : 4 3C y s t - N iN P s , 5 . 0 0 0 0 m g
m W1 0
4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0
C y s t in e , 1 9 . 0 2 . 2 0 0 7 1 7 : 2 4: 2 6C y s t in e , 2 . 5 0 0 0 m g
m W1 0
0 2 4 6 8 1 0 1 2 1 4 1 6 1 8 2 0 2 2 2 4 2 6 2 8 3 0
^ e x o
L a b : M E T T L E R
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Spherical nanoparticles = Range 5 – 35 nm, Average size, 14 nm
Nanorods = Range, 5nm x 10 nm – 50nm x 120 nm Average size, 20nm x 60nm
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250 300 350 400 450 500 550 6000.00
0.05
0.10
0.15
0.20
0.25
0.30
A
nm
1
2a
250 300 350 400 450 500 550 6000.00
0.05
0.10
0.15
0.20
0.25
0.30
A
nm
bNi powder (mg) 0.0 0.1 0.2 0.3 0.4 0.5
250 300 350 400 450 500 550 6000.00
0.05
0.10
0.15
0.20
0.25
0.30
Ni NPs (mg) 0.0 0.1 0.2 0.3 0.4 0.5A
nm
c
250 300 350 400 450 500 550 6000.00
0.05
0.10
0.15
0.20
0.25
0.30
A
nm
1
2a
250 300 350 400 450 500 550 6000.00
0.05
0.10
0.15
0.20
0.25
0.30
A
nm
bNi powder (mg) 0.0 0.1 0.2 0.3 0.4 0.5
250 300 350 400 450 500 550 6000.00
0.05
0.10
0.15
0.20
0.25
0.30
Ni NPs (mg) 0.0 0.1 0.2 0.3 0.4 0.5A
nm
c
Reduction of 4-Nitrphenol Ni NPs
(a) 1, aqueous solution of 7.5 µM 4–NPh; 2,7.5 µM 4–NPh in the presence of 0.05 M NaBH4
(b) (right peak) Reduction of phenolate ions after treatment with 0.0 – 0.5 mg of Ni powder in the Presence of 0.05 M NaBH4
(c) same as ‘‘b’’ but replaced Ni powder with Ni NPs. Each spectrum recorded after 1 minute treatment.
23%
81%
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Cysteine capped NiNps with better size distribution have been synthesized by 1 minute microwave irradiation without using any surfactant or stabilizer.
UV-Visible spectrometry confirmed the formation of Nickel nanoparticles in Ethylene glycol. Further study showed that the formed Ni NPs are stable for a longer time without any change in shape or size.
SEM study revealed that the formed nanoparticles are in the form of nanorods and spherical nanoparticles and evenly distributed. The size is well under the true dimension of nanotechnology.
FTIR study showed that Ni NPs are interacted with cysteine Via Ni-S type of interaction.
XRD study further described strong interaction between Cysteine molecules.
DSC study confirmed the thermal stability of the formed composite between cysteine and Ni NPs.
Reduction of 4-nitrophenolproved the synthesized NiNps as the better reduction catalysts.
CONCLUSION