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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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INTRODUCTION

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Nanotechnology And Nanoscience

A Paradigm Shift

NiNi

Chemistry changes with Size!X

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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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Overview of the Literature About Ni NPs

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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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AIMS AND OBJECTIVES

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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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SCOPE OF STUDY

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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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EXPERIMENTAL

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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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Part I- Fabrication of Ni Nanoparticles

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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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Part II- Characterization of Ni Nanoparticles

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UV-Visible Spectrophotometery

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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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NiC

OO

H

NH

2

HS

COOH

NH2

HS

CO

OH

NH

2H

S

COOH

NH2

HS

COOH

NH2

HS

COOH

NH2

HS

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FTIR SPECTROSCOPY

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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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Scanning Electron Microscopy (SEM)

Longitudinal NPs AggregatedSpherical

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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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Part III- Application of Ni Nanoparticles

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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

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NiC

OO

H

NH

2

HS

COOH

NH2

HS

CO

OH

NH

2H

S

COOH

NH2

HS

COOH

NH2

HS

COOH

NH2

HS

attentionThanks for your