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FROM NANO TECHNOLOGY TO NANO CATALYSTS:

A QUANTUM JUMPA QUANTUM JUMP

S. Tajammul Hussain,S. Tajammul Hussain,Nano Science and catalysis Div (NSCD),Nano Science and catalysis Div (NSCD),

National Centre For Physics (NCP), National Centre For Physics (NCP), QAU Complex,QAU Complex,

Islamabad.Islamabad.

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• “Just wait—the 21st century is going to be incredible. We are about to be able to build things that work on the smallest possible length scales, atom by atom. These nanothings will revolutionize industries and our lives”

--- Richard Smalley, 1999

• “Nanoscience and technology will change the nature of almost every human-made object in the 21st century”

--- M.C. Roco, R.S. Williams, P. Alivisatos, 1999

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CATALYSISCATALYSIS

Industrial catalysis has involved nanoparticles since beginning of the 20th century

NANOSCIENCENANOSCIENCE

Addition of the “nano” prefix to many technical terms is not simple replacement of the unit of Angstroms, this is change in science/Engineering.

Nanoscience gives a great contribution

to a fundamental approach for optimization of the catalyst performance

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From From NanoNano Technology to Technology to NanoNanoCatalysts.Catalysts.

••Irregular Shaped Heterogeneous Particles.Irregular Shaped Heterogeneous Particles.

••Present Nomenclature: Present Nomenclature: NanoNano Materials after 2000.Materials after 2000.

••The Market: US $ 330 Trillion.The Market: US $ 330 Trillion.

90% Chemical Products are produced with the use of 90% Chemical Products are produced with the use of Catalysts.Catalysts.

60% Industrial Processes are based on Catalytic 60% Industrial Processes are based on Catalytic Reactions.Reactions.

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The Emerging Technology(Source: New Scientist, 2009)

• 2800 Patents Filed in 2009 on Nano Materials( The largest in the history)

• 450 patents Filed in 2009 on nano Catalysts.

• Growth Continued Exponentially.

• 650 new nano catalysts Products Developed.

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The Industry Demands, The Industry Demands, maximum Profit withmaximum Profit with--in minimum time.in minimum time.

Add other Chemicals Catalysts!!!!

Disadvantage--Too hot!

Disadvantage--Separate chemicals Disadvantage—Costly/reusable

PressureDisadvantage--Cause Explosions

Temperature

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Need to make chemicals faster

Most Reactions are too slow to be useful...

Why Catalysis?Why Catalysis?

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Catalyst lowers the activation energy for both forward and reverse reactions.

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The Present ScenarioThe Present Scenario•• Today the world faces a variety of Today the world faces a variety of

challenges:challenges:

•• In creating alternative fuels,In creating alternative fuels,•• Searching for cheap new materials with 100% selectivity,Searching for cheap new materials with 100% selectivity,•• Reducing harmful by products in manufacturing,Reducing harmful by products in manufacturing,•• Cleaning up the environment and preventing future pollution, Cleaning up the environment and preventing future pollution, •• Dealing with the cause of global warming, Dealing with the cause of global warming, •• Protecting the common person from release of toxic Protecting the common person from release of toxic

substances and infectious agents, substances and infectious agents, •• Catalysis are needed to meet these Catalysis are needed to meet these

challenge, but their complexity and diversity challenge, but their complexity and diversity demand a revolution in the way catalysts are demand a revolution in the way catalysts are designed and used. designed and used.

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The Catalyst TechnologyThe Catalyst Technology•• This revolution can become reality This revolution can become reality

through the application of new through the application of new methods for synthesizing, methods for synthesizing, characterizing molecular and material characterizing molecular and material systems and testing to find out its systems and testing to find out its industrial applications.industrial applications.

• Consequently an investment in catalysis in this country is not only important, it is essential.

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The Catalysts (Basic Concepts)

•• The rate at which chemical bonds The rate at which chemical bonds are formed and broken and are formed and broken and controlling the yield of chemical controlling the yield of chemical reactions to increase the amount reactions to increase the amount of desirable products from these of desirable products from these reactions and reduces the amount reactions and reduces the amount of undesirable productsof undesirable products

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Scales in Catalysis

http://www.inano.au.dk/da/research/research-areas/nano-energy-materials/nanocatalysis/

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Examples of Reactions w/o Examples of Reactions w/o NanoNano--catalysiscatalysis(source: Catalyst Initiatives, DOE, Netherlands, 2008).(source: Catalyst Initiatives, DOE, Netherlands, 2008).

Oxygen in theair mixes with iron to formrust

HydrogenPeroxideforms a chemicalreaction withyour body

1 week to several months

Plants & animals decompose to oil & coal

Millions of years

Seconds

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How Does How Does NanoNano--catalyst catalyst Work?Work?

Surface Area!!Catalysts are not solid Catalysts are porous

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What Does Surface Area Do?

Increases the amount of available reaction sites

2 propanes

Reactive Sites

Benzene Benzene product

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Examples of Reactions with Examples of Reactions with CatalysisCatalysis

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Heterogeneous and Heterogeneous and Homogeneous CatalysisHomogeneous Catalysis

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Why Heterogeneous Why Heterogeneous Catalyst?Catalyst?

•• Heterogeneous Catalysts: Control of Heterogeneous Catalysts: Control of product selectivity.product selectivity.

•• High Surface area, Multiple active sites, High Surface area, Multiple active sites, Large pore volume. Large pore volume.

•• Reusable.Reusable.

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How to measure the global reaction rate?

We need to start from species mass balance equation for particular reactor.

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OUR GOALSOUR GOALS

• Use of Untapped country Natural Resources.

• Cheap Technology.• Could be utilized for the solution of

Country Problems.• Development of skilled human resource

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Fabrication of Nano-Catalysts/MaterialsFabrication of Nano-Catalysts/Materials

Top down approach

Top down approach

Bottom up approach

Bottom up approach

cut into pieces in nanoscale

cut into pieces in nanoscale

assemble atoms to nanostructuresassemble atoms

to nanostructures

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Our Technology:Our Technology:SyedSyed T. T. HussainHussain, et al, EP Patent No. 1511564, et al, EP Patent No. 1511564

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The ProcessThe Process

Parr Reactor

The Catalyst

H2

Furnace

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Size Control Effect of Hydrogen PressureSyed T Hussain et al, Journal of Nano Science Engineering (JNSE) 14(2), 151-160, 2010.

500 Psi500 Psi

300 Psi300 Psi

200 Psi200 Psi

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Natural Gas Conversion Natural Gas Conversion TechnologyTechnology

• World Natural Gas Production : 3.501 trillion Cubic meters in 2009.

• Oil Firms Waste US $ 40 B per year ( up to 180 billion Cubic meters of Natural gas is burned off by the world’s oil producers every year).

– Enormous economic and environmental costs.

Source: World fact book (2008)

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NanoNano Catalytic Conversion of natural gas into Catalytic Conversion of natural gas into Aromatics, Aromatics, SyedSyed T T HussainHussain et al, et al,

J of hydrocarbon Engineering, In Press, 2010J of hydrocarbon Engineering, In Press, 2010

2929

Carbon Nanotubes (CNT’s)

• CNT’s: an innovative nano/micro structural material (discovered in NEC Japan in (1991-92).

• Self assembled carbon structure with diameter as small as 1 nm.

• One CNT is 10,000 times thinner than human hair.

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Present CNTPresent CNT’’S Synthesis S Synthesis ProcessesProcesses

• CVD, PVD, Arc-evaporation, Catalytic Process, Laser Assisted Catalytic Growth, Solution Chemistry, Arrested Evaporation.

• 2-step process– 1. CNT’s Production.– 2. Purification (86-93%)

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The CNTs production ProcessThe CNTs production ProcessUS Patent No. 2009208403US Patent No. 2009208403 Feb. 2010.Feb. 2010.

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STEM AnalysisSTEM Analysis( U of Pittsburg, USA)( U of Pittsburg, USA)

A

7 Walls

B

12 Walls

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The Developed CNTs XPS Analysis

(U of Laval Canada)

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As Hydrogen Storage at 10, 15, 20 As Hydrogen Storage at 10, 15, 20 Psig Pressure and at RT.Psig Pressure and at RT.

0123456

0 100 200 300 400 500 600

Time/minutes

Wt%

H2

adso

rbed

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Ni:Pt/CNTNi:Pt/CNT’’ss nanonano catalyst for SOFC Fuel catalyst for SOFC Fuel CellCell

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The Results.The Results.

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4-1.0-0.8-0.6-0.4-0.20.00.20.4

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4-100.0µ-80.0µ-60.0µ-40.0µ-20.0µ

0.020.0µ

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Application as High Temp. Resistant Application as High Temp. Resistant MaterialMaterial ((Cu:Mo/CNTCu:Mo/CNT’’ss).).

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Cu:Mo/CNTCu:Mo/CNT’’s s (The TGA Study)(The TGA Study)

020406080

100120

0 300 600 900 1200

Temperature 0C

Inte

nsity C-Fibers

C+Cu+Mo

C+Cu+Mo

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CNTs Doped Epoxy CNTs Doped Epoxy Functionalized Functionalized PizzoPizzo MaterialMaterial

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CNTs doped IR SensorsCNTs doped IR Sensors

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Applications of CNTsApplications of CNTs

•• CNTs doped Life Jackets.CNTs doped Life Jackets.

•• CNTs doped Tennis RacketsCNTs doped Tennis Rackets

•• CNTs doped Cricket bat (Few CNTs doped Cricket bat (Few Australian Cricketers bats are doped Australian Cricketers bats are doped with CNTs, with CNTs, Source: Ten Sports, Feb. Source: Ten Sports, Feb. 20102010).).

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The Nano Ceramic Material for 99.9% Pure H2 Production For Fuel Cell, Syed T Hussain et al,

(J. Appl. Catal. A, In Press, 2010).

FURNACEFURNACE

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Reaction and Gas Analysis Reaction and Gas Analysis SchemeScheme

FURNACE

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. Nano Catalyst (Nano Catalyst (Ni:Mo:ZrNi:Mo:Zr) for the ) for the Polymerization of Butadiene for Rubber Polymerization of Butadiene for Rubber

IndustriesIndustries

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The MicrostructuresThe MicrostructuresSyedSyed T T HussainHussain et al, et al,

J. J. CatalCatal (O), 17(3), 271(O), 17(3), 271--280, 2009280, 2009

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Nano Catalyst For Organic Industrial Waste Nano Catalyst For Organic Industrial Waste degradation degradation Ce:MnOCe:MnOxx :K doped nano catalysts.:K doped nano catalysts.

SyedSyed T T HussainHussain et al. et al. EnvoirEnvoir. Tech. 35(5), 2009, 501. Tech. 35(5), 2009, 501--511511

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Mg:Ni:Li/Be nano catalyst as Hydrogen Storage: Mg:Ni:Li/Be nano catalyst as Hydrogen Storage: SyedSyed T. T. HussainHussain et al.et al.

Int. Rev. J. Int. Rev. J. ChemChem EnggEngg. 11(3), 2009, 23. 11(3), 2009, 23--31.31.

N-03

0

1

2

3

4

5

6

0 2 4 6 8 10 12

Pressure (barr)

H2 w

t% A

dsor

ptio

n

25C

50C

70C

90C 0

1

2

3

4

5

6

10 30 50 70 90

H2 Wt% DesorbedTe

mpe

ratu

re 0

C

NO2NO3

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Co:Mo/zeolite nano catalyst For SCo:Mo/zeolite nano catalyst For S--reduction in Dieselreduction in DieselApplAppl. . CatalCatal. (A), 10(1), 119. (A), 10(1), 119--127, 2009127, 2009

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SS--Reduction in Reduction in TharThar and and LakraLakra CoalCoal

•• TiOTiO2:2:ZrOZrOxx:K :K nanonano catalyst.catalyst.• S-reduction 32-38% + 20% Alcohol Production

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Reducing Greenhouse Gas Emissions Using CoalbedMethane Recovery Process.

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Conventional Method

Transesterification

20-29% Biodiesel+

Soap+

Glycerin

Gasification

Crude Oil+

0.01% Ni nano catalyst

Photo catalysis

300°C

Gases Liquid

CH4=3.34%C2H4=65.05%CH3OH=28.23%C3H4=1.96%C3H8=1.38%

Crude Oil (Reaction Time 5 mins)+

0.1% Photo catalyst

1-3% CH4

92.5% Biodiesel

2-7% FatsBiodiesel= 38.25%

Benzene= 39.41%Propene= 22.33%

Catalytic Conversion of Non-edible Oil into Biofuel/HC’s(used tea, Kinno/MSW/Jatropha/Butchery Waste)GP/1073, US Patent application No. 12714730, submitted, March. 2010.

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Photocatalytic Production of Natural Gas from Water Hychin:

Syed T. Hussain et al. J. Biotechnology (A): In press, 2010.

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The Product.

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Green Energy TechnologyUS Patent No. 2009287555

• Conversion of LPG.

• Ce:Mn:Co/TiO2

* 20% less C-emission.

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Component Concentration in Feed Gas(% mol/mol)

Concentration in Strip Gas(% mol/mol)

Hydrogen (H2) 0.00 20.39

Nitrogen (N2) 8.04 8.02

Methane (CH4) 42.39 50.07

Ethane (C2H6) 24.82 3.29

Propane (C3H8) 13.73 13.61

iso-Butane (i-C4H10) 6.01 2.46

normal-Butane (n-C4H10) 4.67 2.05

iso-Pentane (i-C5H12) 0.31 0.10

normal-Pentane (n-C5H12) 0.02 0.00

Hexane plus higher (C6++) 0.01 0.01

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Nano Catalyst For Reduction of Saturated Fats Nano Catalyst For Reduction of Saturated Fats inin Edible Oil Hydrogenation

US Patent No. 2008318766

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Gold Nano ParticlesGold Nano ParticlesJ. J. NanoNano Particle Res. 11(3), 2009, 123Particle Res. 11(3), 2009, 123--131.131.

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AntiAnti--diabetic Activitydiabetic ActivityConjugated Au NPs.Conjugated Au NPs.

Effect of Gold Nano Particles on Blood Glucose Level

50100150200

250300350

0.5 10.5 20.5 30.5 40.5

Time (Hrs)B

lood

Glu

cose

(mg/

dl)

Lintex

Lintex 60:Goldnano 1

5959

Au NPs For Cancer Cell Treatment Au NPs For Cancer Cell Treatment (Biological Applications)(Biological Applications)

Controls (live cells stained)

Incubation withGoldnanoparticles (0.1 ppm)

606060

Ag Nano Particles (BioAg Nano Particles (Bio--medical medical Applications)Applications)

• Incubation with Silver nanoparticles (0.12 ppm)

• LD50 approx 0.06ppm

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Polymer Capped Silver Nano Particles Applications Polymer Capped Silver Nano Particles Applications

US Patent No. 20090068089US Patent No. 20090068089

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20ppm

50ppm

Nano Particles For Agriculture IndustryDG Khan, After 3 months (vegetative Growth)

2 km distance crop of the same age

Normal

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Wheat Variety V2 (Inqalab-91 Susceptible Variety)1, 1.5, 2.0, 2.5, 3, 4 ml 1, 1.5, 2.0, 2.5, 3, 4 ml nanonano particles in 400 ml particles in 400 ml

of water of water

• Applied one week after sowing

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Spray of Spray of NanoNano Particles on Particles on Wheat (Wheat (LodhranLodhran) After 2) After 2--monthsmonthsControlControl 50 50 ppmppm nanonano particlesparticles

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Anti Bacterial & Antifungal Anti Bacterial & Antifungal Activity of Ag NPs.Activity of Ag NPs.

Zone of inhibition = 14 Zone of inhibition = 14 mmmm

200200ppmppm

100100ppmppm

5050ppmppm

2525ppmppm

12.512.5ppmppm

6.256.25ppmppm

Ag Conc.Ag Conc.

Zone of inhibition (mm)Zone of inhibition (mm)E. coliE. coli 2020 1515 77 77 77 00SalmonellaSalmonella 2424 1919 88 77 77 00StreptococcStreptococcusus

1515 1010 55 1010 77 77Staph Staph aurousaurous

1717 1313 1010 00 00 00

BacteriaBacteria

PseudomonPseudomonasas

2424 2020 1717 1212 77 55FungusFungus Candida spCandida sp 2020 1616 1616 1414 1212 1010

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Industrial Use of Polymer capped Industrial Use of Polymer capped AgNPsAgNPsCollaboration with Pakistani Industries.Collaboration with Pakistani Industries.

((Lever Brothers/Service/Bonanza)Lever Brothers/Service/Bonanza)

• Antibacterial tooth paste.• Antibacterial Towels.• Antibacterial Soaps.• Antibacterial Clothes• Antibacterial Soaks.• Antibacterial Shaving Cream• Antibacterial Cosmetics etc etc.

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S doped S doped nanonano TiOTiO22 as as PhotocatalystPhotocatalyst, For Alcohol , For Alcohol Production and degradation of industrial organic Production and degradation of industrial organic

pollutants.pollutants.J. Nat Gas Chem. 17(2), 2009, 112J. Nat Gas Chem. 17(2), 2009, 112--120.120.

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The ResultsThe Results(Pollutants Degradation & (Pollutants Degradation &

COCO22+ H+ H22O Conversion)O Conversion)

2 4 6 8 100

20

40

60

80

100

% M

etha

nol p

rodu

ctio

n

Time (hrs)

TS4(S-doped)In IR TS3(S-doped)In IR TS4(S-doped)In SUN TS3(S-doped)In SUN T3 Undoped T4 Undoped

4 6 8 10 12 14 16 18 20 220

10

20

30

40

50

60

70

80

90

100

110

Time(hrs)

% P

heno

l deg

rada

tion

TS3(S-doped)In IR TS3(S-doped)In IR TS4(S-doped)In Sun TS3(S-doped)In In Sun T3(Undoped) T4(Undoped)

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Increase in Gross Calorific Value (GCV) Increase in Gross Calorific Value (GCV) of MSW (Municipal Solid Waste): of MSW (Municipal Solid Waste):

A A FaujiFauji CementCement--NCP ProjectNCP Project

•• TiOTiO22:ZrO:ZrOxx:K (:K (nanonano catalyst)catalyst)•• 1.0 Kg 1.0 Kg nanonano catalyst for 1.0 TON of catalyst for 1.0 TON of

MSWMSW•• Increase in GCV = 2750Increase in GCV = 2750--4120 4120 KcalsKcals/Kg/Kg•• Ultimate Goal: Replacement of Coal Ultimate Goal: Replacement of Coal

with MSW (Coal GCV = 6000 with MSW (Coal GCV = 6000 KcalsKcals/Kg)/Kg)

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Grant Allocation for Various Grant Allocation for Various Organization (Organization (NanoNano R & D)R & D)

•• PIEASPIEAS = = RsRs. 60 M. 60 M (Synthesis (Synthesis & Characterization, HEC)& Characterization, HEC)

•• QAUQAU= = RsRs. 137 M. 137 M ((NanoNanoMagnetism, HEC)Magnetism, HEC)

•• COMSATSCOMSATS= = RsRs. 189 M. 189 M(Micro/(Micro/NanoNano Electronic Electronic Devices, HEC)Devices, HEC)

•• GIKIGIKI= = Rs.195 MRs.195 M ((NanoNanoComposites, HEC)Composites, HEC)

•• NIBGENIBGE = = RsRs. 155 M. 155 M ((NanoNanoBioBio--Technology, Technology, MoSTMoST))

•• PINSTECHPINSTECH = = 196 M196 M ((NanoNanoDevices, Devices, MoSTMoST) )

•• TOTAL = 932 M TOTAL = 932 M

NCP : 4.5 MNCP : 4.5 MNano Catalysts For:

* Energy*Environment

* Medical Applications

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Concluding RemarksConcluding Remarks

•• A new World awaits our exploration.A new World awaits our exploration.•• Things act differently in this world, but Things act differently in this world, but

that is its attraction.that is its attraction.•• It is a world of small things and of It is a world of small things and of

complex things.complex things.•• When we understand them and control When we understand them and control

them, they will have an enormous them, they will have an enormous impact in our lives.impact in our lives.